EP3429745A1 - Colloidal agents for aquifer and metals remediation - Google Patents
Colloidal agents for aquifer and metals remediationInfo
- Publication number
- EP3429745A1 EP3429745A1 EP17767567.5A EP17767567A EP3429745A1 EP 3429745 A1 EP3429745 A1 EP 3429745A1 EP 17767567 A EP17767567 A EP 17767567A EP 3429745 A1 EP3429745 A1 EP 3429745A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bone
- agent
- iron
- composition
- particulate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0008—Sols of inorganic materials in water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0021—Preparation of sols containing a solid organic phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0034—Additives, e.g. in view of promoting stabilisation or peptisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0047—Preparation of sols containing a metal oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/04—Surfactants, used as part of a formulation or alone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
Definitions
- the present invention is directed to stabilized compositions of particulate materials and the use of such compositions to remediate contaminants from soil and groundwater.
- remediation agents for removing organic and inorganic contaminants from groundwater.
- Such agents can operate in a variety of modes including through sorption, direct destruction, stimulation of biodegradation and/or through stabilization of the contaminants. Through these various modes of action, the remedial agents act to detoxify the water and reduce any health risks associated with the contaminant.
- remedial agents While some remedial agents are completely soluble in water and allow for their relatively straightforward application in both in place (in situ) and out of place (ex situ) systems, many useful remedial agents are not soluble in water. In these cases, the application of the insoluble remedial agents is often limited to above ground treatment systems (e.g., pump and treat systems) or in trench barriers (e.g., permeable reactive barriers). However, it is desirable to use these solid remediation agents in situ and apply them via various injection or percolation techniques in order to increase the range of sites that can be treated and to reduce project costs. The limitation with solid remedial agents is that they are commonly manufactured in granular or powdered forms and therefore lack mobility in the subsurface which limits their contact with contaminants and the efficacy of treatment.
- metal sorbents particularly materials that are derived from or contain apatite-type phosphate minerals, is an established method for remediating water and soil contaminated with metals or radionuclides.
- these materials may include hydroxyapatite, bone char, and apatite II, among others.
- the apatite-containing materials can capture or chemically immobilize metals and radionuclides as insoluble forms with extremely low solubility constants to reduce their bioavailability and decrease human and ecological risks by removing them from the dissolved phase and preventing their migration.
- these materials are used in granular or powdered form within above ground treatment systems or they can be emplaced in situ via various physical methods e.g. soil mixing, back-filling of excavations, fracking, or installing in trenches known as permeable reactive barriers.
- soil mixing e.g. soil mixing, back-filling of excavations, fracking, or installing in trenches known as permeable reactive barriers.
- These relatively disruptive application methods are required for apatite-based materials in powder or granular form because they do not readily distribute through soil to reach areas of contaminated water. This lack of mobility causes the cost of treatment to be very high, whereas the contact with contaminated water remains quite low. The high cost is primarily due to the installation requirements to thoroughly treat a contaminated area.
- activated carbon is commonly used as a sorbent medium for removing organic and inorganic contaminants from water. It is used in treatment systems to detoxify industrial process water, as well as in pump-and-treat systems for above-ground treatment of contaminated groundwater. In use, activated carbon is typically manufactured and used in granular or powder form whereby the particulate is loaded into fluid- or fixed-bed treatment systems or dispersed or distributed over the area subject to contamination.
- GROUNDWATER POLLUTION ABATEMENT discloses drilling of wells in the ground and injecting a sorbent for contaminants into the path of groundwater plume, in order to stop the plume. Such reference further discloses the use of activated carbon as a sorbent and the addition of stabilizing substances to sorbent slurries.
- Dekontamination schadstoffbelasteter Aquifere discloses a process for in-situ decontamination of polluted aquifers- by injection of colloidal carbon. Such reference discloses that a charcoal particle size ⁇ 10 microns is optimal and that ionic strength inhibits colloid transport.
- the objective of the invention is to increase distribution of carbon colloids in subsurface by flushing with deionized water or raising pH of aquifer.
- remediation materials such as activated carbon
- remediation materials cannot distribute through soil to reach areas of contaminated water. Instead, it must be applied in a trench to treat water passing therethrough, or must be injected as a slurry which has limited or no mobility in the aquifer. This lack of mobility causes the cost of treatment to be very high, whereas the contact with contaminated water remains quite low. The high cost is primarily due to the large number of application points required to thoroughly treat a contaminated area.
- the remediating agents be able to transport effectively through an aquifer to reach contaminated zones while remaining highly active toward contaminants.
- the remediating agent should be effective across a wide range of aquifer conditions, including pH and redox.
- colloidal remediation agents including those treating organic and inorganic contaminants (e.g., chlorinated solvents, pesticides, energetics, hydrocarbons, metal contaminants, etc.), much farther in the subsurface than simple carboxymethyl cellulose. It is likewise desirable to provide such a composition that is of simple formulation, easy to deploy, is substantially effective at remediating contaminants from soil and groundwater, and is further substantially more effective in becoming dispersed and capable of being quickly and effectively deployed over a greater area of volume of soil and groundwater than prior art compositions and methods of using the same for environmental remediation.
- organic and inorganic contaminants e.g., chlorinated solvents, pesticides, energetics, hydrocarbons, metal contaminants, etc.
- the present invention specifically addresses and alleviates the above- identified deficiencies in the art.
- the present invention is directed to compositions of particulate remediation agent materials operative to form colloids and the use of such compositions in environmental remediation, and in particular as a means of remediating organic and/or inorganic contaminants in soil and groundwater.
- the invention comprises the combination of one or more particulate remediation agents, preferably formed to have a very fine particulate size, typically ranges from 0.1 to 10 microns, and preferably 0.5 to 2 microns, that is stabilized by at least two additives.
- the first additive is a stabilizing polymer, which may comprise either an anionic or nonionic polymer.
- the second additive is a distribution enhancement agent operative to facilitate the ability of the composition to become distributed and dispersed about a matrix of soil and groundwater.
- the distribution enhancement agent will include one or more agents selected from the group consisting of chelating agents, anionic polymers, anionic surfactants or nonionic surfactants.
- the ratio of particulate remediation agent: first additive: second additive present in amounts relative one another are in the range of 1 (remediation agent) : 0.01-1.0 (first additive) : 0.01-1.0 (second additive).
- the ratio of the aforementioned components of remediation agent: first additive : second additive are in the range of 1 (remediation agent) : 0.05-0.5 (first additive) : 0.025-0.5 (second additive), based upon relative weights of such components.
- such material may comprise activated carbon, animal bone, fish bone, synthetic bone, hydroxylapatite, fluorapatite, chlorapatite, apatite II, bone char, bone charcoal, bone ash, bone black, steel slag, furnace slag, metal oxides, including but not limited to iron oxide, iron oxyhydroxide, and iron hydroxide, alumina, zeolites, coffee beans, polylactic acids, chitin, zero-valent iron, silica, and metal silicates, namely calcium silicate, magnesium silicate and iron silicate. Combinations of the different types of particulate remediation agents are also contemplated.
- the compositions of the present invention are operative to form water- based colloids of the remediation agent, and can be deployed as an aqueous admixture whereby the remediation agent component of the aqueous admixture will range between 0.01% and 70.0% by weight of the water.
- the water based colloids of the present invention can be injected, such as by high pressure injection or fracturing, in the range of 0.02% to 40.0% particulate remediation agent.
- the water-based colloids formed according to the present invention can be applied by gravity feed or percolation into soil.
- the compositions of the present invention can be applied at a rate between approximately 1 and 80 gallons of aqueous admixture per cubic yard of soil and groundwater, and preferably between approximately 4 and 60 gallons per cubic yard.
- compositions and methods have been developed that enable increased distribution of colloids of remediation agents through soil and groundwater. This allows for very cost-effective treatment of contaminated aquifers, and therefore control over mobility of contaminants in groundwater and soil systems.
- compositions of the present invention include a very fine remediation agent material, (0.1 to 10 micron size, and preferably within a 0.5 to 2 micron range).
- the remediation agent materials are operative to sequester, stabilize, directly react with, and/or promote the biodegradation of, and hence prevent further transport of the target contaminant.
- the remediation agent material will comprise activated carbons, an apatite-containing material, which can include, but is not limited to animal bone, fish bone, synthetic bone, hydroxylapatite, fluorapatite, chlorapatite, apatite II, bone char, bone charcoal, bone ash, and bone black, steel slag, furnace slag, metal oxides, including but not limited to iron oxide, iron oxyhydroxide, and iron hydroxide, alumina, zeolites, coffee beans, polylactic acids, chitin, zero-valent iron, silica, and metal silicates, namely calcium silicate, magnesium silicate and iron silicate, as well as combinations.
- an apatite-containing material which can include, but is not limited to animal bone, fish bone, synthetic bone, hydroxylapatite, fluorapatite, chlorapatite, apatite II, bone char, bone charcoal, bone ash, and bone black, steel slag, furnace slag, metal
- compositions of the present invention further comprise at least two additives, wherein the first additive is a stabilizing polymer, and the second additive is a distribution enhancement agent.
- the addition of one or more distribution enhancement agents enables the colloidal material to distribute significantly further through soil and groundwater during application than the compositions and methods of the prior art.
- the first additive, or stabilizing polymer can be an anionic polymer or a nonionic polymer.
- examples include but are not limited to carboxymethyl cellulose (CMC), carrageenan, polyacrylic acid, xanthan gum (nonionic), and combinations thereof.
- the second additive, or distribution enhancement agent is selected from the following list: chelating agents, anionic polymers, anionic surfactants, or nonionic surfactants, and possible combinations thereof.
- Chelating agents include but are not limited to citrates, phosphates (e.g.
- SHMP SHMP, STTP, TSPP), silicates, borates, sulfates, carbonates, aminocarboxylic acids and salts thereof (e.g. EDTA, MGDA and NT A), polyamines such as ethylene diamine, as well as combinations thereof.
- Anionic polymers of the second additive include but are not limited to sulfated or carboxylated polysaccharides, polyacrylates, polyacrylamides, lignosulfonate, polyacrylate copolymers, and combinations thereof.
- Anionic surfactants include but are not limited to dioctyl sodium
- alkyl and aryl sulfates e.g. sodium lauryl sulfate
- alkyl carboxylates e.g. sodium laurate
- Nonionic surfactants include but are not limited to alkyl polyethylene oxides, ethylene oxide polymers, polyethylene oxide lauryl ether (e.g., Brij 30® produced by Croda, Inc.), ethylene oxide-propylene oxide copolymers (e.g., Tergitol XD® produced by the Dow Chemical Company), and combinations thereof.
- Compositions of this invention are preferably formed wherein the relative weight ratios of remediation agent: first additive (stabilizing polymer) : second additive (distribution enhancing agent) are in the range of: 1 : 0.01-1.0 : 0.01-1.0 and preferably in the ranges of 1 : 0.05-0.5 : 0.025-0.5
- the methods of groundwater treatment using the compositions of the present invention include applying a slurry of the aforementioned compositions to the area of contaminated groundwater sought to be treated.
- the slurry will be introduced via a technique well-known to those skilled in the art, such as injection or other application of the above compositions as a water-based colloid such that the remediation agent concentration is between 0.01% and 70.0% by weight in water.
- the material can be injected in the range of 0.02% to 40.0% remediation agent material by weight in water.
- the aqueous admixture containing the compositions of the present invention can be applied by gravity feed or percolation in the amount sufficient to remediate the contaminants believed to be present in a given area of contaminated soil/groundwater.
- a general application rate can range from between approximately 1 to 80 gallons of the aqueous admixture of the water-based colloid of the present invention per cubic yard of soil and groundwater to be treated, and preferably between approximately 4 and 60 gallons of the aqueous admixture per cubic yard treated.
- the slurry may also be co-applied or successively applied with additional amendments that are selected from a group comprised of substances that release hydrogen or oxygen, substances that through biological reactions produce hydrogen or oxygen, an electron donor, an electron acceptor, a nutrient, a microorganism, a chemical oxidant, a chemical reductant, cysteine, cysteinate compounds, a buffer and combinations thereof such that the additional amendment acts in concert with the remediation agent to enhance treatment of the contaminants present in the soil and groundwater .
- additional amendments are selected from a group comprised of substances that release hydrogen or oxygen, substances that through biological reactions produce hydrogen or oxygen, an electron donor, an electron acceptor, a nutrient, a microorganism, a chemical oxidant, a chemical reductant, cysteine, cysteinate compounds, a buffer and combinations thereof such that the additional amendment acts in concert with the remediation agent to enhance treatment of the contaminants present in the soil and groundwater .
- Example 1 Dispersion preparation: A series of colloidal dispersions were prepared with the following general composition: 1% w/w activated carbon as the remediation agent (approximately 1.5 micron average particle size), 0.25% w/w stabilizing polymer, and 0.25% w/w distribution enhancement agent. The dispersions were prepared as follows: The stabilizing polymer and second additive were mixed thoroughly into water with a high-shear mixer and mixed until homogeneous. A slurry of activated carbon in water was then added to the mixture. Each dispersion was mixed for an additional 5 minutes resulting in a very homogeneous, black colloidal suspension. The compositions of the tested dispersions and some comparative samples are shown in Table 1.
- Example 2 Column transport testing: Each of the colloids in Example 1 was diluted with tap water to a carbon concentration of 2,000 mg/L. A 25 g aliquot of each diluted colloid was eluted through a glass column (bed dimensions 2.5 x 24.0 cm) packed with saturated soil having a sand/silt/clay ratio of 93.7/3.9/2.4. The 25 g sample was eluted through the column and flushed with additional tap water until the column effluent was clear. Activated carbon in the combined effluent from each column study was measured by UV- visible spectroscopy. The total mass of carbon eluted was calculated using a calibration curve.
- Example #1 For comparison to the prior art, a standard colloid sample stabilized only by CMC was studied (Sample #1). The mass of carbon eluted by each sample is reported in table 1, and the amount of carbon eluted is also reported as a percentage relative to the standard.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Soil Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201662309193P | 2016-03-16 | 2016-03-16 | |
US15/460,003 US10512957B2 (en) | 2013-08-02 | 2017-03-15 | Colloidal agents for aquifer and metals remediation |
PCT/US2017/022795 WO2017161178A1 (en) | 2016-03-16 | 2017-03-16 | Colloidal agents for aquifer and metals remediation |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3429745A1 true EP3429745A1 (en) | 2019-01-23 |
EP3429745A4 EP3429745A4 (en) | 2019-11-20 |
Family
ID=59850824
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17767567.5A Withdrawn EP3429745A4 (en) | 2016-03-16 | 2017-03-16 | Colloidal agents for aquifer and metals remediation |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP3429745A4 (en) |
WO (1) | WO2017161178A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108031433A (en) * | 2017-12-14 | 2018-05-15 | 湖南科技大学 | A kind of preparation method of mesoporous calcium silicates load nano zero-valence iron composite material |
CN114749472A (en) * | 2022-04-14 | 2022-07-15 | 浙江工业大学 | Application method of uranium contaminated soil remediation agent |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001008825A1 (en) * | 1999-07-29 | 2001-02-08 | Hazama Corp. | Soil purification agent and method for purifying soil |
CA2700772A1 (en) * | 2007-09-26 | 2009-04-02 | Verutek Technologies, Inc. | System for soil and water remediation |
US8748331B2 (en) * | 2007-10-01 | 2014-06-10 | The United States Of America As Represented By The Secretary Of The Army | Biogenic template for enhanced sorption of contaminants |
EP3027562B1 (en) * | 2013-08-02 | 2018-04-18 | Regenesis Bioremediation Products | Colloidal agents for aquifer remediation |
US9776898B2 (en) * | 2014-02-14 | 2017-10-03 | Regenesis Bioremediation Products | Treatment of aquifer matrix back diffusion |
-
2017
- 2017-03-16 EP EP17767567.5A patent/EP3429745A4/en not_active Withdrawn
- 2017-03-16 WO PCT/US2017/022795 patent/WO2017161178A1/en active Application Filing
Also Published As
Publication number | Publication date |
---|---|
EP3429745A4 (en) | 2019-11-20 |
WO2017161178A1 (en) | 2017-09-21 |
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