Abstract:
A laser ablation and filtration process and apparatus wherein liquid containing hydrocarbons or other contaminates is purified. The liquid is exposed to laser energy at one or more selected wavelengths wherein the laser energy travels through the liquid and reaches the hydrocarbons or other contaminates and vaporizes, denatures, breaks down, neutralizes, renders inert and/or separates the hydrocarbons or contaminates from the liquid. A laser source is positioned in or on a vessel based on pre-set parameters to maximize exposure of the liquid to the laser energy, including sizing parameters, angle and inclination of the laser, retention time for the laser process to be applied and geometry of the containment for proper inclination. One or more collection chambers, which may include perforated membranes may be included to collect gases, separated hydrocarbons or contaminates and other by-products of the process. The vessel utilized may be submergible in water to pull or flow contaminated water therethough. The vessel may also be utilized outside a body of water wherein contaminated water from a source is introduced within the vessel.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    This application claims the benefit of and/or priority to U.S. Provisional Patent Application Ser. No. 62/255,156, filed on 13 Nov. 2015, which is hereby incorporated herein by reference. 
     
    
     STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT 
       [0002]    Not applicable 
       REFERENCE TO A “MICROFICHE APPENDIX” 
       [0003]    Not applicable 
       BACKGROUND OF THE INVENTION 
       [0004]    1. Field of the Invention 
         [0005]    The present invention relates to a laser ablation and filtration process and apparatus, wherein laser ablation and filtration is utilized to remove hydrocarbons, including oil, natural gas, grease and/or other contaminants, including pathogens, bacteria, and/or other unwanted organisms, from a liquid or fluid, e.g., fresh or salt water. 
         [0006]    2. General Background of the Invention 
         [0007]    Removing hydrocarbons and contaminants from water is a continuous worldwide challenge in many industries, including in the oil and natural gas industry. Conventional prior art methods require the use of chemicals and filtration media, which become exhausted and need to be continuously disposed of and replaced. The disposal of filtration materials generates additional waste and expense. Water filtration to remove contaminants such as hydrocarbons has a direct impact on oil and gas industries, the shipping industry, naval operations, and many other industries, entities, and organizations. 
         [0008]    For example, several common standards per government regulation (including, for example, International Maritime Organization requirements MEPC.107(49)), for water from various processes is that it must have less than 15 ppm of hydrocarbons (15 microliter/liter), before dilution, before it can be discharged or disposed of back into the ocean. There are also regulations for reinjection of fluid down hole, which include the Federal Safe Water Act and UIC Regulations. 
         [0009]    There is thus a need in the art for a method for removal of hydrocarbons that reduces or eliminates the use of chemicals and/or filtration media when removing hydrocarbons and other contaminates from water or other liquids. 
         [0010]    There is also a need in the art to reduce or eliminate the amount of chemical and filtration waste associated with conventional prior art methods for removing hydrocarbons from a liquid, wherein chemicals and/or filtration media become exhausted and continually need to be disposed of and replaced. 
         [0011]    There is also a need in the art to reduce the amount of expense associated with replenishing chemicals and filtration media and disposing of the chemicals and filtration media via conventional prior art methods for removing hydrocarbons from a liquid, wherein chemicals and/or filtration media become exhausted and continually need to be disposed of and replaced. 
       BRIEF SUMMARY OF THE INVENTION 
       [0012]    The apparatus(es) and process(es) of the present invention solves the problems confronted in the art in a simple and straightforward manner. In various embodiments, a laser ablation and filtration apparatus and process of the present invention offers a more environmentally safe and effective alternative to purifying water containing hydrocarbons or other contaminates because it uses laser light energy, which does not require the use of consumable materials such as chemicals. 
         [0013]    Various embodiments of the laser filtration method and apparatus of the present invention can be used to assist filtration methods that utilize chemicals and filtration media to remove hydrocarbons and other contaminates from water, wherein less chemicals and filtration media will be used. 
         [0014]    Various embodiments of the laser filtration method and apparatus of the present invention can be used to replace conventional prior art filtration methods that utilize chemicals and filtration media to remove hydrocarbons and other contaminates from water wherein no chemicals or filtration media are needed for use with the process. 
         [0015]    Generally, laser light is an intense, collimated and/or focused beam of visible or invisible light radiation. When exposed to laser light, hydrocarbons, including grease, natural gas and oil, and other contaminants, including pathogens or bacteria or other organisms absorb the laser light energy. The laser light energy can denature, vaporize, break down, alter, kill, or otherwise render inert the hydrocarbon or contaminate, respectfully. 
         [0016]    Different hydrocarbons and contaminates have different laser energy absorption and fluorescence characteristics. The laser energy absorption and fluorescence characteristics of a hydrocarbon or contaminate may also vary depending on the concentration of the hydrocarbon or contaminate. Laser light at one wavelength may be more effective on one type of hydrocarbon or contaminate present in a liquid, while laser light at a different wavelength may be more effective on a second type of hydrocarbon or contaminate present in the liquid. 
         [0017]    In various embodiments the laser ablation and filtration process of the present invention comprises: 
         [0018]    Obtaining samples of contaminated liquid that will undergo the laser ablation and filtration process; 
         [0019]    Gathering data on absorption and fluorescence characteristics of the liquid and of the hydrocarbons present in the liquid, e.g., absorption and fluorescence characteristics that help identify the liquid and the particular type(s) of hydrocarbon or contaminants in the liquid, wherein absorption characteristics help inform the decision on which laser light wavelengths will be effective in the laser ablation and filtration process, e.g., the ability of the laser light to travel through the liquid to the targeted hydrocarbon or contaminate, to be absorbed by the liquid and to be absorbed by the targeted hydrocarbon or other contaminate; 
         [0020]    Selecting a specific wavelength of pulsed, modulated, or continuous wave laser energy at a sufficient energy density to target one or more unwanted hydrocarbons or other contaminants; 
         [0021]    Flowing the contaminated water into a containment vessel comprising a desired laser scanner configuration; 
         [0022]    Applying laser energy throughout the contaminated liquid, within the containment vessel at the selected wavelength and frequency; 
         [0023]    Preferably applying laser energy for a selected time interval and at a selected temperature; 
         [0024]    Wherein the hydrocarbon, gas, grease and/or other targeted contaminates are vaporized, denatured, rendered inert and/or separated from the liquid, e.g., rises to the top of the liquid, where they can be separated, and flowed to a collection reservoir; 
         [0025]    Gathering data on the amount of hydrocarbon or other contaminant remaining in the liquid after performing the above-steps; 
         [0026]    Repeating the above-steps if necessary until only a desired amount of the hydrocarbon or other contaminants remains in the liquid, e.g. under 15 ppm (15 microliter/liter); and/or 
         [0027]    Repeating the above-steps with one or more different wavelengths to target one or more different hydrocarbons or contaminates that are present in the liquid. 
         [0028]    In various embodiments the laser ablation and filtration process of the present invention comprises obtaining samples of contaminated liquid that will undergo the laser ablation and filtration process. 
         [0029]    Data on absorption and fluorescence characteristics of the liquid and of the hydrocarbons present in the liquid is obtained, e.g., through running tests on the contaminated liquid. Absorption and fluorescence characteristics help identify the liquid and the particular type(s) of hydrocarbon or contaminants in the liquid. Absorption characteristics also help inform the decision on which laser light wavelengths will be effective in the laser ablation and filtration process, e.g., the ability of the laser light to travel through the liquid to the targeted hydrocarbon or contaminate, to be absorbed by the liquid and to be absorbed by the targeted hydrocarbon or other contaminate. 
         [0030]    Selecting a specific wavelength of pulsed, modulated, or continuous wave laser energy at a sufficient energy density to target one or more unwanted hydrocarbons or other contaminant. 
         [0031]    A sufficient energy density can be 0.5 J/cm2, for example, if targeting hydrocarbons, or 1.5 J/cm2, if targeting a pathogen. 
         [0032]    The contaminated water can then be flowed, pulled, sucked, or otherwise drawn into a containment vessel or pipe comprising a desired laser scanner configuration. 
         [0033]    Laser energy is applied throughout the contaminated liquid, within the containment vessel at the selected wavelength. 
         [0034]    Preferably laser energy is applied for a selected time interval and at a selected temperature. 
         [0035]    The selected time interval preferably is chosen to maximize absorption, vaporization, denaturalization, or the rendering inert of the contaminants in the water. The desired time interval can be optimized by testing and adjusting based on data obtained from one or more processed samples of the liquid after undergoing a laser ablation process. The longer the contaminated water is exposed to the laser energy, the cleaner the water will become. 
         [0036]    For example, if laser energy is applied to a closed container or vessel, laser energy may be applied for 1 to 5 minutes. After the 1 to 5 minutes, the water should be visibly clearer. Also, produced gas, e.g., bubbles rising in the liquid, or other evidence of a contaminate having been separated from the liquid, can be present as visible indictors that the laser ablation process was effective to clean or purify the water. The selected time interval can be extended as necessary to achieve cleaner or maximum desired results. Optionally, the process can be repeated for 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 minute intervals, or longer as desired, for example. Testing of samples of the processed water can be performed after running each, or after one or more selected, laser ablation processes to determine if a desired result has been achieved, e.g., if the processed liquid will pass regulations for purification that will allow the water to be returned to the source. 
         [0037]    If contaminated water is flowed through a vessel or pipe for example, the length of time the laser energy is applied will be based on the length of time it takes for the liquid to flow through the vessel or pipe with exposure to the laser path. In this embodiment, using mirrors to bounce the laser energy around the vessel or pipe, or adjusting the configuration of the laser beam, e.g., so that it is a cone or tube configuration, can be desirable to maximize exposure of the liquid to the laser energy while the contaminated liquid is traveling through the vessel or pipe, for example. 
         [0038]    The selected temperature can be room temperature. The temperature of the liquid is not as important as other parameters and can vary and still be effective at a wide range of temperatures. 
         [0039]    Preferably during the laser ablation process, the hydrocarbon, gas, grease and/or other targeted contaminates are vaporized, denatured, rendered inert and/or separated from the liquid, e.g., rises to the top of the liquid to be separated and flow to a collection reservoir. 
         [0040]    Data preferably is gathered on the amount of hydrocarbon remaining in the liquid after performing the above-steps. 
         [0041]    The above-steps can be repeated if necessary until only a desired amount of the hydrocarbon remains in the liquid, e.g. under 15 ppm (15 microliter/liter. 
         [0042]    The laser ablation process can also be repeated with one or more different wavelengths to target one or more different hydrocarbons or contaminates that are present in the liquid. 
         [0043]    In various embodiments, after purifying the liquid, the liquid may be flowed to a reservoir, the ocean, downhole, or otherwise returned to a source for the water. 
         [0044]    In various embodiments, a specific wavelength of pulsed, modulated, or continuous wave laser energy at a sufficient energy density is used to target unwanted contaminants, such as hydrocarbons from crude oil, in water, or other liquids, and used to decrease and/or completely remove their concentration from the liquid. 
         [0045]    Pulse duration of a wavelength can be at 10 nanoseconds, or 100 nanoseconds, for example, or it can be Continuous Wave (CW) or modulated wave. Preferably the pulse duration and type of pulse parameter is selected so that the laser energy reaches an effective energy density of light that causes the reaction with the contaminate in the liquid. As indicated pulse duration can be set at 10 or 100 nanoseconds. A continuous wave or CW is a continuous laser beam without pulses that is very intense. A modulated CW wave is also a continuous laser beam with high and low peaks of energy. 
         [0046]    An energy density will be sufficient if it facilitates the desired reaction or process to denature the targeted contaminants. A desired energy density can be determined by testing one or more samples of processed liquid, after it has undergone a laser ablation process, and then adjusting the energy density to help achieve more effective results. The process can be repeated for a particular liquid to undergo the ablation process, until optimal parameters are identified for the particular contaminated liquid. 
         [0047]    The above-described testing process can also be conducted to determine other optimal parameters for the laser ablation process for a particular contaminated liquid. 
         [0048]    Various embodiments of the apparatus and process of the present invention will use absorption characteristics and/or fluorescence of the contaminant material, and will use tuned high power lasers to vaporize, denature, and/or separate the contaminants from water. Examples of high power lasers include laser sources, such as pulsed, continuous wave, or modulated continuous wave lasers that typically emit ten watts or more of average power, up to multiple kilowatts or megawatts. 
         [0049]    For example, 70 W and 100 W units have been tested and more powerful laser sources foreseeably will increase efficacy of the process. Repeated testing with high frequency 1064 nm laser pulses, e.g., 200,000 to 1,000,000 pulses per second, has established that hydrocarbon levels in water are successfully reduced every time. Preliminary testing with low frequency 532 nm laser pulses, e.g., 10 pulses per second, has effectually produced clearer water, visually, and appears to successfully vaporize hydrocarbon contaminants. It is foreseen that testing with high frequency, e.g., 200,000 to 1,000,000 million pulses per second, of 532 nm laser sources will provide even better production rates and measurements. It is foreseen that testing with low or high frequency, e.g., 10 to 1,000,000 million pulses per second, of 532 nm laser energy will effectively process and clean contaminated liquid. 
         [0050]    In various embodiments tuning parameters may include, but are not limited to, wavelength, fluence, pulse duration, modulation rate, pulse profile, beam diameter, pulse frequency, energy, and/or focal distance. 
         [0051]    In various embodiments the laser light energy can be fired directly into the liquid from a source or with the assistance of a delivery system such as mirrors, fiber optics, articulated arms, and laser scanners. The necessary energy density or fluence of the laser that is needed to facilitate the reaction can be achieved by firing the laser directly from a source or by using optics such as collimators, mirrors, prisms, custom optics, and focusing lenses to achieve desired parameters. 
         [0052]    In various embodiments, the laser energy is absorbed by the contaminant and can convert a part or all of the contaminant from a liquid state into a gaseous state, allowing it to float to the surface and separate from the liquid. The laser energy can also disrupt bonds and/or denature or decompose the contaminant. For example, molecular bonds can be broken, resulting in both chemical and/or physical changes of the material. This process may render hazardous materials to chemically and/or physically change to be inert. Laser pulses result in photomechanical, photochemical, and photothermal processes that act upon and affect the hydrocarbon and/or other contaminant. 
         [0053]    In various embodiments, the path and intensity of the laser may be absorbed into the liquid over a long distance of travel and/or terminate at a target or surface. A target can be simply an inert energy dump material or can be made of a material that will facilitate plasma formation and cavitation bubbles. An inert energy dump material may be selected based on the wavelengths to be utilized in the laser ablation apparatus and/or process wherein the energy dump will sufficiently absorb the laser energy and terminate or end the laser path. An energy dump can be made of a material such as metal or ceramic that is appropriate for the wavelength or wavelengths being used. A metal commonly used in energy dumps is aluminum. Titanium is an example of another metal that may be used as an energy dump. Other suitable metals may also be utilized based on capability to absorb the wavelengths to be used. 
         [0054]    A target could also be an energy dump that is a chamber containing a liquid or fluid or other material that strongly, or will sufficiently, absorb the laser wavelength or wavelengths used in the process or apparatus. 
         [0055]    Ceramic, titanium and aluminum are examples of materials that may be used as an energy dump and which facilitate formation of cavitation bubbles, e.g., for use with 1064 nm, 532 nm, 355 nm, and/or 266 nm wavelengths. Other examples of inert energy dumps include graphite and glass, e.g., for use with 1064 nm, 532 nm, 355 nm, and/or 266 nm wavelengths. Bubbles can also form in the liquid itself without need of hitting a solid surface. 
         [0056]    The laser energy can also be used to create bubbles and micro-bubbles or cavitation bubbles which help facilitate the separation of the contaminant from the liquid. These cavitation bubbles can help carry the contaminant material to the surface for flowing to a collection reservoir. The bubbles may assist in contaminant removal by facilitating the formation of a hydrophobic and/or hydrophilic film around each bubble that is carried up to the surface. The contaminant may also develop an electrostatic or other attraction to the bubbles that are formed and/or to itself. 
         [0057]    Laser energy can also be used to break down and denature contaminants. A specific wavelength is preferably selected to target a contaminant in the water. 
         [0058]    In various embodiments, the laser ablation process may also break down the contaminant into small particles such as microparticles or nanoparticles. 
         [0059]    In various embodiments, the laser ablation process may also produce micro-bubbles, which aid in separating the hydrocarbon or contaminant from the liquid. 
         [0060]    A key principle with this technology is choosing a wavelength, or multiple wavelengths, that penetrates through the liquid, such as water, and absorbs into the contaminant. If the wavelength cannot pass through the liquid, then it will not reach the contaminant. In various embodiments, a wavelength with some absorption into the liquid may be desirable as it will still reach the contaminant, will weaken and dissipate after a certain distance, and will cause additional reactions such as heating up the liquid, which may be beneficial to the process in various embodiments. Heating the liquid with the laser or with other methods is foreseen to be beneficial as there is an inverse relationship between temperature and the solubility of gas in water. A higher temperature of the liquid foreseeably will help the reaction go faster. 
         [0061]    In various embodiments, one or more wavelengths can be used individually or simultaneously, e.g., 532 nm and 1064 nm used simultaneously or individually. 
         [0062]    In various embodiments, the laser ablation process may operate efficiently on its own to purify liquid and remove unwanted hydrocarbons and contaminants, without use of an additive or other conventional filtration methods. 
         [0063]    In various embodiments, the laser ablation process is used in conjunction with additives, e.g., adding emulsifiers or surfactants, that at a Critical Micelle Concentration level help isolate and remove the contaminant from the liquid. 
         [0064]    In various embodiments, the laser ablation process is used in conjunction with chemicals and/or filtration medium to assist in separating or removing hydrocarbons and other contaminates from the liquid. 
         [0065]    In various embodiments, the laser ablation process is used in conjunction with additives and other chemicals and filtration medium to assist in separating or removing hydrocarbons and other contaminates from the liquid. 
         [0066]    In various embodiments, the apparatus of the present invention comprises a containment vessel. The containment vessel is for containing liquid to be purified. The containment vessel may comprise a laser source, e.g. a laser scanner, for providing and directing laser light energy into and through the liquid to be purified. The containment vessel can contains the contaminated liquid to be purified and the laser energy during the treatment process. In some embodiments, contaminated water can flow through a vessel, e.g., continuously flow through vessel, during the laser ablation process, and exit the vessel when it reaches the end of the vessel as processed or purified or clean water. 
         [0067]    The position of a laser source, e.g. a laser scanner within or outside of a vessel, e.g., a containment vessel, is important to the laser removal process. Preferably the laser is positioned within or outside the vessel so as to maximize exposure of the liquid to the laser energy. The position of the scanner affects the path of the laser energy. To provide this controlled containment, preferably certain sizing parameters are applied including angle and inclination of the laser, retention time for the laser process to be applied and geometry of the containment for proper inclination, preferably to achieve maximum exposure of the liquid to the laser energy. After evaluating the contaminated liquid and applying selected parameters, and re-testing the water, the parameters can be adjusted based on the type and amount of contaminants still present in the liquid, to help achieve maximum exposure and effective removal of contaminants for the laser ablation process. 
         [0068]    Additionally certain mechanical devices may be included to assist in removal of the oil, grease, gas or other contaminate and for removal of byproduct created by the laser, i.e. residual oil. 
         [0069]    Preferably compartmental containment is provided as a vital feature for separation and removal. 
         [0070]    In addition to residual oil, micro-bubbles may be produced as a byproduct of the laser process. Due to their size and physical characteristics, sub 50 micron by definition, the containment and compartmentalization process becomes more important and crucial to the management of the process. Compartmentalization and sizing of the compartments based on flow and flow characteristics will add to the success of the overall process of laser ablation and micro-bubbles. 
         [0071]    In addition to the laser ablation process and any micro bubbles that may be formed, additional micro bubbles can be added to the system to better facilitate filtration and separation of materials. These bubbles can be created by mechanical means, which include mechanical agitation, eductor, and dissolved air pump. 
     
    
     
       BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS 
         [0072]    For a further understanding of the nature, objects, and advantages of the present invention, reference should be had to the following detailed description, read in conjunction with the following drawings, wherein like reference numerals denote like elements and wherein: 
           [0073]      FIGS. 1-1A  illustrate an example of absorption and fluorescence spectra data of hydrocarbons in contaminated water, as obtained in an embodiment of the process of the present invention; 
           [0074]      FIGS. 2-2A  illustrate a prior art graph depicting absorption spectra of oil; 
           [0075]      FIGS. 3-3A  illustrate a prior art graph depicting absorption spectrum of liquid water across a wide wavelength range; 
           [0076]      FIGS. 4-4A  illustrate a view of contaminated water (on the left) and the same water after applying a laser ablation and filtration process of the present invention (on the right) and the absorption spectra of the contaminated and cleaned water; 
           [0077]      FIG. 5  illustrates a laser scanner positioned near a corner junction of pipes, firing parallel to the flow direction in an embodiment of the method of the present invention; 
           [0078]      FIG. 6  illustrates a top view of a laser scanner above a pipe, firing perpendicular to the flow direction; 
           [0079]      FIGS. 6A-6C  illustrate side views of a laser scanner above a pipe, firing perpendicular to the flow direction; 
           [0080]      FIGS. 7A-7E  illustrates examples of laser source or scanner configurations in various embodiments of the method of the present invention; 
           [0081]      FIGS. 8A-8D  illustrate examples of how one or more laser scans can be bounced around inside a vessel, chamber, tube or pipe for maximum exposure in various embodiments of the method of the present invention; 
           [0082]      FIG. 9  illustrates a laser path in a vessel, chamber, tube, or pipe having liquid therein wherein the laser light “wall” bounces around in the vessel, chamber, tube, or pipe increasing the amount of exposure of the liquid to the laser as the liquid flows therethrough in an embodiment of the method and apparatus of the present invention; 
           [0083]      FIG. 10  is a schematic diagram of an embodiment of the process of the present invention wherein contaminated liquid flows into a container to undergo a laser ablation process, wherein separated or transformed hydrocarbons are separated from the contaminated liquid and flowed to a collection chamber, and wherein clean water exits the container or pipe; 
           [0084]      FIGS. 11-12  are images of bubbles formed in water during a laser ablation process; and 
           [0085]      FIG. 13  is an image of contaminated water with a red aiming beam used in the dark to show the path that the laser energy would follow. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0086]    The apparatus and process of the present invention offers a more environmentally safe and effective alternative to purifying water containing hydrocarbons because it uses laser light energy, which does not require the use of consumable materials such as chemicals. Embodiments of the laser ablation and filtration method and apparatus of the present invention can be used to assist and/or replace current filtration methods. 
         [0087]    Before turning to  FIGS. 1 and 4-13 , which illustrate examples of various embodiments of the method and apparatus of the present invention, reference is made to  FIGS. 2-3 . 
         [0088]      FIGS. 2-2A  illustrate a chart showing absorption spectra of oil, from Open Journal of Marine Science: Detecting Oil Spill Contamination Using Airborne Hyperspectral Data in the River Nile, Egypt (available at: http://file.scirp.org/Html/htmlimages/9-1470129x/297a010a-dc5f-4305-adf9-a7cd430 31658.png), which is hereby incorporated herein by reference. As discussed in detecting Oil Spill Contamination Using Airborne Hyperspectral Data in the River Nile, Egypt, the interaction between the oil slick and the optical electromagnetic radiation is governed by the light transmission and reflection through the oil slick. Four recognizable windows of absorption of electromagnetic radiation with oil contamination, are 1) visible range from 400-800 μm; 2) near infrared range from 1100 μm to 1220 μm; 3) near infrared range from 1600 μm to 1760 μm; and 4) short wave infrared range from 2200 μm to 2350 μm [12]-[14].  FIG. 2  shows the spectral response of the in-situ sampling sites in the Nile River in correlation with the predefined four absorption windows. 
         [0089]      FIGS. 3-3A  illustrate a chart showing absorption spectrum of liquid water across a wide wavelength range. Strong Bands: 2900 nm, 1950 nm, 1450 nm. Medium bands: 1200 nm, 900 nm. Weak bands: 820 nm, 730 nm. The hydroxide (OH) bonds of water, for example have a strong absorption near 3,000 nm or 3 microns. (The chart shown is available at: http://omlc.org/spectra/water/abs/index.html (which is hereby incorporated herein by reference). 
         [0090]    Turning now to  FIGS. 4-13 , the laser ablation apparatus  10  of the present invention comprises a vessel  11  (see  FIGS. 5-6, 8-9 ). A vessel  11 , which may be a containment vessel or other container or a pipe or tube, contains or houses a liquid  20  to be processed and/or purified during the laser ablation and filtration process, wherein the contaminated liquid  20  may be flowed therethrough, or contained within a vessel  11  while undergoing laser ablation. The laser ablation apparatus  10  has a laser source or scanner  40  for providing and directing laser light energy  12  to the liquid  20  to be purified. In various embodiments, the vessel  11  contains the contaminated liquid  20  that will undergo the ablation and filtration process and the laser energy  12  during the treatment process. The process may utilize a wide range of wavelengths from the electromagnetic spectrum such as, but not limited to UV light, wavelengths from the visible color spectrum such as green and blue lasers, infrared lasers, as well as others. For example, 1064 nm, 532 nm, 355 nm, and/or 266 nm lasers can be used individually or simultaneously for optimal effects. For example, 1064 nm, 532 nm, 355 nm, and/or 266 nm laser radiation can be obtained from a Nd:YAG laser. 
         [0091]    The laser  40  may be positioned within or outside a vessel  11 . A vessel  11  may be a containment vessel or container manufactured for the laser ablation and filtration process. A vessel  11  may also be an existing or prior art vessel or container adapted for use with the laser filtration process. Alternatively, the vessel  11  may be a pipe or tube in the field, for example, and the process may be applied within a pipe or tube in the field. The process may be applied directly to a vessel/pipe/tube  11  in the field via inserting a laser source  40  into the vessel/pipe/tube  11  or adding a laser source  40  attachment to the vessel/pipe/tube pipe  11 . 
         [0092]    If a laser  40  is positioned outside a vessel  11 , a window  90  preferably is provided on the vessel  11 , which will allow the laser energy  12  to travel through the window  90  and within the vessel  11  to the liquid  20  housed within (see  FIG. 8 ). 
         [0093]    The position of a laser source  40  within or outside a vessel  11  is important to the laser removal process. Preferably the laser  40  is positioned so as to maximize exposure of the liquid  20  and contaminates to be removed by the laser energy. The position of the scanner affects the path  15  of the laser energy  12 . To provide a desired controlled containment and laser ablation and filtration process, certain sizing parameters are preferably applied including angle and inclination of the laser source  40 , retention time for the laser process to be applied and based on geometry of the containment or vessel  11  for proper inclination. 
         [0094]    In various embodiments one or more mirrors  80  may be utilized to affect the path  15  of the laser energy  12  wherein laser energy  12  will bounce off the one or more mirrors  80 . 
         [0095]    Additionally certain mechanical devices can be included for removal of oil, grease, gas or other contaminates and for removal of one or more by-products created by the laser process, i.e. residual oil or microbubbles. 
         [0096]    Preferably compartmental containment is provided as a vital feature for separation and removal of unwanted contaminates. In addition to residual oil, micro-bubbles may be produced as a byproduct of the laser process. Due to their size and physical characteristics, sub 50 micron by definition, the containment and compartmentalization process becomes more important and crucial to the management of the process. Compartmentalization and sizing of the compartments based on flow and flow characteristics will add to the success of the overall process of laser ablation and micro-bubbles. 
         [0097]    A vessel or container  11  may comprise a collection chamber, or a series of chambers. In various embodiments, the chambers may have perforated membranes, which allow clean water to pass therethrough but captures separated contaminates. 
         [0098]    In various embodiments a ventilation system may be integrated to collect and separate gasses that are created in the ablation process. Preferably a gas collection area or mechanism will be physically, and/or optically separated from the path  15  of the laser beam  12  in order to avoid any risk of potentially igniting flammable gasses or materials. 
         [0099]    Turning now to the laser ablation process, in various embodiments the laser ablation process preferably comprises obtaining one or more samples of contaminated water or liquid that will undergo the laser ablation process. Absorption, fluorescence, and microscopy, of the one or more samples are preferably evaluated. Absorption, fluorescence and microscopy information, characteristics and/or data can be evaluated and recorded by using absorption spectroscopy such as ultraviolet-visible spectroscopy. For example, a spectrometer such as a SILVER-Nova, that is commercially available at http://www.stellarnet.us, can be used. 
         [0100]    Absorption and fluorescence characteristics, information and data help with identifying the type of liquid or fluid, the type of hydrocarbon(s) within the fluid and also other types of contaminates that may be present. Video microscopy can help with identifying physical changes of the oil droplets, solid particles, and gas bubbles. The data may be collected by spectroscopic instruments, video microscopy instruments, gravimetric testing, and/or with other suitable analytical tools, currently existing or which may be developed in the future. Absorption characteristics also help inform the decision on which wavelengths are selected for the laser based on the wavelength&#39;s ability to travel through the particular liquid, the capability of being absorbed by the liquid and capability of being absorbed by the hydrocarbon or other targeted contaminate. 
         [0101]    After evaluating absorption, fluorescence and microscopy characteristics and/or other collected data for the purpose of determining the liquid composition and contaminants present therein, the process includes selecting a specific or desired wavelength of pulsed, modulated, or continuous wave laser energy at a sufficient energy density to target a particular, or more than one, unwanted hydrocarbon or other contaminant, based on the absorption characteristics of the hydrocarbons, contaminates and the liquid. 
         [0102]    Next, contaminated water will be flowed, pulled or otherwise into the containment vessel. A desired laser source and configuration will be selected. Laser energy can then be supplied throughout the contaminated liquid, within the containment vessel, at the selected wavelength. A selected time interval and temperature may also be utilized. The laser energy will travel through the liquid and be absorbed by the hydrocarbon, gas, grease and/or other targeted contaminate for vaporizing, denaturing, rendering inert, killing and/or separating from the liquid, e.g., rising to the top of the liquid wherein it may flow to a collection reservoir or chamber. Examples of laser scanner configurations will be discussed further below with reference to  FIGS. 5-9 . 
         [0103]    In various embodiments, separated hydrocarbon, gas, grease, and/or other targeted contaminates are disposed of after removal, e.g. flowed to a collection chamber or reservoir or sump  16 . 
         [0104]    A vessel  11  may be configured so that separated or transformed hydrocarbons or contaminates flow to the top of the liquid, wherein the separated or transformed hydrocarbons can be separated from the liquid through gravity separation, for example, and then flowed to a collection chamber or reservoir or sump  16 . To remove separated contaminates, skimmer devices such as spillover weirs, rotatable paddles, or flight and rake systems, may be used to assist with removal and flow of separated materials to a collection chamber or collections sump  16 .  FIG. 10  is a schematic diagram illustrating an embodiment of the method, wherein contaminated water  20  flows into vessel  11 . Separated or transformed hydrocarbons or contaminates can flow to the top of the liquid and to a collection chamber  16 . Prior to flowing to a collection chamber they could also be flowed through skimmer devices such as spillover weirs, rotatable paddles, or flight and rake systems. Processed water exits vessel  11  after the laser ablation process is complete. 
         [0105]    A collection chamber or series of chambers, perforated membranes, or a ventilation system preferably will be integrated to collect and separate the gasses that are created in the ablation process. Preferably this gas collection area or mechanism is physically and/or optically separated from the path of the laser beam in order to avoid any risk of potentially igniting flammable gasses. 
         [0106]    Additional reference is made to U.S. Pat. Nos. 8,834,723; 8,834,724; 9,095,786; and to U.S. Patent Application Publication No. US20160009571A1, each of which is hereby incorporated herein by reference, which are directed to apparatuses and methods for separation and removal of hydrocarbons or other contaminates from a liquid. 
         [0107]    After laser energy is applied under selected parameters and for a selected time interval, data may be gathered and collected on the one or more samples of the processed or purified liquid, including on the amount of hydrocarbon or contaminants remaining in the liquid, as well as the type of hydrocarbon or contaminants that remain in the liquid. If necessary, the process may be repeated until only a desired minimum amount of the hydrocarbon or contaminate remains in the liquid, e.g. under 15 ppm (15 microliter/liter) hydrocarbon. The same liquid may also undergo the laser ablation and filtration process again wherein one or more different selected wavelengths are utilized to target one or more different hydrocarbons or contaminates that may be present in the liquid. 
         [0108]    In various embodiments, after purifying the liquid, the liquid may be returned to a reservoir, or to the source of the liquid or used downhole. 
         [0109]    In various embodiments, more than one laser source or scanner, e.g. two, three, four, five or more, may be used, each laser source or scanner tuned to the same parameters, to increase exposure of the liquid to the laser beam by having multiple laser paths directed through the liquid at the same time. 
         [0110]    In various embodiments, more than one laser source or scanner, e.g. two, three, four, five or more, may be used, each laser source or scanner tuned to one or more different parameters, e.g., one or more different wavelengths, to send laser beams at different wavelengths and/or different parameters through the liquid at the same time. 
         [0111]    Turning now to  FIG. 1 , an example will be discussed.  FIG. 1  illustrates absorption and fluorescence data  13  gathered while performing the laser ablation process on a sample of contaminated water. The absorption and fluorescence spectra of hydrocarbons is shown. The lines designated by A-A highlight the 500-550 nm peak. 
       EXAMPLE 
       [0112]    The following example is illustrative and is not exhaustive. Hydrocarbons present in a liquid are measured via an ASD spectroradiomete, to absorb around 400-800 nm, with a peak fluorescence around 500-550 nm (see  FIGS. 1-1A  and  FIGS. 2-2A ). Laser radiation can be used to target the entire hydrocarbon that is known to fluoresce at these wavelengths. For example a 532 nm laser radiation is an effective wavelength because this particular wavelength passes through both fresh and salt water fairly well ( FIG. 3 ) and is also strongly absorbed by hydrocarbons. Other wavelengths, selected based on their absorption characteristics into a particular contaminant, and the fluid can also be used. For example, wavelengths may be selected that will penetrate the liquid and will be absorbed by the hydrocarbon and cause vaporization, denaturing or separation of the hydrocarbon from the fluid. Also, in various embodiments a wavelength will be selected so the liquid absorbs some of the laser light energy while the laser light energy is passing through the liquid. 
         [0113]    UV laser radiation can also be used to neutralize pathogens, bacteria, and other unwanted organisms in water. 
         [0114]    The laser ablation and filtration apparatus and process offers a more environmentally safe and effective alternative to purifying water because it uses laser light energy, which does not require the use of consumable materials such as chemicals. Laser ablation filtration methods can be used to assist and/or replace prior art or current filtration methods. 
         [0115]    In various embodiments, laser filtration methods can be used to assist and/or replace current filtration methods. 
       Experimental Study 
       [0116]      FIGS. 4-4A  illustrate before and after results for water  20  processed and/or purified with a laser ablation process.  FIG. 4A  is a photograph view illustrating a sample of contaminated water  20 , and then a sample of processed water  30 . Contaminated water  20  had hydrocarbon levels measuring at 21.42 ppm. After going through a laser ablation and filtration process the processed water  30  had hydrocarbon levels measuring at 6.70 ppm. During the experimental study, 1064 nm 100 ns laser pulses in a prototype system were used to successfully reduce the concentration of a Gulf of Mexico offshore location for a Major Oil Company oil dispersion in water, at room temperature, by 75% by vaporizing the oil that was emulsified in the water. As shown in  FIG. 4A , the water turned visibly clearer after exposure to the laser pulses, a gas was generated, and the measured parts per million of the hydrocarbon content decreased by 75%. 
         [0117]    In various embodiments one or more different selected wavelengths may be used individually or at the same time to achieve optimal results while purifying water and to target one or more different kinds of contaminates at the same time. 
         [0118]    In various embodiments a wavelength between 266 nm and 1064 nm may be utilized to purify water containing hydrocarbons. In other embodiments a wide range of wavelengths from the electromagnetic spectrum can be utilized to target varying hydrocarbons or other contaminates based on the particular wavelengths effect on the contaminants or hydrocarbons. 
         [0119]    In various embodiments multiple different wavelengths may be utilized to process and/or clean water containing a plurality of different types of hydrocarbons or other containments, the wavelengths selected based on absorption and/or florescence and/or microscopy characteristics or data of the liquid and particular hydrocarbons at issue so that the laser energy will be able to travel through the liquid, reach the hydrocarbon or other contaminate, and vaporize, denature, separate or otherwise render inert the hydrocarbon or other contaminate. 
         [0120]    It is foreseen that laser radiation at 532 nm, e.g. high frequency 532 nm, will be even more effective at exciting and removing hydrocarbons than a 1064 nm wavelength, from water based on the known absorption characteristics of water and hydrocarbons. 
         [0121]    In various embodiments a combination of more than one wavelength, used simultaneously, is foreseen to provide optimal results. When using multiple wavelengths, multiple hydrocarbons and contaminants having different absorption characteristics may be targeted at one time. For example wavelengths such as, but not limited to, 1064 nm and 532 nm and 355 nm and 266 nm can be used at the same time to achieve optimal desired results while purifying water. 
         [0122]    In various embodiments, one or more wavelengths, for example wavelengths such as, but not limited to, 1064 nm and 532 nm and 355 nm and or 266 nm can be used individually, in sequence when processing the liquid more than one time, to achieve optimal desired results while purifying or cleaning the liquid. 
         [0123]    In various embodiments the same wavelength, e.g. 1064 nm and 532 nm and 355 nm and or 266 nm, can be used in sequence when processing the liquid more than one time to achieve optimal desired results while purifying or cleaning the liquid. 
         [0124]    In various embodiments wavelengths of 1064 nm and 532 nm are preferably selected for targeting hydrocarbons in water, including fresh or salt water, and the 1064 nm or 532 nm wavelengths may each be utilized alone, and/or together, and/or in sequence in a laser ablation process. 532 nm and 1064 nm are related harmonically as 532 nm is the second harmonic of 1064 nm laser light. 1064 divided by 2=532. 
         [0125]    In various embodiments, the laser ablation process may be used in a mobile device or incorporated into a floating or submerged vessel (e.g., a motorized vessel) or incorporated into an apparatus that can filter water around it or process water that passes through it as it floats or moves. Such a vessel system could be placed inside of a water holding tank and purify the water or it could be, for example, released into the ocean to deal with an oil spill. Instead of the water flowing through a stationary system, the system may be mobile and move through the water and process the water while the vessel moves through the water. For example, a self-contained vessel may comprise a laser filter, wherein the vessel can suck or gather or flow water into it as it moves, or while it is stationary, and process the water. In various embodiments the self-contained floating or moveable vessel can also be equipped with sensors, e.g., an EX-100 sensor, commercially available at http://www.advancedsensors.co.uk, that measures parts per million (ppm) of oil or other contaminates present in water. The vessel may be configured to activate once a designated level of hydrocarbons or contaminates is reached. Activation could be automatically set to occur when a certain level of hydro-carbon or contaminate is measured. Alternatively, activation could occur, manually or remotely, or via other suitable means when a hydro-carbons or other contaminates measure at a specified level. 
         [0126]      FIG. 5  illustrates an arrangement wherein a laser scanner  40  is positioned at or near a corner of a vessel  11 , for example a corner junction of a pipe system or containment vessel  11 . As shown, a laser scanner  40  is at corner of pipes or vessel  11 , firing parallel to the flow direction. A laser path  15  is illustrated. Such a configuration includes incorporation of a laser scanning system  40 , such as, but not limited to, those manufactured by G.C. Laser Systems Inc. for the GC-1 laser system. Additional scanning systems  40  can also be used in which the laser energy of beam  12  exits the system  40  as a cone to trace out a closed curve of a circle or oval. The laser energy  12  cone can be fired down the length of the pipe or containment vessel  11  until it terminates on the walls. All water or liquid  20  passing through the pipe  11  must pass through the laser  12  cone as it flows through the pipe  11 . The pipe  11  can for example be round or square or rectangle, or other desired shape. 
         [0127]      FIGS. 6-6C  illustrate an arrangement wherein a laser scanner  40  is positioned above a pipe or vessel  11 , firing perpendicular to the flow direction. Such a configuration utilizes a scanning system  40  in which the laser beam  12  exits the system  40  as a cone to trace out a closed curve of a circle or oval. The top view and side views show that as liquid  20  passes past the laser beam  12  circular scan, it is exposed to the laser beam  12  twice: 1 &amp; 2. The first exposure is as the liquid  20  enters the circle, and the second exposure is as the liquid  20  exits the circle. 
         [0128]    The liquid material  20  is processed twice as efficiently in such a configuration with a laser beam  12  circular scan as with a linear scan method, by comparison, because the liquid  20  gets double the exposure. A laser beam  12  linear scan, running a line perpendicular to the direction of the flow, in such a configuration allows the material to react with the laser beam  12  once as the liquid  20  passes. 
         [0129]    The side views in  FIGS. 6A-6C  show different configurations of how the laser beam  12  cone can be shaped to interact with the material: A: direct shot from scanner into liquid  20  at an angle, e.g., preferably a 5 to 45 degree angle (see  FIG. 6A ). B: Scanner  40  interacts with and optic  60  such as a telecentric f-theta lens that creates a more perpendicular tube out of the incoming cone (see  FIG. 6B ). C: laser  12  Cone is fired into a focusing lens  70  such as a regular lens or f-theta lens to create more intense focus in a particular focal plane or zone (see  FIG. 6C ). 
         [0130]    In various embodiments a laser beam can be directed into a chamber at an angle other than 90 degrees. 
         [0131]    This type of design can be executed by having a window  90  composed of a material which transmits the laser radiation on the pipe or containment vessel to allow the laser beam to enter the pipe. Fused silica is an example of such a material for a window. The pipe or containment vessel  11  can be square or round or any other desired shape. A square shape, in cross section, pipe or container  11  is preferred as allowing a more efficient exposure of the liquid  20  to a laser beam  12 . One face of a square pipe  11  would preferably feature a fused silica, or other suitable material, window  90  to allow the laser beam  12  to enter. 
         [0132]      FIGS. 7A-7E  illustrate examples of some possible laser scanner  40  configurations. The laser source or scanner  40  can be designed, for example, with different optics to create a laser beam  12  having a 2 dimensional flat plane (A+C) (see  FIGS. 7A-7C ), a three dimensional tube (A+D) (see  FIGS. 7A and 7D ), or a cone scan pattern (B+E) (see  FIGS. 7B and 7E ). Each scan pattern or path  15  has unique benefits and attributes, for example a scan pattern or path that creates a flat plane (A+C) can produce a laser field wall that is easy to manipulate, while a laser tube (A+D) or cone path (B+E) can allow for two exposures of the material that passes through it. Line scanning and/or circular or oval scanning laser systems  40  can be used. 
         [0133]      FIGS. 8A-8D  illustrates examples of how one or more laser beams  12  can be bounced around in a path  15  inside a tube  11  for maximum exposure. The laser light or beam  12  enters a vessel/chamber/tube/pipe  11 , which has a liquid or fluid therein, or flowing through it, e.g., contaminated liquid  20 , at an angle other than 90 degrees, and can be bounced around with mirrors  80  that are placed either inside the vessel/chamber/tube/pipe  11  (see  FIGS. 8C-8D ) or on the outside of the vessel/chamber/tube/pipe  11  (see  FIG. 8A-8B ) behind fused silica (or other appropriate material) windows  90 , for example. Having the mirrors  80  on the outside of a fused silica window  90  can help keep the mirrors clean. The laser path  15  can terminate at a target  100 , in the liquid over a distance (see  FIG. 8D ), or on the wall of the tube (see  FIG. 8A-C ). The target  100  can be simply an inert energy dump material or can be made of a material that will facilitate plasma formation and cavitation bubbles. 
         [0134]    As illustrated in  FIG. 8A , the mirrors  80  can be spaced apart from one another a selected distance on top and bottom portions of a vessel/container/tube/pipe  11 , wherein the top mirrors  80  are positioned offset from the bottom mirrors  80 . As illustrated in  8 B- 8 D, alternatively a single larger mirror  80  can be placed on interior or exterior top and bottom portions, over the entire length of the vessel/tube/container/pipe  11  for which the laser energy  12  will travel in a path  15 . In the examples of  FIG. 8A-C  a single laser source or scanner  40  is used to provide laser energy  12  that bounces around the mirrors within the container in a path  15 . In FIG.  8 D two lasers  40  are utilized. The two laser scanners  40  may be set to the same or different wavelengths to target one or more types of hydrocarbons or contaminates present in the liquid. If both laser scanners  40  are set to the same wavelength, it will increase the exposure of the liquid to the laser energy of the particular wavelength. If the laser scanners  40  are set to different wavelengths, then more than one type of hydrocarbon or contaminate may be targeted at the same time. In various embodiments any desired number of laser scanners  40 , e.g., 1 or 2 or 3 or 4 or 5 or 6 or more as desired may be utilized to maximize exposure of the liquid to a particular laser wavelength or to target multiple contaminants at one time. 
         [0135]      FIG. 9  is a three dimensional rendering example of a laser path  15  from  FIG. 8 . As illustrated, the laser light or energy  12  “wall” or plane bounces around in the vessel/container/tube/pipe  11 , increasing the amount of exposure the liquid  20  gets to the laser energy  12  as it flows through the vessel/container/tube/pipe  11 . 
         [0136]      FIG. 10  is a schematic diagram of an embodiment of the process of the present invention wherein contaminated liquid  20  flows into a container or vessel or pipe  11  to undergo a laser ablation process, wherein separated or transformed hydrocarbons or other contaminants are separated from the contaminated liquid  20  and flowed to a collection chamber  16 , e.g., continuously flowing therethrough, and wherein clean or processed water  30  exits the container or pipe or vessel  11  after being exposed to the laser energy. A similar process can be performed with a submergible vessel. A similar process can also be performed wherein rather than continuously flowing through vessel or pipe  11 , the contaminated water enters a vessel or pipe or chamber  11  and stops flowing to undergo a laser ablation process. After the laser ablation process it can then be flowed to an exit. After the laser ablation process contaminants can also be flowed to a collection chamber or series of chambers. Skimmer devices such as spillover weirs, rotatable paddles, or flight and rake systems, may be used to assist with removal and flow of separated materials to a collection chamber or collections sump  16 . A collection chamber or series of chambers, perforated membranes, or a ventilation system can also be integrated to collect and separate the gasses that are created in the ablation process. 
         [0137]      FIGS. 11-13  show bubbles  18  formed during a laser ablation process.  FIG. 11  illustrates contaminated liquid  20  that is darker in color than the contaminated liquid  20  of  FIG. 12 . Bubbles are starting to form in  FIG. 11 , with more present in  FIG. 12  and with the bubbles rising.  FIG. 13  illustrates a photo that was taken after a red aiming beam was used in the dark, that shows the path of the laser energy through the liquid. This red aiming beam is replaced by the actual laser beam during the process. 
         [0138]    In order to confirm repeatability, depending on the parameters and laser power being used, 1-5 minutes exposure to laser energy such as shown in the figures, gives noticeable, visible, purifying results. 
         [0139]    The following is a list of parts and materials suitable for use in the present invention: 
         [0000]    
       
         
               
             
               
               
             
               
               
             
           
               
                   
               
               
                 PARTS LIST: 
               
             
          
           
               
                 PART NUMBER 
                 DESCRIPTION 
               
               
                   
               
             
          
           
               
                 10 
                 laser ablation apparatus 
               
               
                 11 
                 vessel/container/tube/pipe 
               
               
                 12 
                 laser energy/light/radiation/beam 
               
               
                 13 
                 absorption and fluorescence data 
               
               
                 15 
                 path 
               
               
                 16 
                 collection chamber/reservoir/sump 
               
               
                 18 
                 bubble 
               
               
                 20 
                 contaminated water/liquid/fluid 
               
               
                 30 
                 purified/processed water 
               
               
                 40 
                 laser source/laser scanner 
               
               
                 60 
                 optic 
               
               
                 70 
                 focusing lens 
               
               
                 80 
                 mirror 
               
               
                 90 
                 window 
               
               
                 100 
                 target 
               
               
                   
               
             
          
         
       
     
         [0140]    All measurements disclosed herein are at standard temperature and pressure, at sea level on Earth, unless indicated otherwise. All materials used or intended to be used in a human being are biocompatible, unless indicated otherwise. 
         [0141]    The foregoing embodiments are presented by way of example only; the scope of the present invention is to be limited only by the following claims.