CA2605824A1 - A process for the removal of hydrocarbons and heavy metals from contaminated solid and aqueous media - Google Patents
A process for the removal of hydrocarbons and heavy metals from contaminated solid and aqueous media Download PDFInfo
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- CA2605824A1 CA2605824A1 CA 2605824 CA2605824A CA2605824A1 CA 2605824 A1 CA2605824 A1 CA 2605824A1 CA 2605824 CA2605824 CA 2605824 CA 2605824 A CA2605824 A CA 2605824A CA 2605824 A1 CA2605824 A1 CA 2605824A1
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- heavy metals
- aqueous media
- removal
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Classifications
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- 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
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
-
- 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
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- 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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Soil Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
Abstract
The present invention relates to a process for the removal of petroleum hydrocarbons and heavy metals from contaminated soils and solids including oil sands and aqueous solutions including wastewater, oil lagoons and tailings, and a method for remediating said soils and solids and aqueous media which are contaminated with one or more organic chemicals where at least one water soluble dialkyldithiocarbamate is admixed with one non- ionic surfactant within an initial soil/aqueous slurry so as to obtain a product aqueous soil slurry which insoluble complexes may be physically separated from the slurry to leave behind a product having a metal contamination level lower than that of the initial contaminated soil. In the case of contaminated soils and wastewater streams, the presence of heavy metals and petroleum hydrocarbons is lower then the initial contamination present in the media.
Description
Process for the Recovery of Petroleum I=Iydrocarbons and heavy metals from Solid and Aqueous Media Background to the Invention The present invention relates to removal and recovery of heavy metals and petroleum hydrocarbons which mav be present in the contarninated soil, clays, and sand and aqueous media and a method for remediating the soil and aqueous media with one or more organic chernicals where at least one water soluble dialkldithiocarbamate is admixed with one water soluble dioctyl sodium sulfosuc:cinate so as recover the petroleum hydrocarbons and heavy metals contained in the contaminated soil and aqueous media.
The invention also relates to the field of petraleum hydrocarbons recovery from contaminated soils and aqueous media. 'vIore specifically the invention relates to improving a petroleum. hydrocarbon recovery system and method for not only rernoving hydrocarbons from contaminated soils and aqaeous media but from other media including subte:ranean oil deposits, sludge deposits on machines and 'oore hole equipment including pumping equipment and piping, in addition treating petroleum sludge deposits on the bottom of crude oil tanks.
Contaminated solids( soils) and aqueous media including groundwater contain high levels of toxic organic and inortanic compounds and therefore need to be treated. Soils containinb hazardous organic pollutants and/or heavy metals pose a serious environmental threat and over time if left untreated leads to huge groundwater contamination particularly if the toxic contaminates make their way into groundwater aquifers. These aquifers will carry these toxic contaminltes into the groundwater which in turn will eventually impact the ecological balance of the environment and will end up in the food chain.
In most cases, the contamination occurred as a result of ccrtain industrial activities which took place and as sucli were left in the ground by these industrial activities. Due to the potential environmental problems associated with not treating the contaminated soils and aqueous media are well documented and have led to novernment agencies establishing guidelines or limits in terms of the levels of bv which these conlpounds can remain in the soil. In Ontario, tlte Waste Management Branch of the Province has issued "Guidelines for the decommissioning and clean up sites in Ontario Typically, metal contaminates include metals which occur naturall,v in the environment such as arsenie as well as metals which are not normally present in the solids or aqueous media( i.e. man ntade metals) such lead, zinc, mereury, cadmium, copper, nickel, chromium, and cobalt, as well as other metals such as silver, ai-senic and vanadium. Soils which contain excessive amounts of these heavy metals are restricted in their land use must be treated so as to remove and encapsulate these excessive amounts of heavy metals.
The invention relates to the removal and recovery of these heavy metals. The removal of these metals involves contacting the soils with an aqueous solution containing one or more surfaetants which when admixed with the soil create slurry. The chemical reaction associated with the contacting of the surfactant with the contaminated soils creates separation between the heavy metals and the soil particles and the "washed soils are conveyed to separate staging area and the heavy metals are "drawn of7 and filtered out using a number of methods including but not limited to a centrifuge. The treated soil is usually land6lled or used as subsoil for other industrial uses.
Description of Prior Art In US. PAT# 5,772,776 a method is proposed that a soluble dialkyldithiocarbomate can effectively recover Pb and other heavy metals by admixing at least one water soluble dialkyldithiocarbomate with initial soil slurry so as to obtain product aqueous soil slurry comprising one or more water insoluble metal-dialkyklithio-carbamate complexes whiehcan be physically separated from the soil slurry. This invention intends to incorporate a similar compound in its polishing phase as described later in this invention.
US.PAT 6797195 discloses a process for recovering metals from waste streams for separating the tecovering precious metals from industrial waste streams, adjusting the pH of an industri.al waste stream and containing the precious and non-precious metals to be recovered; adding a metal coinplexing agent to promote the aggregation of the said metal ions; adding a flocculating agent to the increase the said metal ions and form a solution thereof. Dewatering said solution to form a supernatant, dewatering and drying said sludge to form an ionic metal concentrate to selectively remove and recover the desired metal therefore.
US. PAT #5,882,429 discloses a process for the fixation of metals and removal of hydrocarbons from contaminated soils whereby liquid phase agglomeration techniques, in combination \vith solvent extraction were used to remediate organic contarninated soils. The combined process aPows concurrent removal of the organics and fixation of the heavy metals. The removal of hydrocarbons is well understood in the art, however the process fails to address the problem of separating the hydrocarbons from the liquid while at the same removing the heavy metals from the contaminated soils. Fixation of the heavy metals may not meet the guidelines in the Province of Ontario as the metals still remain in the soil albeit in an encapsulated state.
A more effective method would be to completely remove the heavy metals from the contaminated media as such would eliminate any future leaching that may occur in the soils.
Further, fine te:ctured fines such as clays and sledges containing fines, separation of the hydrocarbons and heavy metals has proven to be a difficult technical problem particularly in the case of mature fine tailings created by the {Clark hot water extraction process" used in the extraction of bitumen from the oil sands in Alberta. In addition, processes for removing metals and hydrocarbons from contaminated soils and aqueous media have: long been associated with the high costs and storage problems. Long term liability of the waste management still exists in the environment. Although many technologies exist including ion exchange or,.-lectrolyte recovery of metals from waste streams, the problem is its is difficult to apply the technology in continuous process method such as water filtration systems. None of the known prior art technologies separate and recover both hydrocarbons and a variety of heavy metals in one eontinuous "washing"
process.
US.PAT #5264135 discloses a process for the stabilization of inetals in wastewater sluclge whereby certain metal complexing agents are added to the sludge and the coniplexing agents are :>elected from a group consisting of ditnethyldithiocarabamate, diethylcarbamate, trithiocarbamate. The wastewater is treated in a clarifier with either caustic (NaOH) or lime (Ca (OH)2).
Once mixed in the clarifier, the heavy metals will precipitate out of the solution and drop to the bottom of the clarifier. The precipitate is then periodically drawn off from the bottom to form sludge. This sludge is then transporl:ed to a dewaterine press and at this stage the above compounds are added in sufficient amounts as to stabilize the heavy rnetals. The removal of the heavy metals from the sludge is difficult and requires a very sophisticated complexing agent.
The dewatered sludge is then tested using the requirements of the TCLP test.
The maxirr um acceptable levels for certain metals, as defined in the Federal Register (Toxicity Characteristic Fina:l Rule, March, 29 1990) are illustrated in the following table TCLP Maximum Limits for Organics Parts per Million m) Arsenic 5 Barium 100 Cadmium I
Chromium 5 Lead 5 Vlercu 0.2 Selenium I
Silver ~
The amount of complexing agent according to this invention which is added to the sludge is in the range of 5 to 50,000 ppm. There are number of problems with this process which in part make it economically unfeasible in terms of being cost- effective and if more stringent TCLP tests are introduced in the future, the tests in fact, may be able to leach out the metals thereby impacting the feasibility of using this invention in the fie1d.
In addition, the process relies on a settling process which is undesirable for large quantities of solid hazardous or toxic wastes and in most cases cannot be regenerated.
U.S. Pat. No. 5,008,017 (Kiel, et al.) discloses a process for recovering metals form a waste stream where the dewatered sludge is heated to 900 F to recover silver. However this would be unfeasible in a process type removable method as the energy costs would exceed the revenue stream that could be generated from such a process.
None of the above are technologies actually separates the hydrocarbons and the heavy metals from the waste stream without additional separation steps. It is therefore a need for a method to efficiently remove and recover heavy -metais- and-petroleum hydrocarbons from contamiuated solid and aqr.eous waste streams in one completely integrated process system.
U.S. Pat. No_ 6,099,206 (Pennell) discloses a process for remediating contaminated aqu: fers by modifying the density of the non-aqueous phase liquids (NAPL) including petroleum-bE.sed products such as gasoline. The process also addresses the problem with remediating denser non-aqueous phase liquids (DNAI'L's). Pennell's approach to recovering or removing hydrocarbons is to "flush a surfactant-based solution down into the subsurface containing the above contaminates through an injection well.
The process modifies the density of the DNAPL by flushing the aquifer with a suitable alcohol; and displacing the NAPL by flushing the aquifer with a suitable surfactant. The surfactant <<sed to lower the interfacial tension between the DNAPL's and the solid ( subsurface soil) was (4% Aerosol MA/OT 4%
Aersol AYIOT) The combination of 4% Aerosol MA/OT ( sodium diamvl sulfosuccin,tte) and 4%
Aerosol AY/OT ( sodium dioctylsulfosuccinate ) worked the most efficientlv in terms of removing the DNAPL.
The present invention is an improvement over this invention and the prior art with resQect to the removal of hydrocarbons in two instances; firstly, it utilizes only a 0,5 %
surfactant to water process solution ( 99.5% water to 0.5% surfactant) to displace the hydrocarbons making it extremely cost-effective over the prior invention, and secondly, injecting process solutions into subsurface media is difficult to monitor in terms of its effectiveness. In other words, the volunie of DNAPL`s actually that were displaced during the process is never fully calculated.
The improvements in the method to extract petroleum-based contaminates found in the current invention, as shown in Figure 1.0 , is firstly, the process can be monitored and tailored at every stage to ensure complete removal of the contaminates. The primary reason for this is a improvernent over other methods, is the fact that the process is carried out above ground in a closed-loop mecl:anical separation system. The known art as described in the above invention is cost-prohibitive. The cost of chenuca]s to remove contaminates from solids and aqueous media is an extremely important factor in determining what recovery method is employed in the field.
Detailed Description of the Invention The present invention relates to the removal of petroleum hydrocarbons and heavy meta.ls from contaminated soil, and aqueous solutions. The term "soil" is used in a generic sense to refer to the various materials which can be found in the earth and which can be subject to contamination.
Common contaminates include, crude oils, that is mineral oils, petroleum, solvents or acid treated mineral oils, and oils derived from coal such as cresol and heavy metals such lead, mercury, titanium.zinc,lead,arsenie etc . Also included are refined hydrocarbons such as gasoline's, diesel, kerosene's: and commercial oil-containing compositions such as motor oils, lubricants aad hydraulic fluids.
An important material contained in the invention is the unique use of "Gemini surfactarts. Additional surfactants, preferably in the amounts within the ranges 0.01- 15% can be used and can be characterized as non-ionic, anionic, cationic, or amphoeric. Non-ionic surfactants include nonylpenol, sorbitan monooleate, glycerol monooleate poly (ethylene oxide). non ionic surfactants used in the invention may include the following, sodium exylene suflonate, dioctyl sodi.um sulfosuccinate, di-2-ethylhexyl sodium sulfosuccinate ( Manufacturers Chemicals). These surfactants influence the properties of surfaces and interfaces such as the interfaces between hydrocarbons and water. In scientific terms, th~,.se surfactants are considered shoet-chained fatty acids and form monolayers at the interfaces and show surface activity.
In other words, these molecules are capable of associating to form micelles.
The uniqueness of the surfactants employed by this invention is the fact that these molecules have two hydrophilic (chiefly ionic) groups and two tails and are linked by a unique spacer group. Sodium dioetylsull'osuccinate is commercially available from chemical manufactures , the sodium dioctylsulfosuccinate used in this invention is supplied by Manufacturers Chemical LLP, Cleveland Tennessee under th,s Trade Name DOSS.
Another embodiment of the invention relates to the field of petroleum hydrocarbon production recovery and handling and a method of fluidizing, separating, and recovering highly viscous residual petroleum product such as sludge, process equipment and or inorganic solids and may relate to subterranean oil deposits whereby the invention may make the oil flow more easily thereby improving the method of extracting the said oil from the below surface reservoir. More particular as in the case of sludge in the aforementioned paragraph or what is referred as "slop oil", the invention may extract ctude oil commonly included as a percentage of the suspended solids contaminates particularly such as inorganic sand and clay particles contained in certain waste streams and solids which are contained in the residual media in the bottom of oil storage tanks, bulk crude oil tankers and but not limited the aforementioned and may include media such as oil sand tailings referred in the industry as Mature Fine Tailings. In addition to the foregoing, the invention may remove certain waxes which are contained in the crude and which form deposits, such deposits consist of linear paraffin hydrocarbons and naphtenic hydrocarbons, and such hydrocarbons can exist in either liquid state or solid state. Solid state paraffins caused flow rate reduction in pipelines and oil pumping operations.
Currently toxic solvents are used in some cases to remove the above waxes.
In the current invention, the final removal of heavy metals from waste streams of the he.avy metal recovery operation will be flowed through a fixed bed tower containing a chelating resin manufactured by AICO Chemical, Chattanooga Tennessee and more specifically this resin which will capture zinc, mercury, selenium, arsenic, copper, lead, and silver from mature fine tailings including but not limited to mine tailing, offshore drilling mud tailings. Fig 1.0 illustrates the process whereby the extracted heavy metals will be solidified for use in other industrial processes.
Description of the Drawing Figure Fig.1.0 is schematic diagram of surfactant- enhanced petroleum hydrocarbon and heavy metals recovery and extraction system apparatus. The apparatus consists generally of a sample of contaminated soi11. A
conveyor to transport the soil to screener 2. At screener/crusher where the soil is crushedl to appropriate size 3. A screw conveyor containing a power shaft where the soil is transported to the pugmill/mixer 4.
The process solution containing the surfactants may be injected at this stage and is an option to be cons.idered for those who will practice the art. A pugmill/mixer where the soil mixed with the process solution 5. A reagent tank which pumps the process solution to the pugmill/mixer 6. A screw conveyor which transport the mixed slurry to centrifuge 7. A centrifuge which separates the solids from the liquids ( optional ) S. The solids are drawn off the bottom and transported to a clean soil staginl; area 9. The remaining liquids containing the contaminates ( i.e. petroleum hydrocarbons and heavy metals are transported to liquid/clarifier 10. The liquids are separated whereby more process solution is injected. At this stage the petroleum hydrocarbons are decantered off into a holding tank. 11. The remaining wastewater stream is pumped through fluidired bed containing the aforementioned resin( AICO Chemicals) 12. The metals are solidified and dried in closed vessel 19. A flocculant maybe added during the clarification phase to settle any clays or fines still remaining in the wa.stewater 24. The flocculant is pumped to the liquid separator 21.After the heavy metals are removed the wastewater is pumped into a holding tank 17. The recvcled water is then pumped back into the pugmilUmixer. The recycled water contains 90-97% of the surfactants useci in the extraction of the petroleum hydrocarbons 16.
Further Notes The above schematic can be fabricated as one completely integrated system and is intended to be a mobile process plant.
Examples In a preferred working embodiment of the invention, sodium dioctylsulfosuccinate is provided with 99 grams water at a concentration of from about 0.05% to about 10.0% by volume, and preferably about 1%
to achieve final solution. The 100 grams of process solution was then added to 200 granis of contaminated soil. The contents were agitated at a high shear for 2 minutes.
The solutioil was allowed to stand for 5 minutes thereby creating two phases. The upper phase contained the solubilized heavy metals and the lower phase contained solids and other metals. The soil was solubilized heavy metals and the lower phase contained solids and other metals. The soil was spiked with a variety of heavy metals as illustrated in Table 2 The upper stage (i.e. the wastewater stream) was treated with additional complexing agents.
Table 2.0 Represents soil being spike with heavy metals Base Dirt # 2 Solid Lab Report 199517 Result MDL t'tqetJi D Th MeraLs Scaa Alutninum (Al) 9870 2000 6010 6 Antimuny (Sb) < 1.5 1.5 6010 6 Arsenic (As) <2 2 6010 6 Bariurn (Ba) 103 0.1 6010 6 Berypium (Be) 1.59 0.1 6010 6 Cadmium (Ctl) 2.41 0.15 6010 6 Calcium (Ca) 199300 500 6010 6 Chromium (Cr) 2.96 0.25 6010 6 Cobalt (Co) 6.78 1 6010 6 Copper (Cu) 32.6 0.2 6010 6 Iron (Fe) 29340 250 6010 6 Lead (Pb) < 1.5 1.5 0010 6 Magneslum (Mg) 20840 1000 5010 6 Manganese (Mn) 607 100 6010 6 Niclte: (Ni) 3_17 0.5 6010 6 Selenium (Se) <2.5 2.5 6010 6 Silver (Ag) <0.5 0.5 6010 6 Zinc (Zn) 227 0.1 6010 6 Mercury (Hg) < 0.1 0.1 7471 The next table illustrates the remaining heavv metals in the soil after it was treated with the process solution as described above Table 3.0 Illustrating Treated Soils and Remaining Heavy Metals Base Solid Lab 199525 Result MDL MetltQa' Dcue Metals Scan Alumirrtrm (Al) 4238 mc}mg 2000 6010 61121r07 Antlmony (Sb) < 1.5 mg/Kg 1.5 6010 6'21/07 Arsenic (As) <2 mg/Kg 2 6010 6,21i07 Barium (Ba) 68.3 mg/Kg 0.1 6010 6,12 1107 Beryllirart (Be) 1.1 mg/Kg 0.1 6010 6121:07 Cadmium (Ccg 1.28 mg/Kg 0.15 60'0 W21.107 Calcium (Ca) 91100 mglKg 500 6010 6!21707 Chromium (Cr) 2.03 mg/Kg 0.25 6010 6/21:07 Cobalt(Co) 4.49 mg/Kg 1 6010 6l21l07 Copper (Cu1 21.9 mgJKg 0.2 6010 642 V07 tron 16400 mg/Kg 250 6010 6/21107 Lead < 1.5 mg/Kg 1.5 6010 6121/07 Magnesium (Mg) < 1 mglKg 1 6010 6/21/07 Manganese (Mn) 256.3 mgrKg 100 6010 5/21/07 Nidcel (Ni) 2.1 mglKg 0.5 6010 6121/07 Selenium (Se) <2.5 mgACg 2.5 6010 612907 Silver (Ag) <0.5 mg'Kg 0.5 6010 6121/07 Zinc <0.1 rng'Kg 0.1 6010 6i21107 Mercury (Hg) < 0,1 mg(Kg 0.1 7471 Table 4.0 Represerlts the Treated llecante.red Wast.evc'ater ( i.e. 1%
Diso(liumsulfosuccinate (DOSS)) Ec:oSzfe Envit'onmenral Decant Water Mansurf Liauid Lcrb Reporr 199523 Result IVIDL Method Dp:e TErne Anal hletals 5can Aluminum (Al) 2.3.7 ^~gfKg 2 6010 6/21107 13:25 IFH
Antimany(&b) 7.56 mglKg 1.5 6010 612110"7 13: :5 IF~i Arsenic (AS) <2 mg!Kg 2 6010 6/21-711 13:25 IFH
Barium (Ba) 2.: mgrK.g 0.1 6310 6!2110",' 1.125 1FH
Beryllium (Be) <0.1 mgrKg 0.1 6010 W216i, 13:25 FH
Cadmium (Cd) 0.363 nig(Kg 0.15 6010 GP2 1!07 1325 FH
Calcium (Ca) 1106 mg!Kg S00 601ci 6121!07 14:47 tFH
Chromlum (Cr) <0.25 mg'Kg 0.25 6010 6J2!10? 13:25 FH
Coball (Co) <1 mg/Kg 1 6010 W21r07 13:25 IFH
Copper iCu) 0.216 mgrKg 0.2 6010 6/21/Q7 13:--, ti F'ri Iron (Foi 65 1 myVKg 0.25 9)10 (il21h)7 -13:25 IFH
Lead (P5) < 1.5 rng'Kg 1.5 6010 621hTI 13.35 1FH
Magnesium (Mg) 60.7 mglKg 1 6010 6/?Ih37 13:25 IFH
tvlanganese (Mn) 7.8 mgXg 0.1 6010 6211-J? 13:25 'IFH
Nickel (Ni) <0.5 mghCg 0.5 601C 621I07 13:25 IFH
Seienium (Se) Q5 mg/Kg 2,5 601C6I31!D7 13:25 !FH
Silver (Ag) <0.5 mg/Kg 0.5 6010 6G'.V07 13:25 FH
Zinc (Zn) 53 mglKg 0.1 6010 6/21U07 13:25 FH
m;,rKg Metal removat H'as accornplished in 2 minutes whercby the contents were agitated for ' 2 minutes at high shear and the water was decantered off and collected in a 250171I gIass measuring flask. The extraction and recovery of the heavy metals procedure was accotnplished in two-step process_ Further, more efficient extraction procedures are continued to be investigated. The common practice in the art of extraction technology is to employ a centrifuge. The heavy metals remaining in the " treated wastewater stream can be polished using a resin filtration system.
Heavy metal leaching potential af the treated solids was determined by the U.S. -EPA toxicity test method 1320A and Toxicity Characteristics Leaching Process Procedure i47ethod 1311.
Long term stability was tested using the agency's multiple extraction procedure tnethod 1320
The invention also relates to the field of petraleum hydrocarbons recovery from contaminated soils and aqueous media. 'vIore specifically the invention relates to improving a petroleum. hydrocarbon recovery system and method for not only rernoving hydrocarbons from contaminated soils and aqaeous media but from other media including subte:ranean oil deposits, sludge deposits on machines and 'oore hole equipment including pumping equipment and piping, in addition treating petroleum sludge deposits on the bottom of crude oil tanks.
Contaminated solids( soils) and aqueous media including groundwater contain high levels of toxic organic and inortanic compounds and therefore need to be treated. Soils containinb hazardous organic pollutants and/or heavy metals pose a serious environmental threat and over time if left untreated leads to huge groundwater contamination particularly if the toxic contaminates make their way into groundwater aquifers. These aquifers will carry these toxic contaminltes into the groundwater which in turn will eventually impact the ecological balance of the environment and will end up in the food chain.
In most cases, the contamination occurred as a result of ccrtain industrial activities which took place and as sucli were left in the ground by these industrial activities. Due to the potential environmental problems associated with not treating the contaminated soils and aqueous media are well documented and have led to novernment agencies establishing guidelines or limits in terms of the levels of bv which these conlpounds can remain in the soil. In Ontario, tlte Waste Management Branch of the Province has issued "Guidelines for the decommissioning and clean up sites in Ontario Typically, metal contaminates include metals which occur naturall,v in the environment such as arsenie as well as metals which are not normally present in the solids or aqueous media( i.e. man ntade metals) such lead, zinc, mereury, cadmium, copper, nickel, chromium, and cobalt, as well as other metals such as silver, ai-senic and vanadium. Soils which contain excessive amounts of these heavy metals are restricted in their land use must be treated so as to remove and encapsulate these excessive amounts of heavy metals.
The invention relates to the removal and recovery of these heavy metals. The removal of these metals involves contacting the soils with an aqueous solution containing one or more surfaetants which when admixed with the soil create slurry. The chemical reaction associated with the contacting of the surfactant with the contaminated soils creates separation between the heavy metals and the soil particles and the "washed soils are conveyed to separate staging area and the heavy metals are "drawn of7 and filtered out using a number of methods including but not limited to a centrifuge. The treated soil is usually land6lled or used as subsoil for other industrial uses.
Description of Prior Art In US. PAT# 5,772,776 a method is proposed that a soluble dialkyldithiocarbomate can effectively recover Pb and other heavy metals by admixing at least one water soluble dialkyldithiocarbomate with initial soil slurry so as to obtain product aqueous soil slurry comprising one or more water insoluble metal-dialkyklithio-carbamate complexes whiehcan be physically separated from the soil slurry. This invention intends to incorporate a similar compound in its polishing phase as described later in this invention.
US.PAT 6797195 discloses a process for recovering metals from waste streams for separating the tecovering precious metals from industrial waste streams, adjusting the pH of an industri.al waste stream and containing the precious and non-precious metals to be recovered; adding a metal coinplexing agent to promote the aggregation of the said metal ions; adding a flocculating agent to the increase the said metal ions and form a solution thereof. Dewatering said solution to form a supernatant, dewatering and drying said sludge to form an ionic metal concentrate to selectively remove and recover the desired metal therefore.
US. PAT #5,882,429 discloses a process for the fixation of metals and removal of hydrocarbons from contaminated soils whereby liquid phase agglomeration techniques, in combination \vith solvent extraction were used to remediate organic contarninated soils. The combined process aPows concurrent removal of the organics and fixation of the heavy metals. The removal of hydrocarbons is well understood in the art, however the process fails to address the problem of separating the hydrocarbons from the liquid while at the same removing the heavy metals from the contaminated soils. Fixation of the heavy metals may not meet the guidelines in the Province of Ontario as the metals still remain in the soil albeit in an encapsulated state.
A more effective method would be to completely remove the heavy metals from the contaminated media as such would eliminate any future leaching that may occur in the soils.
Further, fine te:ctured fines such as clays and sledges containing fines, separation of the hydrocarbons and heavy metals has proven to be a difficult technical problem particularly in the case of mature fine tailings created by the {Clark hot water extraction process" used in the extraction of bitumen from the oil sands in Alberta. In addition, processes for removing metals and hydrocarbons from contaminated soils and aqueous media have: long been associated with the high costs and storage problems. Long term liability of the waste management still exists in the environment. Although many technologies exist including ion exchange or,.-lectrolyte recovery of metals from waste streams, the problem is its is difficult to apply the technology in continuous process method such as water filtration systems. None of the known prior art technologies separate and recover both hydrocarbons and a variety of heavy metals in one eontinuous "washing"
process.
US.PAT #5264135 discloses a process for the stabilization of inetals in wastewater sluclge whereby certain metal complexing agents are added to the sludge and the coniplexing agents are :>elected from a group consisting of ditnethyldithiocarabamate, diethylcarbamate, trithiocarbamate. The wastewater is treated in a clarifier with either caustic (NaOH) or lime (Ca (OH)2).
Once mixed in the clarifier, the heavy metals will precipitate out of the solution and drop to the bottom of the clarifier. The precipitate is then periodically drawn off from the bottom to form sludge. This sludge is then transporl:ed to a dewaterine press and at this stage the above compounds are added in sufficient amounts as to stabilize the heavy rnetals. The removal of the heavy metals from the sludge is difficult and requires a very sophisticated complexing agent.
The dewatered sludge is then tested using the requirements of the TCLP test.
The maxirr um acceptable levels for certain metals, as defined in the Federal Register (Toxicity Characteristic Fina:l Rule, March, 29 1990) are illustrated in the following table TCLP Maximum Limits for Organics Parts per Million m) Arsenic 5 Barium 100 Cadmium I
Chromium 5 Lead 5 Vlercu 0.2 Selenium I
Silver ~
The amount of complexing agent according to this invention which is added to the sludge is in the range of 5 to 50,000 ppm. There are number of problems with this process which in part make it economically unfeasible in terms of being cost- effective and if more stringent TCLP tests are introduced in the future, the tests in fact, may be able to leach out the metals thereby impacting the feasibility of using this invention in the fie1d.
In addition, the process relies on a settling process which is undesirable for large quantities of solid hazardous or toxic wastes and in most cases cannot be regenerated.
U.S. Pat. No. 5,008,017 (Kiel, et al.) discloses a process for recovering metals form a waste stream where the dewatered sludge is heated to 900 F to recover silver. However this would be unfeasible in a process type removable method as the energy costs would exceed the revenue stream that could be generated from such a process.
None of the above are technologies actually separates the hydrocarbons and the heavy metals from the waste stream without additional separation steps. It is therefore a need for a method to efficiently remove and recover heavy -metais- and-petroleum hydrocarbons from contamiuated solid and aqr.eous waste streams in one completely integrated process system.
U.S. Pat. No_ 6,099,206 (Pennell) discloses a process for remediating contaminated aqu: fers by modifying the density of the non-aqueous phase liquids (NAPL) including petroleum-bE.sed products such as gasoline. The process also addresses the problem with remediating denser non-aqueous phase liquids (DNAI'L's). Pennell's approach to recovering or removing hydrocarbons is to "flush a surfactant-based solution down into the subsurface containing the above contaminates through an injection well.
The process modifies the density of the DNAPL by flushing the aquifer with a suitable alcohol; and displacing the NAPL by flushing the aquifer with a suitable surfactant. The surfactant <<sed to lower the interfacial tension between the DNAPL's and the solid ( subsurface soil) was (4% Aerosol MA/OT 4%
Aersol AYIOT) The combination of 4% Aerosol MA/OT ( sodium diamvl sulfosuccin,tte) and 4%
Aerosol AY/OT ( sodium dioctylsulfosuccinate ) worked the most efficientlv in terms of removing the DNAPL.
The present invention is an improvement over this invention and the prior art with resQect to the removal of hydrocarbons in two instances; firstly, it utilizes only a 0,5 %
surfactant to water process solution ( 99.5% water to 0.5% surfactant) to displace the hydrocarbons making it extremely cost-effective over the prior invention, and secondly, injecting process solutions into subsurface media is difficult to monitor in terms of its effectiveness. In other words, the volunie of DNAPL`s actually that were displaced during the process is never fully calculated.
The improvements in the method to extract petroleum-based contaminates found in the current invention, as shown in Figure 1.0 , is firstly, the process can be monitored and tailored at every stage to ensure complete removal of the contaminates. The primary reason for this is a improvernent over other methods, is the fact that the process is carried out above ground in a closed-loop mecl:anical separation system. The known art as described in the above invention is cost-prohibitive. The cost of chenuca]s to remove contaminates from solids and aqueous media is an extremely important factor in determining what recovery method is employed in the field.
Detailed Description of the Invention The present invention relates to the removal of petroleum hydrocarbons and heavy meta.ls from contaminated soil, and aqueous solutions. The term "soil" is used in a generic sense to refer to the various materials which can be found in the earth and which can be subject to contamination.
Common contaminates include, crude oils, that is mineral oils, petroleum, solvents or acid treated mineral oils, and oils derived from coal such as cresol and heavy metals such lead, mercury, titanium.zinc,lead,arsenie etc . Also included are refined hydrocarbons such as gasoline's, diesel, kerosene's: and commercial oil-containing compositions such as motor oils, lubricants aad hydraulic fluids.
An important material contained in the invention is the unique use of "Gemini surfactarts. Additional surfactants, preferably in the amounts within the ranges 0.01- 15% can be used and can be characterized as non-ionic, anionic, cationic, or amphoeric. Non-ionic surfactants include nonylpenol, sorbitan monooleate, glycerol monooleate poly (ethylene oxide). non ionic surfactants used in the invention may include the following, sodium exylene suflonate, dioctyl sodi.um sulfosuccinate, di-2-ethylhexyl sodium sulfosuccinate ( Manufacturers Chemicals). These surfactants influence the properties of surfaces and interfaces such as the interfaces between hydrocarbons and water. In scientific terms, th~,.se surfactants are considered shoet-chained fatty acids and form monolayers at the interfaces and show surface activity.
In other words, these molecules are capable of associating to form micelles.
The uniqueness of the surfactants employed by this invention is the fact that these molecules have two hydrophilic (chiefly ionic) groups and two tails and are linked by a unique spacer group. Sodium dioetylsull'osuccinate is commercially available from chemical manufactures , the sodium dioctylsulfosuccinate used in this invention is supplied by Manufacturers Chemical LLP, Cleveland Tennessee under th,s Trade Name DOSS.
Another embodiment of the invention relates to the field of petroleum hydrocarbon production recovery and handling and a method of fluidizing, separating, and recovering highly viscous residual petroleum product such as sludge, process equipment and or inorganic solids and may relate to subterranean oil deposits whereby the invention may make the oil flow more easily thereby improving the method of extracting the said oil from the below surface reservoir. More particular as in the case of sludge in the aforementioned paragraph or what is referred as "slop oil", the invention may extract ctude oil commonly included as a percentage of the suspended solids contaminates particularly such as inorganic sand and clay particles contained in certain waste streams and solids which are contained in the residual media in the bottom of oil storage tanks, bulk crude oil tankers and but not limited the aforementioned and may include media such as oil sand tailings referred in the industry as Mature Fine Tailings. In addition to the foregoing, the invention may remove certain waxes which are contained in the crude and which form deposits, such deposits consist of linear paraffin hydrocarbons and naphtenic hydrocarbons, and such hydrocarbons can exist in either liquid state or solid state. Solid state paraffins caused flow rate reduction in pipelines and oil pumping operations.
Currently toxic solvents are used in some cases to remove the above waxes.
In the current invention, the final removal of heavy metals from waste streams of the he.avy metal recovery operation will be flowed through a fixed bed tower containing a chelating resin manufactured by AICO Chemical, Chattanooga Tennessee and more specifically this resin which will capture zinc, mercury, selenium, arsenic, copper, lead, and silver from mature fine tailings including but not limited to mine tailing, offshore drilling mud tailings. Fig 1.0 illustrates the process whereby the extracted heavy metals will be solidified for use in other industrial processes.
Description of the Drawing Figure Fig.1.0 is schematic diagram of surfactant- enhanced petroleum hydrocarbon and heavy metals recovery and extraction system apparatus. The apparatus consists generally of a sample of contaminated soi11. A
conveyor to transport the soil to screener 2. At screener/crusher where the soil is crushedl to appropriate size 3. A screw conveyor containing a power shaft where the soil is transported to the pugmill/mixer 4.
The process solution containing the surfactants may be injected at this stage and is an option to be cons.idered for those who will practice the art. A pugmill/mixer where the soil mixed with the process solution 5. A reagent tank which pumps the process solution to the pugmill/mixer 6. A screw conveyor which transport the mixed slurry to centrifuge 7. A centrifuge which separates the solids from the liquids ( optional ) S. The solids are drawn off the bottom and transported to a clean soil staginl; area 9. The remaining liquids containing the contaminates ( i.e. petroleum hydrocarbons and heavy metals are transported to liquid/clarifier 10. The liquids are separated whereby more process solution is injected. At this stage the petroleum hydrocarbons are decantered off into a holding tank. 11. The remaining wastewater stream is pumped through fluidired bed containing the aforementioned resin( AICO Chemicals) 12. The metals are solidified and dried in closed vessel 19. A flocculant maybe added during the clarification phase to settle any clays or fines still remaining in the wa.stewater 24. The flocculant is pumped to the liquid separator 21.After the heavy metals are removed the wastewater is pumped into a holding tank 17. The recvcled water is then pumped back into the pugmilUmixer. The recycled water contains 90-97% of the surfactants useci in the extraction of the petroleum hydrocarbons 16.
Further Notes The above schematic can be fabricated as one completely integrated system and is intended to be a mobile process plant.
Examples In a preferred working embodiment of the invention, sodium dioctylsulfosuccinate is provided with 99 grams water at a concentration of from about 0.05% to about 10.0% by volume, and preferably about 1%
to achieve final solution. The 100 grams of process solution was then added to 200 granis of contaminated soil. The contents were agitated at a high shear for 2 minutes.
The solutioil was allowed to stand for 5 minutes thereby creating two phases. The upper phase contained the solubilized heavy metals and the lower phase contained solids and other metals. The soil was solubilized heavy metals and the lower phase contained solids and other metals. The soil was spiked with a variety of heavy metals as illustrated in Table 2 The upper stage (i.e. the wastewater stream) was treated with additional complexing agents.
Table 2.0 Represents soil being spike with heavy metals Base Dirt # 2 Solid Lab Report 199517 Result MDL t'tqetJi D Th MeraLs Scaa Alutninum (Al) 9870 2000 6010 6 Antimuny (Sb) < 1.5 1.5 6010 6 Arsenic (As) <2 2 6010 6 Bariurn (Ba) 103 0.1 6010 6 Berypium (Be) 1.59 0.1 6010 6 Cadmium (Ctl) 2.41 0.15 6010 6 Calcium (Ca) 199300 500 6010 6 Chromium (Cr) 2.96 0.25 6010 6 Cobalt (Co) 6.78 1 6010 6 Copper (Cu) 32.6 0.2 6010 6 Iron (Fe) 29340 250 6010 6 Lead (Pb) < 1.5 1.5 0010 6 Magneslum (Mg) 20840 1000 5010 6 Manganese (Mn) 607 100 6010 6 Niclte: (Ni) 3_17 0.5 6010 6 Selenium (Se) <2.5 2.5 6010 6 Silver (Ag) <0.5 0.5 6010 6 Zinc (Zn) 227 0.1 6010 6 Mercury (Hg) < 0.1 0.1 7471 The next table illustrates the remaining heavv metals in the soil after it was treated with the process solution as described above Table 3.0 Illustrating Treated Soils and Remaining Heavy Metals Base Solid Lab 199525 Result MDL MetltQa' Dcue Metals Scan Alumirrtrm (Al) 4238 mc}mg 2000 6010 61121r07 Antlmony (Sb) < 1.5 mg/Kg 1.5 6010 6'21/07 Arsenic (As) <2 mg/Kg 2 6010 6,21i07 Barium (Ba) 68.3 mg/Kg 0.1 6010 6,12 1107 Beryllirart (Be) 1.1 mg/Kg 0.1 6010 6121:07 Cadmium (Ccg 1.28 mg/Kg 0.15 60'0 W21.107 Calcium (Ca) 91100 mglKg 500 6010 6!21707 Chromium (Cr) 2.03 mg/Kg 0.25 6010 6/21:07 Cobalt(Co) 4.49 mg/Kg 1 6010 6l21l07 Copper (Cu1 21.9 mgJKg 0.2 6010 642 V07 tron 16400 mg/Kg 250 6010 6/21107 Lead < 1.5 mg/Kg 1.5 6010 6121/07 Magnesium (Mg) < 1 mglKg 1 6010 6/21/07 Manganese (Mn) 256.3 mgrKg 100 6010 5/21/07 Nidcel (Ni) 2.1 mglKg 0.5 6010 6121/07 Selenium (Se) <2.5 mgACg 2.5 6010 612907 Silver (Ag) <0.5 mg'Kg 0.5 6010 6121/07 Zinc <0.1 rng'Kg 0.1 6010 6i21107 Mercury (Hg) < 0,1 mg(Kg 0.1 7471 Table 4.0 Represerlts the Treated llecante.red Wast.evc'ater ( i.e. 1%
Diso(liumsulfosuccinate (DOSS)) Ec:oSzfe Envit'onmenral Decant Water Mansurf Liauid Lcrb Reporr 199523 Result IVIDL Method Dp:e TErne Anal hletals 5can Aluminum (Al) 2.3.7 ^~gfKg 2 6010 6/21107 13:25 IFH
Antimany(&b) 7.56 mglKg 1.5 6010 612110"7 13: :5 IF~i Arsenic (AS) <2 mg!Kg 2 6010 6/21-711 13:25 IFH
Barium (Ba) 2.: mgrK.g 0.1 6310 6!2110",' 1.125 1FH
Beryllium (Be) <0.1 mgrKg 0.1 6010 W216i, 13:25 FH
Cadmium (Cd) 0.363 nig(Kg 0.15 6010 GP2 1!07 1325 FH
Calcium (Ca) 1106 mg!Kg S00 601ci 6121!07 14:47 tFH
Chromlum (Cr) <0.25 mg'Kg 0.25 6010 6J2!10? 13:25 FH
Coball (Co) <1 mg/Kg 1 6010 W21r07 13:25 IFH
Copper iCu) 0.216 mgrKg 0.2 6010 6/21/Q7 13:--, ti F'ri Iron (Foi 65 1 myVKg 0.25 9)10 (il21h)7 -13:25 IFH
Lead (P5) < 1.5 rng'Kg 1.5 6010 621hTI 13.35 1FH
Magnesium (Mg) 60.7 mglKg 1 6010 6/?Ih37 13:25 IFH
tvlanganese (Mn) 7.8 mgXg 0.1 6010 6211-J? 13:25 'IFH
Nickel (Ni) <0.5 mghCg 0.5 601C 621I07 13:25 IFH
Seienium (Se) Q5 mg/Kg 2,5 601C6I31!D7 13:25 !FH
Silver (Ag) <0.5 mg/Kg 0.5 6010 6G'.V07 13:25 FH
Zinc (Zn) 53 mglKg 0.1 6010 6/21U07 13:25 FH
m;,rKg Metal removat H'as accornplished in 2 minutes whercby the contents were agitated for ' 2 minutes at high shear and the water was decantered off and collected in a 250171I gIass measuring flask. The extraction and recovery of the heavy metals procedure was accotnplished in two-step process_ Further, more efficient extraction procedures are continued to be investigated. The common practice in the art of extraction technology is to employ a centrifuge. The heavy metals remaining in the " treated wastewater stream can be polished using a resin filtration system.
Heavy metal leaching potential af the treated solids was determined by the U.S. -EPA toxicity test method 1320A and Toxicity Characteristics Leaching Process Procedure i47ethod 1311.
Long term stability was tested using the agency's multiple extraction procedure tnethod 1320
Claims (14)
1. A
process for the removal of contaminates namely petroleum hydrocarbons and heavy metals comprising the steps of: introducing a suitable amount of at least one surfactant solution within the surfactant solution contains at least a mixture of one anionic surfactant and at least one polymer from solid and aqueous media.
process for the removal of contaminates namely petroleum hydrocarbons and heavy metals comprising the steps of: introducing a suitable amount of at least one surfactant solution within the surfactant solution contains at least a mixture of one anionic surfactant and at least one polymer from solid and aqueous media.
2. The preferred surfactant used in this invention is sodium di-2-ethylhexyl sulfosuccinate. The preferred polymer but not limited to is sodium trithiocarbanate and may include one or more products containing water soluble sodium dithiocarbamate-related compounds.
3. The contaminates removal process of claim 1 contains a dispersion fluid which contains dioctyl sodium sulfosuccinate at a concentration within the range of 0.05% by volume to about 101% by volume
4. The contaminates removal process of claim 1 contains a dispersion fluid which contains at least one water soluble dialkyldithiocarbamate at a concentration with the range of 0.05% by volume to about 10% by volume.
5. The process for removal of petroleum hydrocarbons from contaminated soils and aqueous media whereby the process comprises contacting the contaminated soils and aqueous media with process solution which contains dioctyl sodium sulfosuccinate.
6. The contaminates removal process of claim 5 contains a process fluid which contains dioctyl sodium sulfosuccinate at a concentration with the range of 0.05% by volume to about 10% by volume.
7. A
process to remove and recover heavy metals such as lead, mercury from contaminated solids and aqueous media.
process to remove and recover heavy metals such as lead, mercury from contaminated solids and aqueous media.
8. The contaminate removal process of claim 7 contains a solubilizing fluid which contains at least one water soluble dialkyldithiocarbamate at concentration with a range of 0.05% by volume to about 10% by volume.
9. The contaminate removal process of claim 7 contains a solubilizing fluid which contains at least one water soluble surfactant which contains at least one part di-2-ethylhexylsulfosuccinate at concontration with a range of 0.05% by volume to about 10% by volume.
10. A
process to recover one or more of the metal-dialkyldithiocarbamates from the process solution used to recover the heavy metals from the contaminated solids and aqueous media.
process to recover one or more of the metal-dialkyldithiocarbamates from the process solution used to recover the heavy metals from the contaminated solids and aqueous media.
11. A
process to recover one or more of the chemical reagents from the process solution used to recover the petroleum hydrocarbons from the contaminated solids and aqueous media.
process to recover one or more of the chemical reagents from the process solution used to recover the petroleum hydrocarbons from the contaminated solids and aqueous media.
12. A
process to remove and recover any heavy metals including mercury, zinc and other such metals which behind in the waste water created during the heavy metal removal process
process to remove and recover any heavy metals including mercury, zinc and other such metals which behind in the waste water created during the heavy metal removal process
13. A heavy metal removal process of claim 12 contains chelating resin consisting of a polycarboxylic acid resin which is capable of removing mercury, zinc and other such metals which remain in the water with the objective to render the waste water to a potable state whereby it can be discharged into the environment.
14.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3001961A1 (en) * | 2013-02-13 | 2014-08-15 | Commissariat Energie Atomique | SOL-GEL PROCESS FOR SEPARATING METAL IONS FROM AQUEOUS SOLUTION |
| CN104438305A (en) * | 2013-09-20 | 2015-03-25 | 重庆文理学院 | Drum type soil heavy metal elution system |
| CN109180541A (en) * | 2018-09-04 | 2019-01-11 | 陕西科技大学 | The method and recovery method of Cd in a kind of functional ionic liquids and preparation method thereof, intensified by ultrasonic wave washed off soil |
| CN113233824A (en) * | 2021-06-02 | 2021-08-10 | 昆明理工大学 | Preparation method of tin tailing based low-permeability heavy metal solidified body for underground filling |
-
2007
- 2007-10-24 CA CA 2605824 patent/CA2605824A1/en not_active Abandoned
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3001961A1 (en) * | 2013-02-13 | 2014-08-15 | Commissariat Energie Atomique | SOL-GEL PROCESS FOR SEPARATING METAL IONS FROM AQUEOUS SOLUTION |
| WO2014124901A1 (en) * | 2013-02-13 | 2014-08-21 | Commissariat à l'énergie atomique et aux énergies alternatives | Sol-gel method for separating metal ions from an aqueous solution |
| CN104438305A (en) * | 2013-09-20 | 2015-03-25 | 重庆文理学院 | Drum type soil heavy metal elution system |
| CN109180541A (en) * | 2018-09-04 | 2019-01-11 | 陕西科技大学 | The method and recovery method of Cd in a kind of functional ionic liquids and preparation method thereof, intensified by ultrasonic wave washed off soil |
| CN113233824A (en) * | 2021-06-02 | 2021-08-10 | 昆明理工大学 | Preparation method of tin tailing based low-permeability heavy metal solidified body for underground filling |
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