This patent application relates generally to systems for use in surface and subsurface remediation of soil, rocks, sand, groundwater, and/or surface water, etc., and related methods. For example, this patent application relates to injection systems and related methods for remediating contaminants in situ, for example, using surfactants or surfactant-cosolvent mixtures and oxidants. This patent application also relates to injection systems and extraction systems used together, for example, for a combination of contaminant extraction and in situ remediation, and related methods.
Soil and/or groundwater remediation typically involves injecting chemicals or other substances into the soil or groundwater to locations proximate the contaminants of concern (COC). The injected chemicals or other substances react with the COCs in situ to eliminate them, to break them down into less harmful substances, and/or to otherwise neutralize them. One type of in situ remediation is referred to as surfactant enhanced in situ chemical oxidation (S-ISCO) remediation, disclosed in applicant's U.S. Published Patent Application No. 2008/0207981, published Aug. 28, 2008, the entire content of which is incorporated herein by reference. S-ISCO remediation can be useful for remediating, for example, manufactured gas plant (MGP) sites, as well as sites with chlorinated solvents, petroleum hydrocarbons, pesticides, herbicides, polychlorinated biphenyls, and other nonaqueous phase liquids (NAPLs) or sorbed COCs.
Some soil remediation processes, such as S-ISCO, may operate entirely in-situ, e.g., without extraction wells or pumps for recovering the injected chemicals and/or by-products of the remediation process. Other soil remediation processes may incorporate a combination of in-situ remediation (e.g., S-ISCO) and extraction. In order to ensure optimum remediation of the COCs, and at the same time, to minimize the level of leftover remediation chemicals and/or by-products of the remediation process, the chemicals should be injected to the proximity of the COCs in precise quantities, compositions, concentrations, and in specific temporal patterns. In addition, since the quantity, composition, and characteristics of the COCs can vary from zone to zone within a given treatment area, it may be necessary to vary the quantity, composition, and concentration of the injected chemicals on a zone-to-zone basis within a single treatment site.
Known injection systems have failed to provide adequate control and precision in the quantity (e.g., flow rate), composition, and concentration of the injected chemicals. For example, some known injection systems, such as the RegenOx™ manufactured by Regenesis, use a batch mixture of chemicals that is injected into a single fluid stream that is subsequently split into multiple fluid streams directed to different zones (e.g., wells) within a single treatment site. This type of system typically does not provide sufficient precision and/or control in the composition, concentration, and/or flow rate of injected chemicals, especially on a well-to-well basis.
Further objectives and advantages, as well as the structure and function of exemplary embodiments, will become apparent from a consideration of the description, drawings, and examples.
According to an exemplary embodiment, a system for soil, groundwater, or surface water remediation comprises a water supply including a first fluid stream in fluid communication with a first injection point, and a second fluid stream in fluid communication with a second injection point; a first surfactant pump adapted to inject a surfactant into the first fluid stream, and a second surfactant pump adapted to inject a surfactant into the second fluid stream; and a first oxidant pump adapted to inject an oxidant into the first fluid stream, and a second oxidant pump adapted to inject an oxidant into the second fluid stream.
According to another exemplary embodiment, a system for soil, groundwater, or surface water remediation includes a water supply including at least a first fluid stream in fluid communication with a first injection point; a surfactant storage container containing a surfactant; an oxidant storage container containing an oxidant; a surfactant pump adapted to inject the surfactant into the first fluid stream; and an oxidant pump adapted to inject the oxidant into the first fluid stream.
According to another exemplary embodiment, a method of remediating soil, groundwater, or surface water comprises pumping a first fluid stream of water to a first injection point proximate a first contaminant of concern; injecting a surfactant into the first fluid stream using a first surfactant pump; and injecting an oxidant into the first fluid stream using a first oxidant pump.
According to another exemplary embodiment, a system for soil, groundwater, or surface water remediation, comprises a water supply including at least a first fluid stream in fluid communication with a first injection point; a surfactant pump adapted to inject a surfactant into the first fluid stream; an oxidant pump adapted to inject an oxidant into the first fluid stream; and a contaminant extraction system located proximate the first injection point.
The foregoing and other features and advantages of the invention will be apparent from the following drawings wherein like reference numbers generally indicate identical, functionally similar, and/or structurally similar elements.
Embodiments of the invention are discussed in detail below. In describing embodiments, specific terminology is employed for the sake of clarity. However, the invention is not intended to be limited to the specific terminology so selected. A person skilled in the relevant art will recognize that other equivalent parts can be employed and other methods developed without parting from the spirit and scope of the invention. All references cited herein are incorporated by reference as if each had been individually incorporated.
“Contaminants” encompasses any substance present in a location that, by its presence, diminishes the usefulness of the location for productive activity or natural resources, or would diminish such usefulness if present in greater amounts or if left in the location for a length of time. The location may be subsurface, on land, in or under the sea or in the air. As used herein, “contaminated soil” encompasses any soil that contains at least one contaminant according to the present invention. “Contaminant” thus can encompass trace amounts or quantities of such a substance. Examples of productive activities include, without limitation, recreation; residential use; industrial use; habitation by animal, plant, or other life form, including humans; and similar such activities. Examples of natural resources are aquifers, wetlands, sediments, soils, plant life, animal life, and ambient air quality.
“Introduce” means to cause to be present in a location. A material or item can be introduced into a location even if the material or item is released somewhere else and must travel some distance in order to reach the location. For example, if a substance is released at location A, and the substance will migrate over time to location B, the substance has been “introduced” into location B when it is released at location A. An item can be introduced in any manner appropriate under the circumstances for the substance to be introduced into the location.
An “effective amount” encompasses an amount of a material or item that will bring about a decrease in the amount of one or more contaminants in a location. An “effective amount” also encompasses an amount that brings about a stabilization of contaminant amounts or quantities in a location where they would otherwise increase or remain constant. It also encompasses an amount that brings about a reduction in the rate of increase of the amount or quantity of a contaminant in a location, as compared to the rate that would have obtained had the material or item not been introduced.
“Activate” means to modify or alter a substance in such a way that the substance is able to perform a function it was unable, or less able, to perform prior to activation. For example, “activation” encompasses the conversion of a persulfate ion into sulfate free radical, which is then able to oxidize other substances in a location.
“Expose” means to cause to be, or become, available for interaction with other substances in the surroundings. For example, once a polymer-coated nanoparticle is “exposed,” it is available to come into contact, chemically react, or otherwise interact with chemicals in the location into which it has been introduced.
A “reducing environment” or “reducing zone” is an environment in which substances are generally more likely to be reduced—e.g., have their oxidation numbers reduced, or gain electrons—than they are in another location. A reducing environment can also be conducive to the growth and metabolism of anaerobic organisms, as a reducing environment will eliminate species, such as oxygen, that might otherwise interfere with their growth or development.
An “oxidizing environment” or “oxidizing zone” is an environment in which substances are generally more likely to be oxidized—e.g., have their oxidation numbers increased, or lose electrons—than they are in another location. An oxidizing environment can also be conducive to the growth and metabolism of aerobic organisms.
Referring to
Injection system 10 can be used to inject chemicals or other substances to one or more injection points at a treatment site. According to an exemplary embodiment, system 10 can be used to inject an oxidant, a surfactant or surfactant/co-solvent mixture (referred to herein generally as a “surfactant”), and optionally an activator to each of the injection points to remediate COCs proximate the injection points. In the exemplary embodiment shown in
The injection points 100-300 can be located subsurface, and can comprise, for example, injection wells, injection trenches, or temporary injection sites. The injection points 100-300 can additionally or alternatively be located above surface, and can comprise, for example, the surface of the ground, such as surface-contaminated soils, rocks, beaches, or orchards. The injection points 100-300 can additionally or alternatively comprise, for example, the surface or subsurface of water, such as an ocean, lake, river, or reservoir. One of ordinary skill in the art will know that other types and locations of injection points known in the art are possible. The COCs can be the same at each injection point 100-300, or alternatively, can vary from one injection point to another. The injection points 100-300 can all be spaced apart from one another, or alternatively, one or more of the injection points 100-300 can partially or fully overlap one another, for instance, were the concentration of the COC is very high in a specific location.
It may be advantageous to vary the composition, concentration, and/or quantity of injected chemicals from one injection point to another, for example, to account for the quantity, composition, and/or characteristics of the COC proximate each injection point. It may also be advantageous to vary the composition, concentration, and/or quantity of the injected chemicals based on the spatial distribution of the COC at each injection point, and/or based on the properties of the soil, groundwater, subsurface, etc., surrounding the COC at each injection point. It may also be advantageous to modify the amounts of materials delivered over time. In order to provide increased precision and control over the substances injected to each injection point, the system 10 can include a dedicated pump for each chemical component injected at each injection point, as will be described in more detail below.
Referring to
The water can enter a holding tank 16 that can act, for example, as a capacitor, in case of sudden increases in the demand for water which may exceed the pressure or flow capabilities of the water supply 12. According to an exemplary embodiment, the holding tank 16 can comprise a Baker tank having a capacity of 5,000 to 20,000 gallons, however, other types and sizes of holding tank(s) are possible.
A water pump 18 can pump water from the holding tank 16 to one or more of the injection points 100-300. According to the exemplary embodiment shown in
According to the exemplary embodiment where a common water pump 18 is used, an adjustable flow meter can be included in each fluid flow upstream of the respective injection point, to control the flow rate of water to that injection point. For example, as shown in
The system 10 can include injectors adapted to inject the chemicals proximate each injection point 100, 200, 300. For example, a first injector can inject chemicals proximate injection point 100, a second injector can inject chemicals proximate injection point 200, and a third injector can inject chemical proximate injection point 300.
As mentioned previously, the system 100 can include a dedicated injection pump for each chemical component injected to each injection point. For example, with reference to injection point 100 in
Still referring to
According to an exemplary embodiment of the invention, the surfactant can comprise a substance made from a naturally occurring biodegradable plant oil. A surfactant and/or cosolvent can be or can be derived from a plant extract or a biodegradable plant extract. Additionally or alternatively, the surfactant can comprise a substance made from castor oil, coca oil, coconut oil, soy oil, tallow oil, cotton seed oil, or a naturally occurring plant oil. Additionally or alternatively, the surfactant can comprise Citrus Burst 1, Citrus Burst 2, Citrus Burst 3, or E-Z Mulse. Additionally or alternatively, the surfactant can comprise ALFOTERRA 53, ALFOTERRA 123-8S, ALFOTERRA 145-8S, ALFOTERRA L167-7S, ETHOX HCO-5, ETHOX HCO-25, ETHOX CO-5, ETHOX CO-40, ETHOX ML-5, ETHAL LA-4, AG-6202, AG-6206, ETHOX CO-36, ETHOX CO-81, ETHOX CO-25, ETHOX TO-16, ETHSORBOX L-20, ETHOX MO-14, S-MAZ 80K, T-MAZ 60 K 60, TERGITOL L-64, DOWFAX 8390, ALFOTERRA L167-4S, ALFOTERRA L123-4S, or ALFOTERRA L145-4S. As mentioned previously, the surfactant can comprise a surfactant/co-solvent mixture, in which case, the co-solvent can comprise of dilimnone, terpinoids, alchohols, or plant-based solvents. Further examples of surfactants and surfactant/co-solvent mixtures include terpenes, citrus-derived terpenes, limonene, d-limonene, castor oil, coca oil, coconut oil, soy oil, tallow oil, cotton seed oil, and a naturally occurring plant oil. The surfactant and/or cosolvent can be a nonionic surfactant, such as ethoxylated soybean oil, ethoxylated castor oil, ethoxylated coconut fatty acid, and amidified, ethoxylated coconut fatty acid. For example, a composition of surfactant and cosolvent can include at least one citrus terpene and at least one surfactant. A citrus terpene may be, for example, CAS No. 94266-47-4, citrus peels extract (citrus spp.), citrus extract, Curacao peel extract (Citrus aurantium L.), EINECS No. 304-454-3, FEMA No. 2318, or FEMA No. 2344. A surfactant may be a nonionic surfactant. For example, a surfactant may be an ethoxylated castor oil, an ethoxylated coconut fatty acid, or an amidified, ethoxylated coconut fatty acid. An ethoxylated castor oil can include, for example, a polyoxyethylene (20) castor oil, CAS No. 61791-12-6, PEG (polyethylene glycol)-10 castor oil, PEG-20 castor oil, PEG-3 castor oil, PEG-40 castor oil, PEG-50 castor oil, PEG-60 castor oil, POE (polyoxyethylene) (10) castor oil, POE(20) castor oil, POE (20) castor oil (ether, ester), POE(3) castor oil, POE(40) castor oil, POE(50) castor oil, POE(60) castor oil, or polyoxyethylene (20) castor oil (ether, ester). An ethoxylated coconut fatty acid can include, for example, CAS No. 39287-84-8, CAS No. 61791-29-5, CAS No. 68921-12-0, CAS No. 8051-46-5, CAS No. 8051-92-1, ethyoxylated coconut fatty acid, polyethylene glycol ester of coconut fatty acid, ethoxylated coconut oil acid, polyethylene glycol monoester of coconut oil fatty acid, ethoxylated coco fatty acid, PEG-15 cocoate, PEG-5 cocoate, PEG-8 cocoate, polyethylene glycol (15) monococoate, polyethylene glycol (5) monococoate, polyethylene glycol 400 monococoate, polyethylene glycol monococonut ester, monococonate polyethylene glycol, monococonut oil fatty acid ester of polyethylene glycol, polyoxyethylene (15) monococoate, polyoxyethylene (5) monococoate, or polyoxyethylene (8) monococoate. An amidified, ethoxylated coconut fatty acid can include, for example, CAS No. 61791-08-0, ethoxylated reaction products of coco fatty acids with ethanolamine, PEG-11 cocamide, PEG-20 cocamide, PEG-3 cocamide, PEG-5 cocamide, PEG-6 cocamide, PEG-7 cocamide, polyethylene glycol (11) coconut amide, polyethylene glycol (3) coconut amide, polyethylene glycol (5) coconut amide, polyethylene glycol (7) coconut amide, polyethylene glycol 1000 coconut amide, polyethylene glycol 300 coconut amide, polyoxyethylene (11) coconut amide, polyoxyethylene (20) coconut amide, polyoxyethylene (3) coconut amide, polyoxyethylene (5) coconut amide, polyoxyethylene (6) coconut amide, or polyoxyethylene (7) coconut amide. Examples of surfactants derived from natural plant oils are ethoxylated coca oils, coconut oils, soybean oils, castor oils, corn oils and palm oils. Many of these natural plant oils are US FDA GRAS.
Additional surfactants and surfactant/co-solvent mixtures, and details regarding the same, are described in the aforementioned U.S. Published Patent Application No. 2008/0207981.
A surfactant pump can be dedicated to each injection point 100-300, and inject surfactant from the surfactant container 32 to the respective injection point. For example, as shown in
According to another exemplary embodiment, the system can comprise multiple surfactant containers. For example, a different surfactant container may be associated with each surfactant pump, or one surfactant container may be associated with subsets of surfactant pumps. According to this configuration, different surfactants may be stored in different surfactant containers, allowing different surfactants to be introduced into each injection site, or groups of injection sites. This can permit the surfactant to be tailored to the COC, soil conditions, or other parameters at each injection site.
An activator storage container can hold a chemical activator, for example, in liquid form. In the exemplary embodiment of
According to an exemplary embodiment of the invention, the activator can comprise, for example, a metal, a zero valent metal (e.g., zero valent iron, manganese, cobalt, palladium, or silver), a chelated metal, a chelated iron, Fe-NTA, Fe(II)-EDTA, Fe(III)-EDTA, Fe(II)-citric acid, and/or Fe(III)-citric acid. Additional exemplary activators can include a base (e.g., NaOH), heat, hydrogen peroxide, or oxidants. Additional activators and details regarding the same are described in the aforementioned U.S. Published Patent Application No. 2008/0207981.
An activator pump can be dedicated to each injection point 100-300, and can inject activator from one or both of the activator containers 42a, 42b to the respective injection point. For example, as shown in
As described above, according to an exemplary embodiment, the activator container 42a can contain a different activator than container 42b. According to this embodiment, some of the activator pumps may draw activator from container 42a, while others may draw activator from container 42b, allowing different activators to be introduced into different injection sites. According to another exemplary embodiment, a different storage container can be associated with each injection site 100-300, allowing a different activator to be injected into each injection site 100-300. This can permit the activator to be tailored to the COC, soil conditions, or other parameters at each injection site.
Referring to
According to an exemplary embodiment of the invention, the oxidant can comprise a persulfate, sodium persulfate, ozone, oxygen, air, peroxide, hydrogen peroxide, a peroxide compound, a permanganate compound, or a percarbonate compound. Additional oxidants and details regarding the same are described in the aforementioned U.S. Published Patent Application No. 2008/0207981.
An oxidant pump can be dedicated to each injection point 100-300, and can inject oxidant from one or both of the oxidant containers 50a, 50b to the respective injection point. For example, as shown in
As described above, according to an exemplary embodiment, the oxidant container 50a can contain a different oxidant than container 50b. According to this embodiment, some of the oxidant pumps may draw oxidant from container 50a, while others may draw oxidant from container 50b, allowing different oxidants to be introduced into different injection sites. According to another exemplary embodiment, a different oxidant storage container can be associated with each injection site 100-300, allowing a different oxidant to be injected into each injection site 100-300. This can permit the oxidant to be tailored to the COC, soil conditions, or other parameters at each injection site.
Still referring to
Another inline mixer 162 can also be located in the fluid stream leading up to the first injection point. Inline mixer 162 can be located downstream of mixer 160, and/or can be located downstream of the point where the oxidant enters the fluid stream 122. Accordingly, inline mixer 162 can mix the oxidant with the water stream containing the already mixed activator and surfactant. Similar inline mixers 262, 362 can be provided in fluid communication with the fluid flows 222, 322 leading up to the second and third injection points 200, 300, respectively. Combining and mixing the surfactant, oxidant, and/or activator prior to injection can enhance the coelution of the chemicals, making the remediation process more efficient.
According to an exemplary embodiment, the system 10 can be mounted on a skid 11 to facilitate transportation of the system 10, for example, from site to site. According to an exemplary embodiment, the storage containers, pumps, mixers, and/or other components of the system 10 can be secured to the skid 11.
As mentioned previously, system 10 can be used in a method of remediating soil or groundwater, for example, organic contaminated soil or groundwater. According to an exemplary embodiment, the system 10 can be used to remediate manufactured gas plant sites. Additionally or alternatively, system 10 can be used in remediating sites with chlorinated solvents, petroleum hydrocarbons, pesticides, herbicides, polychlorinated biphenyls, and other NAPLs or sorbed COCs. The method can begin with assessing the condition of the soil, groundwater, etc., to be treated. This can be done, for example, using one or more monitoring wells to determine the type, quantity, and distribution of the various COCs.
The method can generally include pumping a first fluid stream of water to a first injection point 100, for example, proximate a first contaminant of concern, injecting a surfactant into the first fluid stream using, for example, the first surfactant pump 126, and injecting an oxidant into the first fluid stream using, for example, the first oxidant pump 128. The method can further include injecting an activator into the first fluid stream using, for example, the first activator pump 130. The method can further include pumping at least second and third fluid streams of water to second and third injection points 200, 300, and injecting surfactant, oxidant, and/or activator into each of the second and third fluid streams using, for example, respective second and third surfactant pumps 226, 326, second and third oxidant pumps 228, 328, and/or second and third activators pumps 230, 330.
By having independent pumping systems for each injection point, different chemical compositions, quantities, and/or concentrations can be deployed over a given treatment site on a zone-to-zone basis. For example, it is possible to vary the flow rate, concentration, and/or composition of the injected compounds (e.g., surfactant, oxidant, and/or activator) from one injection point to another. This can allow the type and quantity of injected substances to be tailored to the specific COCs proximate each injection point, and/or to the geological or hydrogeological conditions proximate each injection point—which can be determined using one or more monitoring wells prior to, or concurrently with the pumping steps.
According to an exemplary subsurface embodiment of the remediation method, the injected chemicals (e.g., surfactant, oxidant, and activator) are not extracted from the ground following the remediation process. For example, the activator and oxidant react completely with the COCs to neutralize them, and the surfactant biodegrades. Additionally or alternatively, by-products of the remediation process, if any, are not extracted after the remediation process.
The surfactant pumps 126, 226, 326, oxidant pumps 128, 228, 328, and/or activator pumps 130, 230, 330, as well as the flow meters 124, 224, 324 can be controlled to perform the remediation process using, for example, PLC 41 or some other computer-based controller, as will be appreciated by one of ordinary skill in the art. The process can be performed manually, automatically, or by some combination of manual and automatic processes. According to an exemplary embodiment, the process can be controlled using telemetry. For example, the metering pumps and/or centrifugal pump can be connected through a PLC, which can be dialed into via telephone and controlled by a computer using telemetry software.
Once the remediation process is complete, the condition of the soil, groundwater, etc., can again be evaluated, for example, using one or more monitoring wells.
The system and method described herein can further provide for physical extraction of the COCs. For example, in certain circumstances, it may be advantageous to extract a portion of the COCs from the soil or groundwater before, during, or after remediation using the S-ISCO process. For example, extraction may be used to remove gross amounts of a NAPL prior to, or concurrently with the S-ISCO process, which may help reduce oxidant demand and cost. A surfactant may be injected into or near the COC prior to the extraction in order to aid the extraction process.
Additionally or alternatively, an extraction system may be used to create a man-made water flow during the S-ISCO process, which may be particularly helpful in cases where natural water flow provides very low or no transport of the S-ISCO chemicals (e.g., with a stagnant pocket or pool of COC). Additionally or alternatively, an extraction well can be placed between the COC and a sensitive receptor, such a house, in order to provide a buffer between the S-ISCO chemicals and the sensitive receptor.
Referring to
As shown in
Once the in-situ remediation process has sufficiently removed the residual COCs 412, the injection well 406 can be removed, as shown in
The embodiments illustrated and discussed in this specification are intended only to teach those skilled in the art the best way known to the inventors to make and use the invention. Nothing in this specification should be considered as limiting the scope of the present invention. All examples presented are representative and non-limiting. The above-described embodiments of the invention may be modified or varied, without departing from the invention, as appreciated by those skilled in the art in light of the above teachings. It is therefore to be understood that, within the scope of the claims and their equivalents, the invention may be practiced otherwise than as specifically described.
This patent application claims the priority benefit under 35 U.S.C. §119(e)(1) of U.S. Provisional Application No. 60/960,341, filed on Sep. 26, 2007, the entire content of which is incorporated herein by reference.
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/US08/11228 | 9/26/2008 | WO | 00 | 3/25/2010 |