WO2024145372A1 - Treatment of tailings using synergistic combination of flocculant, coagulant, and 'process additive' - Google Patents
Treatment of tailings using synergistic combination of flocculant, coagulant, and 'process additive' Download PDFInfo
- Publication number
- WO2024145372A1 WO2024145372A1 PCT/US2023/086056 US2023086056W WO2024145372A1 WO 2024145372 A1 WO2024145372 A1 WO 2024145372A1 US 2023086056 W US2023086056 W US 2023086056W WO 2024145372 A1 WO2024145372 A1 WO 2024145372A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tailings
- flocculant
- coagulant
- chloride
- acid
- 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.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/148—Combined use of inorganic and organic substances, being added in the same treatment step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D3/00—Differential sedimentation
- B03D3/02—Coagulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D3/00—Differential sedimentation
- B03D3/06—Flocculation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
- C10G1/045—Separation of insoluble materials
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/127—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering by centrifugation
-
- 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
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
Definitions
- the present disclosure generally relates to novel methods of treating tailing, e.g., tailings obtained from oils sands or mining operations, by the addition of at least one flocculant, process additive, and coagulant and tailing compositions obtained using these methods.
- Oil sands reserves are an important part of the world's oil reserves, particularly as higher oil prices and new technology enable oil sands reserves to be profitably extracted and upgraded to usable products.
- Oil sands are often referred to as unconventional oil or crude bitumen, in order to distinguish the bitumen extracted from oil sands from the free ⁇ flowing hydrocarbon mixtures known as crude oil traditionally produced from oil wells.
- the sands may be extracted by strip mining or the oil is made to flow into wells by in situ techniques that reduce the viscosity, such as by injecting steam, solvents, and/or hot air into the sands.
- Water ⁇ based oil sand extraction processes generally include ore preparation, extraction, and tailings treatment stages wherein a large volume of solids ⁇ laden aqueous tailings may generally be produced.
- the composition of mature fine tailings tends to be highly variable. Near the top of the stratum the mineral content may be about 10% by weight and over time may consolidate and comprise up to 50% by weight of the materials contained at the bottom of the stratum. Overall, mature fine tailings may have an average mineral content of about 30% by weight.
- Flocculants are chemicals, e.g., polymers, that promote flocculation by causing colloids and other suspended particles in liquids to aggregate, thereby forming a floc. Flocculants are generally used in water treatment processes to improve the sedimentation or filterability of small particles. Various inorganic and/or organic flocculants including dry polyacrylamide (DPAM) find known usage in tailings treatments.
- DPAM dry polyacrylamide
- Centrifugation is commonly applied together with the addition of flocculants and/or coagulants during tailings treatment to facilitate dewatering. Unfortunately, conventional additives do not achieve optimal results.
- the present invention solves these problems by treating tailings by a method which include the introduction of a process or process additive which boosts cake solids content when added after flocculation and prior or simultaneous, preferably prior to the addition of a coagulant, e.g., a cationic or acidic coagulant.
- a process or process additive which boosts cake solids content when added after flocculation and prior or simultaneous, preferably prior to the addition of a coagulant, e.g., a cationic or acidic coagulant.
- at least one flocculant preferably an anionic, nonionic, and/or cationic flocculant, more preferably an anionic polymer flocculant, and allowing at least a portion of the solids to flocculate
- at least one process additive optionally a sulfur containing
- the at least one process additive comprises a sulfur containing compound, which differs from the added coagulant, and optionally comprises a sulfite or sulfate compound. It is a specific object of the invention to provide a method for treating tailings of any one of the foregoing method of any one of the foregoing, wherein the at least one process additive comprises sodium sulfite (RED agent, antioxidant), sodium persulfate (OX agent), sodium sulfate (buffer, weak base), sodium metabisulfate (alternatively known as sodium dithionate, or Na2S2O6).
- the oil sands ore tailings stream may comprise process tailings.
- Any of the above terms referencing “tailings” additionally generally comprises fluid fine tailings ("FFT") such as mature fine tailings (“MFT”) from tailings ponds and fine tailings from ongoing extraction operations (for example, froth treatment tailings or thickener underflow) which may bypass a tailings pond.
- FFT fluid fine tailings
- MFT mature fine tailings
- fines generally may refer to mineral fractions that may comprise a particle diameter less than 44 microns.
- “fluid fine tailings” or “FFT” may comprise a liquid suspension of oil sand fines in water with a solids content greater than 2%.
- Exemplary coagulants may comprise but are not limited to comprising “inorganic coagulants” such as aluminium sulfate (“ALS”) or Al 2 (SO 4 ) 3 ) and other metal sulfates and gypsum, “organic coagulants” such as polyamines and polyDADMACs, and other inorganic and organic coagulants known in the art.
- Exemplary coagulants may comprise highly acidic coagulants or cationic coagulants.
- organic coagulants include poly(diallyldimethyl ammonium chloride) compounds; epi ⁇ polyamine compounds; polymers that may comprise one or more quaternized ammonium groups, such as acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride, acrylamidopropyltrimethylammonium chloride; or a mixture thereof.
- the polymer in a may be thoroughly dissolved or may be a partially dissolved suspension, dispersion, or slurry.
- An “aqueous polymer mixture” or “hydrated polymer composition” refers to a combination of at least one polymer and an aqueous liquid. When a dry polymer is combined with an aqueous liquid, the polymer is initially partially hydrated at the polymer– 9 Docket No.: 1149704.054013 water interface. Polymers do not dissolve instantaneously in aqueous or non ⁇ aqueous solvents. Dissolution is controlled by either the disentanglement of the polymer chains or by the diffusion of the chains through a boundary layer adjacent to the polymer–solvent interface.
- the term “monomer” generally refers to nonionic monomers, anionic monomers, cationic monomers, zwitterionic monomers, betaine monomers, and amphoteric ion pair monomers.
- nonionic monomer generally refers to a monomer that possesses a neutral charge.
- any of said one or more nonionic monomers may be substituted with a side chain selected from: an alkyl, arylalkyl, dialkyl, ethoxyl, and/or hydrophobic group.
- anionic monomers may refer to either anionic monomers that are substantially anionic in whole or (in equilibrium) in part, at a pH in the range of about 6.0 to about 8.0.
- the "anionic monomers” may be neutral at low pH (from a pH of about 2 to about 6), or to anionic monomers that are anionic at low pH.
- anionic monomers examples include acrylic acid, methacrylic acid, maleic acid monomers and the like, calcium diacrylate, and/or any monomer substituted with a carboxylic acid group or salt thereof.
- anionic monomers which may be substituted with a carboxylic acid group include, for example, acrylic acid, and methacrylic acid.
- an anionic monomer may be a (meth)acrylamide monomer wherein the amide group has been hydrolyzed to a carboxyl group. Said monomer may be a derivative or salt of a monomer according to the embodiments. Additional examples of anionic monomers comprise but are not limited to comprising sulfonic acids or a sulfonic acid group, or both.
- the anionic monomers may comprise a sulfonic function that may comprise, for example, 2 ⁇ acrylamido ⁇ 2 ⁇ methylpropane sulfonic acid ("ATBS").
- Anionic monomers herein specifically include anionic monomers that are neutral at low pH Such anionic monomers include acrylic acid, methacrylic acid, maleic acid monomers, any monomer substituted with a carboxylic acid group, or salt of any of the foregoing, or combination thereof.
- anionic monomers herein include anionic monomers that are anionic at low 10 Docket No.: 1149704.054013 pH.
- sulfonic acids examples thereof: sulfonic acids, monomers comprising a sulfonic acid group, 2 ⁇ acrylamido ⁇ 2 ⁇ methylpropane sulfonic acid ("ATBS”), and combinations thereof.
- ATBS 2 ⁇ acrylamido ⁇ 2 ⁇ methylpropane sulfonic acid
- cationic monomer generally refers to a monomer that possesses a positive charge.
- Said cationic monomers may also comprise but are not limited to comprising dialkylaminoalkyl acrylates and methacrylates and their quaternary or acid salts, including, but not limited to, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethyaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethyl acrylate hydrochloric acid salt, diethylaminoethyl acrylate, methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride qua
- Alkyl groups may generally be C1 ⁇ C8 alkyl.
- the terms "polymer,” “polymers,” “polymeric,” and similar terms are used in their ordinary sense as understood by one skilled in the art, and thus may be used herein to refer to or describe a large molecule (or group of such molecules) that may comprise recurring units. Polymers may be formed in various ways, including by polymerizing monomers and/or by chemically modifying one or more recurring units of a precursor polymer. Unless otherwise specified, a polymer may comprise a "homopolymer” that may comprise substantially identical recurring units that may be formed by, for example, polymerizing, a particular monomer.
- a polymer may also comprise a "copolymer” that may comprise two or more different recurring units that may be formed by, for example, copolymerizing, two or more different monomers, and/or by chemically modifying one or more recurring units of a precursor polymer.
- a polymer or copolymer may also comprise a "terpolymer” which generally refers to a polymer that comprises three or more different recurring units. Any one of the one or more polymers discussed herein may be used in any exemplary process, for example, as a flocculant.
- said flocculants may comprise a polymer, copolymer, and/or terpolymer comprising one or more monomers, wherein said monomers may be one or more nonionic, one or more anionic, and/or one or more cationic monomers.
- said flocculants may comprise one or more polymers, copolymers, and/or terpolymers comprising, but not limited to comprising, one or more monomers of the following: acryloyloxy ethyl trimethyl ammonium chloride ("AETAC”); methacryloyloxyethyltrimethylammonium chloride; methacrylamidopropyltrimethylammonium chloride ("MAPTAC”); acrylamidopropyltrimethylammonium chloride; methacryloyloxyethyldimethylammonium sulfate; dimethylaminoethyl acrylate; dimethylaminopropylmethacrylamide; diallyldimethylammonium chloride (“DADMAC”); calcium diacrylate (“CDA”); acrylamide; acrylic acid; any monomer substituted with a carboxylic acid group or salt thereof; 2 ⁇ acrylamido ⁇ 2 ⁇ methylpropane sulfonic acid (“AMPS”);
- AETAC
- process additive refers to a compound, which differs from the coagulant compound used in the subject tailings treatment processes, that promotes the effects of the coagulant on dewatering, optionally by reducing floc size (e.g., by making flocs less bulky after flocculant addition) and/or by causing floc restructuring to achieve better floc compaction, further optionally a sulfur containing compound; still further a sulfite or sulfate compound, e.g., sodium sulfite (RED agent, antioxidant), sodium persulfate (OX agent), sodium sulfate (buffer, weak base), sodium metabisulfate (alternatively known as sodium dithionate, or Na 2 S 2 O 6 ).
- the term "produced water” generally refers to any aqueous fluids produced during any type of industrial process, e.g., an oil or gas extraction or recovery process, or any portion thereof. Typically the produced water may be obtained during an industrial process involving the use of water, generally copious amounts of water, wherein the end product of such industrial process may be an aqueous material or "produced water” which may be of an undesirable purity. Produced water may be generated during processes or portions thereof which involve oil sands.
- the term “mechanical dewatering” generally refers to any process that may be used to aid in the dewatering of tailings, e.g., oil sands tailings.
- mechanical dewatering may comprise centrifugation, thin lift, and/or thickeners. In some embodiments, mechanical dewatering may comprise centrifugation.
- introduction generally refers to any means known in the art by which addition of a substance, e.g., a polymer flocculant, coagulant or process additive, may occur.
- polymer introduction As used herein, the terms "polymer introduction”, “introduction of a polymer”, and “introduction of one or more polymers” generally refer to one or more introductions of one or more polymers, e.g., one or more polymeric flocculants, to a stream.
- Exemplary methods specifically comprise the addition of one or more flocculants in order to flocculate solids from the tailings, prior to the addition of at least one “process additive” or “process additive” or “additive” or “A”, e.g., a sulfur compound, the addition of which is preferably effected prior to the addition of at least one coagulant or simultaneous thereto.
- the process additive has surprisingly been demonstrated to boost the cake solids content when added after flocculation has been initiated, e.g., by about 0.5 percent by weight.
- To the best of the inventors’ knowledge the use of addition of such process additives to further increase solids content in the recovered dewatered tailings, e.g., in the centrifuge cake has not been previously reported.
- addition of such process additives may further result in one or more of the following: (i) less required energy input compared to mechanical conditioning (e.g., shearing) required to achieve desired cake solids percentages; (ii) shorter mixing times compared to mechanical conditioning (e.g., shearing) required to achieve desired cake solids percentages; (iii) lower dosages of other additives such as flocculants and/or coagulants needed to boost cake solids percentages; and (iv) increased cake solids percentages when the tailings treatment process comprises the addition of the at least one flocculant (F) followed by the addition of the at least one process additive (A), in turn followed by the addition of the at least one coagulant (C) (F ⁇ A ⁇ C); as compared to otherwise similar treatment methods wherein the addition of the at least one flocculant (F) is followed by the addition of at least one coagulant (C) (F ⁇ C); and also compared to otherwise similar tailings treatment methods wherein the addition of the floccul
- said flocculants may comprise a polymer, copolymer, and/or terpolymer comprising one or more monomers, wherein said monomers 14 Docket No.: 1149704.054013 may be one or more nonionic, one or more anionic, and/or one or more cationic monomers.
- said flocculants may comprise one or more polymers, copolymers, and/or terpolymers comprising, but not limited to comprising, one or more monomers of the following: acryloyloxy ethyl trimethyl ammonium chloride ("AETAC”); methacryloyloxyethyltrimethylammonium chloride; methacrylamidopropyltrimethylammonium chloride ("MAPTAC”); acrylamidopropyltrimethylammonium chloride; methacryloyloxyethyldimethylammonium sulfate; dimethylaminoethyl acrylate; dimethylaminopropylmethacrylamide; diallyldimethylammonium chloride (“DADMAC”); calcium diacrylate (“CDA”); acrylamide; acrylic acid; any monomer substituted with a carboxylic acid group or salt thereof; 2 ⁇ acrylamido ⁇ 2 ⁇ methylpropane sulfonic acid (“AMPS”);
- AETAC
- the at least one flocculant will comprise an anionic polymer which comprises one or more anionic monomers, which are selected from acrylic acid, sodium acrylate, ammonium acrylate, methacrylic acid, 2 ⁇ acrylamido ⁇ 2 ⁇ methylpropanesulfonic acid (AMPS), vinyl sulfonic acid, styrene sulfonic acid, maleic acid, sulfopropyl acrylate or methacrylate or other water ⁇ soluble forms of these or other polymerizable carboxylic or sulphonic acids, sulfomethylated acrylamide, allyl sulfonate, 15 Docket No.: 1149704.054013 itaconic acid, acrylamidomethylbutanoic acid, fumaric acid, vinylphosphonic acid, allylphosphonic acid, phosphonomethylated acrylamide, methacrylate, itaconate, 2 ⁇ acrylamido 2 ⁇ methyl propane sulphonate, sulf
- anionic polymer which
- the at least one flocculant will comprise an anionic acrylamide copolymer, further optionally a copolymer comprising PAM acrylic acid (AA), and/or ATBS, e.g., an anionic flocculant which comprises greater than 0% or more to about 100 mol% of a charged monomer or from about 20 mol% to about 95 mol% of a charged monomer, or from about 50% or more to about 95% or more mol% of a charged monomer; or comprises an acrylamide flocculant that comprises from greater than 0 mol% or more to about 100 mol% of a charged monomer, such as an anionic monomer, or from about 50% or more to about 95% or more mol% of a charged monomer, such as an anionic monomer or comprises 20 ⁇ 45 mol% or 50 mol% or more of a charged monomer such as an anionic monomer.
- an anionic flocculant which comprises greater than 0% or more to about 100 mol% of a charged monomer or from about 20
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention generally relates to novel methods of treating tailing, e.g., tailings obtained from oils sands or mining operations, by the addition of at least one flocculant, process additive, and coagulant and tailing compositions obtained using these methods.
Description
Docket No.: 1149704.054013 TREATMENT OF TAILINGS USING SYNERGISTIC COMBINATION OF FLOCCULANT, COAGULANT, AND ‘PROCESS ADDITIVE’ RELATED APPLICATIONS This application claims priority to U.S. Prov. Appl. No. 63/477,328 filed on December 27, 2022 and Finnish application FI20235309 filed on March 15, 2023. FIELD OF THE INVENTION [0001] The present disclosure generally relates to novel methods of treating tailing, e.g., tailings obtained from oils sands or mining operations, by the addition of at least one flocculant, process additive, and coagulant and tailing compositions obtained using these methods. BACKGROUND [0002] Bituminous sands, also referred to as oil sands, are a type of petroleum deposit. Oil sands typically contain naturally occurring mixtures of sand, clay, water, and a dense, extremely viscous form of petroleum technically referred to as bitumen (or colloquially "tar" due to their similar appearance, odor, and color). Oil sands is found in many countries throughout the world, most abundantly so in Canada and Venezuela. Oil sand deposits in northern Alberta in Canada (Athabasca oil sands) are thought to contain approximately 1.6 trillion barrels of bitumen. [0003] Oil sands reserves are an important part of the world's oil reserves, particularly as higher oil prices and new technology enable oil sands reserves to be profitably extracted and upgraded to usable products. Oil sands are often referred to as unconventional oil or crude bitumen, in order to distinguish the bitumen extracted from oil sands from the free‐ flowing hydrocarbon mixtures known as crude oil traditionally produced from oil wells. [0004] Since extra‐heavy oil and bitumen flow very slowly, if at all, towards producing wells under normal reservoir conditions, the sands may be extracted by strip mining or the oil is made to flow into wells by in situ techniques that reduce the viscosity, such as by injecting steam, solvents, and/or hot air into the sands. These processes often require the usage of more water and may require larger amounts of energy than conventional oil extraction. [0005] Water‐based oil sand extraction processes generally include ore preparation, extraction, and tailings treatment stages wherein a large volume of solids‐laden aqueous tailings may generally be produced. The composition of mature fine tailings tends to be highly variable. Near the top of the stratum the mineral content may be about 10% by weight and over time may consolidate and comprise up to 50% by weight of the materials contained at the bottom of the stratum. Overall, mature fine tailings may have an average mineral content of about 30% by weight. While fines may generally be the dominant particle size fraction in the mineral content, the sand content may be 15% by weight of the solids and the clay content may be up to 75% by weight of the solids, reflecting the oil sand ore and extraction process. Additional variation may result from the residual hydrocarbon which may be dispersed in the mineral or may segregate into mat layers of hydrocarbon. The mature fine tailings in a pond may not only contain a wide variation of compositions distributed from top to bottom of the pond, but also may contain pockets of different 1
Docket No.: 1149704.054013 compositions at random locations throughout the pond. Additionally, mature fine tailings generally behave as a fluid‐like colloidal material. [0006] The slow settling of fine (<45 ^m) and ultrafine clays (<0.3 ^m) in tailings as well as the large demand of water during oil sand extraction process have promoted research and development of new technologies or enhancing water release and for improving settling characteristics of tailings streams. These include the addition of additives that modify the pH and/or salinity as well as the addition of chemical substances. Two technologies used in the oil sands industry to treat tailings are the consolidated tailings ("CT") process and the paste technology. Gypsum is typically used in the CT technology as a coagulant while polyelectrolytes, generally polyacrylamides of high density, are generally used as flocculants in the paste technology. [0007] Flocculants, or flocculating agents, are chemicals, e.g., polymers, that promote flocculation by causing colloids and other suspended particles in liquids to aggregate, thereby forming a floc. Flocculants are generally used in water treatment processes to improve the sedimentation or filterability of small particles. Various inorganic and/or organic flocculants including dry polyacrylamide (DPAM) find known usage in tailings treatments. [0008] Centrifugation is commonly applied together with the addition of flocculants and/or coagulants during tailings treatment to facilitate dewatering. Unfortunately, conventional additives do not achieve optimal results. For example in some cases increasing the additive dosage (e.g., an acidic coagulant) lowers the pH too much which undesirably increases Ca++ content in the centrate without significantly improving the cake solids content. Also, while shearing down the floc size by mechanical means can improve cake solids content; this generally requires very high energy input and/or mixing time which are commercially disadvantageous. [0009] Therefore, based on the foregoing, alternative methods and/or additives that further increase the solids content in treated tailings compositions are desired. BRIEF SUMMARY AND INVENTIVE OBJECTS [0010] The present invention solves these problems by treating tailings by a method which include the introduction of a process or process additive which boosts cake solids content when added after flocculation and prior or simultaneous, preferably prior to the addition of a coagulant, e.g., a cationic or acidic coagulant. [0011] It is a specific object of the invention to provide a method for treating tailings, optionally obtained from an oil sands or mining separation process, comprising (a) contacting tailings which are to be dewatered with at least one flocculant, preferably an anionic, nonionic, and/or cationic flocculant, more preferably an anionic polymer flocculant, and allowing at least a portion of the solids to flocculate; (b) adding at least one process additive, optionally a sulfur containing compound; and (c) adding at least one coagulant, optionally an acidic or cationic coagulant; wherein steps (b) and (c) are performed after step (a), in any order or simultaneously. 2
Docket No.: 1149704.054013 [0012] It is a specific object of the invention to provide a method for treating tailings as above, wherein step (b) is effected prior to step (c). [0013] It is a specific object of the invention to provide a method for treating tailings of any of the foregoing, wherein the time between step (a) and (b) typically ranges from about 10 sec – 10 min, more typically is about 30 ‐ 60 sec or is a time sufficient for flocs to form. [0014] It is a specific object of the invention to provide a method for treating tailings of any of the foregoing, wherein the tailings are obtained from an oil sands separation process. [0015] It is a specific object of the invention to provide a method for treating tailings of any of the foregoing, wherein the tailings are obtained from a mining separation process. [0016] It is a specific object of the invention to provide a method for treating tailings of any of the foregoing, wherein: (i) the at least one flocculant comprises an anionic polymer; (ii) the at least one flocculant comprises an anionic polymer which comprises one or more of acrylic acid, sodium acrylate, ammonium acrylate, methacrylic acid, 2‐acrylamido‐2‐methylpropanesulfonic acid (ATBS), vinyl sulfonic acid, styrene sulfonic acid, maleic acid, sulfopropyl acrylate or methacrylate or other water‐soluble forms of these or other polymerizable carboxylic or sulphonic acids, sulfomethylated acrylamide, allyl sulfonate, itaconic acid, acrylamidomethylbutanoic acid, fumaric acid, vinylphosphonic acid, allylphosphonic acid, phosphonomethylated acrylamide, methacrylate, itaconate, 2‐acrylamido 2‐methyl propane sulphonate, sulfoalkyl(meth)acrylic acids, sulfonated styrenes, unsaturated dicarboxylic acids, sulfoalkyl(meth)acrylamides, vinyl acetate, n‐vinylformamide, n‐ vinylacetamide, n‐vinylcaprolactam, n‐vinylimidazole, n‐vinylpyridine, n‐ vinylpyrolidone, acrylamidopropyltrimonium chloride, salts of said acids and the like, or another anionic ethylenically unsaturated compound, and preferably comprises acrylic acid, methacrylic acid, maleic acid monomers, calcium diacrylate, and/or any monomer substituted with a carboxylic acid group or salt thereof, a (meth)acrylamide monomer wherein the amide group has been hydrolyzed to a carboxyl group, monomers comprising sulfonic acids or a sulfonic acid group, or both, 2‐acrylamido‐2‐methylpropane sulfonic acid (“ATBS"), or combinations thereof, and more preferably comprises acrylic acid or ATBS; (iii) the at least one flocculant is an anionic polymer which comprises (meth)acrylic acid or a salt thereof, optionally a sodium, calcium, ammonium salt; (iv) the at least one flocculant comprises an anionic polymer flocculant which comprises a nonionic monomer, optionally acrylamide, N‐alkylacrylamides, N,N‐dialkylacrylamides, methacrylamide, N‐vinylmethylacetamide or formamide, vinyl acetate, vinyl pyrrolidone, alkyl methacrylates, acrylonitrile, N‐vinylpyrrolidone other acrylic (or other ethylenically unsaturated) ester or 3
Docket No.: 1149704.054013 other water insoluble vinyl monomers such as styrene or acrylonitrile and preferably comprises acrylamide; (v) the at least one flocculant comprises an anionic polymer flocculant which comprises an acrylamide copolymer, optionally a copolymer comprising PAM acrylic acid (AA), and/or ATBS; (vi) the at least one flocculant comprises an anionic flocculant which comprises greater than 0% or more to about 100 mol% of a charged monomer or from about 20 mol% to about 95 mol% of a charged monomer, or from about 50% or more to about 95% or more mol% of a charged monomer; (vii) the at least one flocculant comprises an acrylamide flocculant that comprises from greater than 0 mol% or more to about 100 mol% of a charged monomer, such as an anionic monomer, or from about 50% or more to about 95% or more mol% of a charged monomer, such as an anionic monomer or comprises 20‐45 mol% or 50 mol% or more of a charged monomer such as an anionic monomer; (viii) the at least one flocculant comprises an anionic polymer which comprises a copolymer comprising PAM and acrylic acid (AA), optionally 25‐ 35 mol% AA, or 15‐40% AA; (ix) the at least one flocculant comprises an anionic polymer, wherein the anionic polymer flocculant comprises a standard viscosity (SV) ranging from 3‐5, 3.1‐ 4.1, or 3.2‐4.0; (x) the molecular weight of the polymer flocculant ranges from 500 Da to 200,000,000 Da, or from 10,000 Da to 100,000,000 Da, or from 10,000 Da to 50,000,000 Da or from 10,000 Da to 20,000,000 Da, or from 10,000 Da to 10,000,000 Da or from 10,000 Da to 1,000,000 Da or from 10,000 Da to 500,000 Da or from 10,000 Da to 100,000 Da; (xi) the at least one flocculant comprises a dry polymer, an emulsion or an aqueous solution; (xii) the amount of the at least one flocculant added ranges from 50 to about 100000 g/t dry tailings or from about 500 to about 10000 g/t dry tailings; or (xiii) any combination of the foregoing. [0017] It is a specific object of the invention to provide a method for treating tailings of any of the foregoing, wherein the at least one process additive comprises a sulfur containing compound, which differs from the added coagulant, and optionally comprises a sulfite or sulfate compound. It is a specific object of the invention to provide a method for treating tailings of any one of the foregoing method of any one of the foregoing, wherein the at least one process additive comprises sodium sulfite (RED agent, antioxidant), sodium persulfate (OX agent), sodium sulfate (buffer, weak base), sodium metabisulfate (alternatively known as sodium dithionate, or Na2S2O6). 4
Docket No.: 1149704.054013 [0018] It is a specific object of the invention to provide a method for treating tailings of any of the foregoing, wherein the at least one process additive is added in dry form or as an aqueous composition, optionally a 0.2% solution comprising deionized (DI) water. [0019] It is a specific object of the invention to provide a method for treating tailings of any of the foregoing, wherein the dosage of the at least one process additive ranges from about 5‐100 g/ton or about 20‐50 g/ton. [0020] It is a specific object of the invention to provide a method for treating tailings of any of the foregoing, wherein (i) the at least one coagulant comprises a cationic coagulant, and optionally comprises an acidic coagulant; (ii) the at least one coagulant comprises an organic or inorganic coagulant; (iii) the at least one coagulant comprises an inorganic coagulants such as inorganic salts such as aluminum sulfate, polyaluminum chloride, polyaluminum silica sulfate, ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, lime, calcium chloride, calcium sulfate, magnesium chloride, or various commercially available iron or aluminum salts coagulants; (iv) the at least one cationic coagulant is a poly(diallyl dimethyl ammonium chloride) compound; an epi‐polyamine compound; a polymer that contains one or more quaternized ammonium groups, such as acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride, or acrylamidopropyltrimethylammonium chloride; aluminum sulfate, ferric chloride, lime, calcium chloride, magnesium chloride, or another iron or aluminum salts coagulants; (v) the at least one coagulant comprises gypsum; (vi) the at least one coagulant comprises sulfuric acid or aluminum sulfate (ALS); (vii) the at least one coagulant comprises an organic polymeric coagulant, optionally of low MW (e.g., ≈300,000 ‐≈500,000 Da); (viii) the at least one coagulant comprises a cationic organic polyamine, or polyDADMAC coagulant, optionally of low MW (e.g., ≈300,000 ‐≈500,000 Da); (ix) the at least one coagulant is added in liquid form; (x) the dosage range of the at least one coagulant ranges from 200‐8000 ppm or 500‐6000 ppm; or (xi) any combination of the foregoing. [0021] It is a specific object of the invention to provide a method for treating tailings of any of the foregoing, wherein (i) the pH of the tailings is around 8 prior to the addition of the at least one 5
Docket No.: 1149704.054013 flocculant, process additive, and coagulant; (ii) the pH of the tailings after the addition of the coagulant typically is reduced to about 5‐6, and preferably is not reduced to a level which results in the release of Ca into release water; (iii) the at least one flocculant, process additive, and coagulant are added in line prior to mechanical dewatering; (iv) the total dosage of the flocculant is about 500 to about 10000 g/t dry tailings; or (v) any combination of the foregoing. [0022] It is a specific object of the invention to provide a method for treating tailings of any of the foregoing, wherein after the addition of the at least one flocculant, process additive, and coagulant the solids are separated from the tailings stream by one or more of centrifugation, hydrocycloning, decantation, filtration, thickening or another mechanical separation; and optionally further comprises a desanding step. [0023] It is a specific object of the invention to provide a method for treating tailings of any one of the foregoing, which results in one or more of the following; (i) reduction in solids content in tailings; (ii) reduction of turbidity in tailings; (iii) reduced chemical oxygen demand; (iv) improved flocculation at lower flocculant dosages; (v) reduced solids content in treated tailings and changed tailings composition; (vi) improved removal of fine, slow settling clay particles, persistent contaminants, and/or residual bitumen; (vii) reduced formation of non‐segregated tailings; (viii) increased water release; (ix) a desirable degree of floe formation; or (x) a combination of any of the foregoing; as compared to a method wherein the at least one process additive is not added. [0024] It is a specific object of the invention to provide a tailings composition produced by a method according to any one of the foregoing, optionally derived from an oil sands or mining separation process. . DESCRIPTION [0025] This invention provides novel methods of treating tailing, e.g., tailings obtained from oils sands or mining operations, and tailing compositions obtained using these methods. 6
Docket No.: 1149704.054013 [0026] More particularly, the invention relates to a method of treating tailings which includes the introduction of a process or process additive which boosts cake solids content when added after flocculation and prior or simultaneous, preferably prior to the addition of a coagulant, e.g., a cationic or acidic coagulant. [0027] Even more specifically, the invention relates to a method of treating tailings which optionally are obtained from an oil sands or mining separation process, wherein said tailings comprise an aqueous phase with suspended solid particulate material, and wherein the method comprises: (a) contacting tailings which are to be dewatered with at least one flocculant, preferably an anionic, nonionic, and/or cationic flocculant, more preferably an anionic polymer flocculant, and allowing at least a portion of the solids to flocculate; (b) adding at least one process additive which promotes the effects of a coagulant on dewatering, optionally a process additive which reduces floc size (to make flocs less bulky after flocculant addition) and/or by causing floc restructuring to achieve better floc compaction, further optionally a sulfur containing compound; and (c) adding at least one coagulant, optionally an acidic or cationic coagulant; wherein steps (a) and (b) are effected successively, and steps (b) and (c) are effected successively in any order or simultaneously, further optionally wherein said tailings may comprise fluid fine tailings, mature fine tailings, undiluted tailings or diluted tailings, or a combination thereof. [0028] The advantages of the invention and exemplary embodiments are disclosed in further detail infra. DETAILED DESCRIPTION OF THE INVENTION [0029] Before describing the invention in detail, the following definitions are provided. Unless stated otherwise all terms are to be construed as they would be by a person skilled in the art. Definitions [0030] The various exemplary embodiments disclosed herein generally relate to methods for treating tailings such as oil sands tailings or tailings obtained from mining operations. In exemplary embodiments, the methods involve methods for flocculating solids in the tailings and dewatering of the tailings. [0031] Exemplary methods comprise the use of one or more flocculants in order to flocculate solids in the tailings, which is effected prior to the addition of at least one process additive, typically a sulfur containing compound, and further prior to the addition of at least one coagulant, typically a cationic or acidic coagulant. As shown infra, the process additive, typically a sulfur containing compound, elicits synergistic effects, e.g., it boosts cake solids content when added after flocculation and prior to or optionally simultaneous to the addition of at least one coagulant, e.g., an acidic coagulant the addition of which reduces the pH of a solution comprising said tailings. 7
Docket No.: 1149704.054013 [0032] In exemplary embodiments, pH adjustment is performed after the introduction of one or more flocculants and after or simultaneous to the addition of said one or more process additives, e.g., sulfur containing compounds, and further prior to mechanical dewatering, e.g., by use of centrifugation. The present embodiments also generally relate to a product that may be produced by any of the methods described herein. [0033] As used herein the singular forms "a", "and", and "the" include plural referents unless the context clearly dictates otherwise. All technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this invention belongs unless clearly indicated otherwise. [0034] As used herein, the terms "tailings" and "tailings stream" generally refer to the discarded materials that may be generated in the course of extracting a valuable material from an ore. Exemplary tailings include, but are not limited to, tailings from coal mining, copper mining, gold mining, aluminum mining, nickel mining and/or mineral processing. Exemplary tailings also include tailings from the processing of oil sands. While many of the exemplary embodiments are described with reference to oil sands tailings, it is understood that the exemplary compositions, processes, and methods are not limited to applications in oil sands tailings, but also can be applied to various other tailings. The term tailings is meant to be inclusive of but not limited to any of the types of tailings discussed herein, e.g., process oil sand tailings, in‐process tailings, oil sands tailings, and the like. [0035] The terms "process oil sand tailings", "oil sands tailings stream", "oil sands process tailings", or "oil sands tailings", generally refer to tailings that may be directly generated as bitumen is extracted from oil sands. In tar sand processing, tailings may comprise the whole tar sand ore and any net additions of process water less the recovered bitumen. Any tailings fraction obtained from the process, such as tailings from primary separation cell, primary flotation and secondary flotation, process tailings, froth treatment tailings, and mature fine tailings or combination thereof, may be treated by the exemplary processes described herein. The tailings may comprise a colloidal sludge suspension comprising clay minerals and/or metal oxides/hydroxides. In exemplary embodiments, the tailings stream may comprise water and solids. [0036] Tailings generally comprise mineral solids having a variety of particle sizes. Mineral fractions with a particle diameter greater than 44 microns may be referred to as "coarse" particles, or "sand." Mineral fractions with a particle diameter less than 44 microns may be referred to as "fines" and may essentially be comprised of silica and silicates and clays that may be easily suspended in the water. Ultrafine solids, e.g., particles < 1 μm may also be present in the tailings stream and may be primarily composed of clays. The tailings may include but are not limited to including one or more of the coarse particles, fine tailings, MFT, FFT, or ultrafine solids. [0037] The oil sands tailings may additionally include but are not limited to including one or more of any of the tailings streams that may be produced in a process to extract bitumen from an oil sands ore. In some embodiments, the tailings may comprise paraffinic or naphthenic tailings, for example paraffinic froth tailings. The tailings may be combined into a single tailings stream for dewatering or each tailings stream may be dewatered individually. In some embodiments, the tailings stream may be produced from an oil sands ore and may comprise water and solids, for example sand and fines. In exemplary embodiments, the tailings stream may comprise at least one of the coarse tailings, fluid fine 8
Docket No.: 1149704.054013 tailings, MFT, fine tailings, and ultrafine tailings. In some embodiments, the processes may be used to treat ultrafine solids. In some embodiments, the tailings stream may comprise a fine (particle size < 44 m) content of about 10 to about 100 wt%, about 20 to about 100 wt%, about 30 to about 100 wt%, or about 40 to about 90 wt% of the dry tailings. In some embodiments, the tailings stream may comprise about 0.01 to about 5 wt% of bitumen. In some embodiments, the oil sands ore tailings stream may comprise process tailings. [0038] Any of the above terms referencing "tailings" additionally generally comprises fluid fine tailings ("FFT") such as mature fine tailings ("MFT") from tailings ponds and fine tailings from ongoing extraction operations (for example, froth treatment tailings or thickener underflow) which may bypass a tailings pond. [0039] As used herein, "fines" generally may refer to mineral fractions that may comprise a particle diameter less than 44 microns. [0040] As used herein, "fluid fine tailings" or "FFT" may comprise a liquid suspension of oil sand fines in water with a solids content greater than 2%. [0041] The term "mature fine tailings" ("MFT") generally may refer to fine tailings that may comprise a solids content of about 30‐35%, and that generally may comprise almost entirely solids <44 microns. MFT generally may behave as a fluid‐like colloidal material. MFT may comprise FFT with a low sand to fines ratio ("SFR"), i.e., generally less than about 0.3, and a solids content that may be generally greater than about 30%. [0042] As used herein, "sand" generally may refer to mineral fractions that may comprise a particle diameter greater than 44 microns. [0043] As used herein, the term "coagulant" generally may refer to an agent that may typically destabilize colloidal suspensions. Exemplary coagulants may comprise but are not limited to comprising “inorganic coagulants” such as aluminium sulfate ("ALS") or Al2(SO4)3) and other metal sulfates and gypsum, “organic coagulants” such as polyamines and polyDADMACs, and other inorganic and organic coagulants known in the art. Exemplary coagulants may comprise highly acidic coagulants or cationic coagulants. Specific examples of “organic coagulants” include poly(diallyldimethyl ammonium chloride) compounds; epi‐ polyamine compounds; polymers that may comprise one or more quaternized ammonium groups, such as acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride, acrylamidopropyltrimethylammonium chloride; or a mixture thereof. Specific examples of “inorganic coagulants” used in tailing treatment methods to for example, reduce, neutralize or invert electrical repulsions between particles include inorganic salts such as aluminum sulfate, polyaluminum chloride, polyaluminum silica sulfate, ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, lime, calcium chloride, calcium sulfate, magnesium chloride, or various commercially available iron or aluminum salts coagulants. [0044] As used herein, the term “liquid polymer” refers to a combination of at least one polymer and a liquid, typically an aqueous liquid. The polymer in a may be thoroughly dissolved or may be a partially dissolved suspension, dispersion, or slurry. [0045] An “aqueous polymer mixture” or “hydrated polymer composition” refers to a combination of at least one polymer and an aqueous liquid. When a dry polymer is combined with an aqueous liquid, the polymer is initially partially hydrated at the polymer– 9
Docket No.: 1149704.054013 water interface. Polymers do not dissolve instantaneously in aqueous or non‐aqueous solvents. Dissolution is controlled by either the disentanglement of the polymer chains or by the diffusion of the chains through a boundary layer adjacent to the polymer–solvent interface. After thorough mixing, the polymer may become fully hydrated, at which point the wetting process is complete and the polymer may be either partially dissolved or fully dissolved, depending on the nature and composition of the polymer and solvent. The inventive tailings treatment methods may comprise the addition of “aqueous polymer mixtures” or “hydrated polymer compositions”, e.g., those comprising cationic polymer flocculants, e.g., cationic polyacrylamides. [0046] As used herein a “dry polymer” refers to any polymer that does not comprise substantial fluid, typically water. The inventive tailings treatment methods may further comprise the addition of dry polymers, e.g., cationic polymer flocculants, such as cationic polyacrylamides. [0047] As used herein, the term "monomer" generally refers to nonionic monomers, anionic monomers, cationic monomers, zwitterionic monomers, betaine monomers, and amphoteric ion pair monomers. [0048] As used herein the term "nonionic monomer" generally refers to a monomer that possesses a neutral charge. Exemplary nonionic monomers may comprise but are not limited to comprising monomers selected from the group consisting of acrylamide ("AMD"), methacrylamido, vinyl, allyl, ethyl, and the like, all of which may be substituted with a side chain selected from, for example, an alkyl, arylalkyl, dialkyl, ethoxyl, and/or hydrophobic group. Exemplary nonionic monomers include acrylamide, methacrylamide, vinyl monomers, allyl monomers, ethyl monomers, N‐vinylpyridine, N‐vinylimidazole, isopropylacrylamide, isopropylmethacrylamide, polyethylene glycol methacrylate, and combinations thereof. In some embodiments, any of said one or more nonionic monomers may be substituted with a side chain selected from: an alkyl, arylalkyl, dialkyl, ethoxyl, and/or hydrophobic group. [0049] As used herein, the term "anionic monomers" may refer to either anionic monomers that are substantially anionic in whole or (in equilibrium) in part, at a pH in the range of about 6.0 to about 8.0. The "anionic monomers" may be neutral at low pH (from a pH of about 2 to about 6), or to anionic monomers that are anionic at low pH. Examples of anionic monomers include acrylic acid, methacrylic acid, maleic acid monomers and the like, calcium diacrylate, and/or any monomer substituted with a carboxylic acid group or salt thereof. In some embodiments, anionic monomers which may be substituted with a carboxylic acid group include, for example, acrylic acid, and methacrylic acid. In some embodiments, an anionic monomer may be a (meth)acrylamide monomer wherein the amide group has been hydrolyzed to a carboxyl group. Said monomer may be a derivative or salt of a monomer according to the embodiments. Additional examples of anionic monomers comprise but are not limited to comprising sulfonic acids or a sulfonic acid group, or both. In some embodiments, the anionic monomers may comprise a sulfonic function that may comprise, for example, 2‐acrylamido‐2‐methylpropane sulfonic acid ("ATBS"). Anionic monomers herein specifically include anionic monomers that are neutral at low pH Such anionic monomers include acrylic acid, methacrylic acid, maleic acid monomers, any monomer substituted with a carboxylic acid group, or salt of any of the foregoing, or combination thereof. Also, anionic monomers herein include anionic monomers that are anionic at low 10
Docket No.: 1149704.054013 pH. Examples thereof: sulfonic acids, monomers comprising a sulfonic acid group, 2‐ acrylamido‐2‐methylpropane sulfonic acid ("ATBS"), and combinations thereof. [0050] As used herein, the term "cationic monomer" generally refers to a monomer that possesses a positive charge. Examples of cationic monomers may comprise but are not limited to comprising acryloyloxy ethyl trimethyl ammonium chloride ("AETAC"), methacryloyloxyethyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride ("MAPTAC"), acrylamidopropyltrimethylammonium chloride, methacryloyloxyethyldimethylammonium sulfate, dimethylaminoethyl acrylate, dimethylaminopropylmethacrylamide, Q6, Q6o 4, and/or diallyldimethylammonium chloride ("DADMAC"). Said cationic monomers may also comprise but are not limited to comprising dialkylaminoalkyl acrylates and methacrylates and their quaternary or acid salts, including, but not limited to, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethyaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethyl acrylate hydrochloric acid salt, diethylaminoethyl acrylate, methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfuric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt, dimethylaminoethyl methacryloyl hydrochloric acid salt, dialkylaminoalkylacrylamides or methacrylamides and their quaternary or acid salts such as acrylamidopropyltrimethylammonium chloride, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl acrylamide sulfuric acid salt, dimethylaminopropyl acrylamide hydrochloric acid salt, methacrylamidopropyltrimethylammonium chloride, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide sulfuric acid salt, dimethylaminopropyl methacrylamide hydrochloric acid salt, diethylaminoethylacrylate, diethylaminoethylmethacrylate and diallyldialkylammonium halides such as diallyldiethylammonium chloride and diallyldimethyl ammonium chloride. Alkyl groups may generally be C1‐C8 alkyl. [0051] As used herein, the terms "polymer," "polymers," "polymeric," and similar terms are used in their ordinary sense as understood by one skilled in the art, and thus may be used herein to refer to or describe a large molecule (or group of such molecules) that may comprise recurring units. Polymers may be formed in various ways, including by polymerizing monomers and/or by chemically modifying one or more recurring units of a precursor polymer. Unless otherwise specified, a polymer may comprise a "homopolymer" that may comprise substantially identical recurring units that may be formed by, for example, polymerizing, a particular monomer. Unless otherwise specified, a polymer may also comprise a "copolymer" that may comprise two or more different recurring units that may be formed by, for example, copolymerizing, two or more different monomers, and/or by chemically modifying one or more recurring units of a precursor polymer. Unless otherwise specified, a polymer or copolymer may also comprise a "terpolymer" which generally refers to a polymer that comprises three or more different recurring units. Any one of the one or more polymers discussed herein may be used in any exemplary process, for example, as a flocculant. 11
Docket No.: 1149704.054013 [0052] In some embodiments, one or more polymers may comprise one or more monomers of the following: acryloyloxy ethyl trimethyl ammonium chloride ("AETAC"); methacryloyloxyethyltrimethylammonium chloride; methacrylamidopropyltrimethylammonium chloride ("MAPTAC"); acrylamidopropyltrimethylammonium chloride; methacryloyloxyethyldimethylammonium sulfate; dimethylaminoethyl acrylate; dimethylaminopropylmethacrylamide; diallyldimethylammonium chloride ("DADMAC"); calcium diacrylate ("CDA"); acrylamide; acrylic acid; any monomer substituted with a carboxylic acid group or salt thereof; 2‐acrylamido‐2‐methylpropane sulfonic acid ("AMPS"); ethylene oxide; propylene oxide; functionalized ethylene oxide; epoxide; functionalized propylene oxide; epoxy or glycidyl ether functionalized hydrophobic monomers; 1 ,2‐epoxy tetradecane; 2‐ethylhexylglycidyl ether; 2, 2, 3, 3, 4, 4, 5, 5‐ octafluoropentyl ether; benzyl glycidyl ether; 4‐nonylphenyl glycidyl ether; silane‐ or siloxane‐functionalized glycidyl ethers; silane or siloxane‐functionalized monomers; 3‐ glycidyloxypropyl polydimethyl siloxane; 3‐glycidyloxypropyl trimethoxysilane; 3‐ glycidoxypropyldimethylethoxysilane; alkylene oxide; olefin oxide; aliphatic, cycloaliphatic or mixed aliphatic/cycloaliphatic alkylene oxide; alkylene oxide substituted by one or more aromatic radicals; 1,2‐epoxybutane; 2,3‐epoxybutane; the epoxypentanes; the epoxyhexanes; the epoxyoctanes; the epoxydecanes; the epoxydodecanes; 2,4,4‐trimethy1‐1,2‐epoxypentane; 2,4,4‐trimethy1‐2,3‐epoxypentane; cyclohexylepoxythane; 7‐oxabicyclo[4.1.0]heptane; 6‐oxabicyclo[3.1.0]hexane; 3‐methyl‐6‐ oxabicyclo[3.1.0]hexane; 4‐ethy1‐6‐oxabicyclo[3.1.0]hexane; styrene oxide; 1 ‐phenyl‐ 1 ,2‐ epoxypropane; 1,2‐butylene oxide; 2,3‐butylene oxide; the epoxypentanes, the epoxyhexanes; 2,3‐epoxyheptane; nonene oxide; 5‐butyl‐3,4‐epoxyoctane; 1 ,2‐ epoxydodecane; 1,2‐epoxyhexadecane; 1 ,2‐epoxyoctadecane; 5‐benzy1‐2,3‐epoxyheptane; 4‐cyclo‐hexy1‐2,3‐epoxypentane; chlorostyrene oxide; styrene oxide; ortho‐, meta‐, and para‐ethylstyrene oxide; glycidyl benzene; the oxabicycloalkanes; alkyl‐substituted oxabicycloalkanes, e.g., 7‐oxabicyclo[4.1.0]heptane; oxabicyclo[3.1.0]hexane; 4‐propy1‐7‐ oxabicyclo[4.1.0]heptane; and/or 3‐amy1‐6‐oxabicyclo[3.1.0Jhexane.] [0053] As used herein, the term "flocculant" may generally refer to a reagent that may bridge neutralized or coagulated particles into larger agglomerates, typically resulting in more efficient settling. In some embodiments, said flocculants may comprise a polymer, copolymer, and/or terpolymer comprising one or more monomers, wherein said monomers may be one or more nonionic, one or more anionic, and/or one or more cationic monomers. In some embodiments, said flocculants may comprise one or more polymers, copolymers, and/or terpolymers comprising, but not limited to comprising, one or more monomers of the following: acryloyloxy ethyl trimethyl ammonium chloride ("AETAC"); methacryloyloxyethyltrimethylammonium chloride; methacrylamidopropyltrimethylammonium chloride ("MAPTAC"); acrylamidopropyltrimethylammonium chloride; methacryloyloxyethyldimethylammonium sulfate; dimethylaminoethyl acrylate; dimethylaminopropylmethacrylamide; diallyldimethylammonium chloride ("DADMAC"); calcium diacrylate ("CDA"); acrylamide; acrylic acid; any monomer substituted with a carboxylic acid group or salt thereof; 2‐acrylamido‐2‐methylpropane sulfonic acid ("AMPS"); ethylene oxide; propylene oxide; functionalized ethylene oxide; epoxide; functionalized propylene oxide; epoxy or glycidyl ether functionalized hydrophobic monomers; 1 ,2‐epoxy tetradecane; 2‐ethylhexylglycidyl ether; 2, 2, 3, 3, 4, 4, 5, 5‐octafluoropentyl ether; benzyl 12
Docket No.: 1149704.054013 glycidyl ether; 4‐nonylphenyl glycidyl ether; silane‐ or siloxane‐functionalized glycidyl ethers; silane or siloxane‐functionalized monomers; 3‐glycidyloxypropyl polydimethyl siloxane; 3‐glycidyloxypropyl trimethoxysilane; 3‐glycidoxypropyldimethylethoxysilane; alkylene oxide; olefin oxide; aliphatic, cycloaliphatic or mixed aliphatic/cycloaliphatic alkylene oxide; alkylene oxide substituted by one or more aromatic radicals; 1,2‐ epoxybutane; 2,3‐epoxybutane; the epoxypentanes; the epoxyhexanes; the epoxyoctanes; the epoxydecanes; the epoxydodecanes; 2,4,4‐trimethy1‐1,2‐epoxypentane; 2,4,4‐ trimethy1‐2,3‐epoxypentane; cyclohexylepoxythane; 7‐oxabicyclo[4.1.0]heptane; oxabicyclo[3.1.0]hexane; 3‐methyl‐6‐oxabicyclo[3.1.0]hexane; 4‐ethy1‐6‐ oxabicyclo[3.1.0]hexane; styrene oxide; 1 ‐phenyl‐ 1 ,2‐epoxypropane; 1,2‐butylene oxide; 2,3‐butylene oxide; the epoxypentanes, the epoxyhexanes; 2,3‐epoxyheptane; nonene oxide; 5‐butyl‐3,4‐epoxyoctane; 1 ,2‐epoxydodecane; 1,2‐epoxyhexadecane; 1 ,2‐ epoxyoctadecane; 5‐benzy1‐2,3‐epoxyheptane; 4‐cyclo‐hexy1‐2,3‐epoxypentane; chlorostyrene oxide; styrene oxide; ortho‐, meta‐, and para‐ethylstyrene oxide; glycidyl benzene; the oxabicycloalkanes; alkyl‐substituted oxabicycloalkanes, e.g., 7‐ oxabicyclo[4.1.0]heptane; oxabicyclo[3.1.0]hexane; 4‐propy1‐7‐oxabicyclo[4.1.0]heptane; and/or 3‐amy1‐6‐oxabicyclo[3.1.0Jhexane.]. [0054] As used herein the term “process additive” refers to a compound, which differs from the coagulant compound used in the subject tailings treatment processes, that promotes the effects of the coagulant on dewatering, optionally by reducing floc size (e.g., by making flocs less bulky after flocculant addition) and/or by causing floc restructuring to achieve better floc compaction, further optionally a sulfur containing compound; still further a sulfite or sulfate compound, e.g., sodium sulfite (RED agent, antioxidant), sodium persulfate (OX agent), sodium sulfate (buffer, weak base), sodium metabisulfate (alternatively known as sodium dithionate, or Na2S2O6). [0055] As used herein, the term "produced water" generally refers to any aqueous fluids produced during any type of industrial process, e.g., an oil or gas extraction or recovery process, or any portion thereof. Typically the produced water may be obtained during an industrial process involving the use of water, generally copious amounts of water, wherein the end product of such industrial process may be an aqueous material or "produced water" which may be of an undesirable purity. Produced water may be generated during processes or portions thereof which involve oil sands. [0056] As used herein, the term "mechanical dewatering" generally refers to any process that may be used to aid in the dewatering of tailings, e.g., oil sands tailings. In some embodiments, mechanical dewatering may comprise centrifugation, thin lift, and/or thickeners. In some embodiments, mechanical dewatering may comprise centrifugation. [0057] As used herein, the term "introduction" generally refers to any means known in the art by which addition of a substance, e.g., a polymer flocculant, coagulant or process additive, may occur. [0058] As used herein, the terms "polymer introduction", "introduction of a polymer", and "introduction of one or more polymers" generally refer to one or more introductions of one or more polymers, e.g., one or more polymeric flocculants, to a stream. Introductions of polymers may occur one or more times at one or more time‐points and one or more locations during methods of treating tailings. Introductions of polymers may occur by any 13
Docket No.: 1149704.054013 means known in the art that is appropriate for a given polymer and/or for any form of a given polymer, e.g., dry, in emulsion form or, in [aqueous] solution. Detailed Description [0059] Disclosed herein are methods for treating tailings such as oil sands or mining operations derived tailings. In exemplary embodiments, the methods involve flocculating solids in the tailings and the dewatering of tailings. Exemplary methods specifically comprise the addition of one or more flocculants in order to flocculate solids from the tailings, prior to the addition of at least one “process additive” or “process additive” or “additive” or “A”, e.g., a sulfur compound, the addition of which is preferably effected prior to the addition of at least one coagulant or simultaneous thereto. The process additive has surprisingly been demonstrated to boost the cake solids content when added after flocculation has been initiated, e.g., by about 0.5 percent by weight. To the best of the inventors’ knowledge the use of addition of such process additives to further increase solids content in the recovered dewatered tailings, e.g., in the centrifuge cake has not been previously reported. [0060] Also addition of such process additives may further result in one or more of the following: (i) less required energy input compared to mechanical conditioning (e.g., shearing) required to achieve desired cake solids percentages; (ii) shorter mixing times compared to mechanical conditioning (e.g., shearing) required to achieve desired cake solids percentages; (iii) lower dosages of other additives such as flocculants and/or coagulants needed to boost cake solids percentages; and (iv) increased cake solids percentages when the tailings treatment process comprises the addition of the at least one flocculant (F) followed by the addition of the at least one process additive (A), in turn followed by the addition of the at least one coagulant (C) (F‐A‐C); as compared to otherwise similar treatment methods wherein the addition of the at least one flocculant (F) is followed by the addition of at least one coagulant (C) (F‐C); and also compared to otherwise similar tailings treatment methods wherein the addition of the flocculant is followed by the addition of at least one coagulant (C) in turn followed by the addition of at least one process additive (A) (F‐C‐ A). [0061] Further potential advantages of the inventive tailings treatment methods include potentially eliminating the need for pumping the centrifuge cake (in relation to conventional methods wherein the centrifuge cake comprises higher water content and reduced cake solids percentages) thereby potentially permitting the centrifuge cake which comprises high cake solids percentages to be transported off‐site, e.g., by use of truck or train, to a deposition site, thereby further reducing energy costs and increasing process efficiency. [0062] As disclosed herein the at least one flocculant may comprise any reagent that may bridge neutralized or coagulated particles into larger agglomerates, typically resulting in more efficient settling. In some embodiments, said flocculants may comprise a polymer, copolymer, and/or terpolymer comprising one or more monomers, wherein said monomers 14
Docket No.: 1149704.054013 may be one or more nonionic, one or more anionic, and/or one or more cationic monomers. In some embodiments, said flocculants may comprise one or more polymers, copolymers, and/or terpolymers comprising, but not limited to comprising, one or more monomers of the following: acryloyloxy ethyl trimethyl ammonium chloride ("AETAC"); methacryloyloxyethyltrimethylammonium chloride; methacrylamidopropyltrimethylammonium chloride ("MAPTAC"); acrylamidopropyltrimethylammonium chloride; methacryloyloxyethyldimethylammonium sulfate; dimethylaminoethyl acrylate; dimethylaminopropylmethacrylamide; diallyldimethylammonium chloride ("DADMAC"); calcium diacrylate ("CDA"); acrylamide; acrylic acid; any monomer substituted with a carboxylic acid group or salt thereof; 2‐acrylamido‐2‐methylpropane sulfonic acid ("AMPS"); ethylene oxide; propylene oxide; functionalized ethylene oxide; epoxide; functionalized propylene oxide; epoxy or glycidyl ether functionalized hydrophobic monomers; 1 ,2‐epoxy tetradecane; 2‐ethylhexylglycidyl ether; 2, 2, 3, 3, 4, 4, 5, 5‐octafluoropentyl ether; benzyl glycidyl ether; 4‐nonylphenyl glycidyl ether; silane‐ or siloxane‐functionalized glycidyl ethers; silane or siloxane‐functionalized monomers; 3‐glycidyloxypropyl polydimethyl siloxane; 3‐glycidyloxypropyl trimethoxysilane; 3‐glycidoxypropyldimethylethoxysilane; alkylene oxide; olefin oxide; aliphatic, cycloaliphatic or mixed aliphatic/cycloaliphatic alkylene oxide; alkylene oxide substituted by one or more aromatic radicals; 1,2‐ epoxybutane; 2,3‐epoxybutane; the epoxypentanes; the epoxyhexanes; the epoxyoctanes; the epoxydecanes; the epoxydodecanes; 2,4,4‐trimethy1‐1,2‐epoxypentane; 2,4,4‐ trimethy1‐2,3‐epoxypentane; cyclohexylepoxythane; 7‐oxabicyclo[4.1.0]heptane; oxabicyclo[3.1.0]hexane; 3‐methyl‐6‐oxabicyclo[3.1.0]hexane; 4‐ethy1‐6‐ oxabicyclo[3.1.0]hexane; styrene oxide; 1 ‐phenyl‐ 1 ,2‐epoxypropane; 1,2‐butylene oxide; 2,3‐butylene oxide; the epoxypentanes, the epoxyhexanes; 2,3‐epoxyheptane; nonene oxide; 5‐butyl‐3,4‐epoxyoctane; 1 ,2‐epoxydodecane; 1,2‐epoxyhexadecane; 1 ,2‐ epoxyoctadecane; 5‐benzy1‐2,3‐epoxyheptane; 4‐cyclo‐hexy1‐2,3‐epoxypentane; chlorostyrene oxide; styrene oxide; ortho‐, meta‐, and para‐ethylstyrene oxide; glycidyl benzene; the oxabicycloalkanes; alkyl‐substituted oxabicycloalkanes, e.g., 7‐ oxabicyclo[4.1.0]heptane; oxabicyclo[3.1.0]hexane; 4‐propy1‐7‐oxabicyclo[4.1.0]heptane; and/or 3‐amy1‐6‐oxabicyclo[3.1.0Jhexane.]. [0063] In preferred embodiments the at least one flocculant will comprise an anionic polymer which comprises one or more anionic monomers, which comprises greater than 0% or more to about 100 mol% of a charged monomer or from about 20 mol% to about 95 mol% of a charged monomer, or from about 50% or more to about 95% or more mol% of a charged monomer; or comprises an acrylamide flocculant that comprises from greater than 0 mol% or more to about 100 mol% of a charged monomer, such as an anionic monomer, or from about 50% or more to about 95% or more mol% of a charged monomer, such as an anionic monomer or comprises 20‐45 mol% or 50 mol% or more of a charged monomer such as an anionic monomer. [0064] In preferred embodiments the at least one flocculant will comprise an anionic polymer which comprises one or more anionic monomers, which are selected from acrylic acid, sodium acrylate, ammonium acrylate, methacrylic acid, 2‐acrylamido‐2‐ methylpropanesulfonic acid (AMPS), vinyl sulfonic acid, styrene sulfonic acid, maleic acid, sulfopropyl acrylate or methacrylate or other water‐soluble forms of these or other polymerizable carboxylic or sulphonic acids, sulfomethylated acrylamide, allyl sulfonate, 15
Docket No.: 1149704.054013 itaconic acid, acrylamidomethylbutanoic acid, fumaric acid, vinylphosphonic acid, allylphosphonic acid, phosphonomethylated acrylamide, methacrylate, itaconate, 2‐ acrylamido 2‐methyl propane sulphonate, sulfoalkyl(meth)acrylic acids, sulfonated styrenes, unsaturated dicarboxylic acids, sulfoalkyl(meth)acrylamides, vinyl acetate, n‐ vinylformamide, n‐vinylacetamide, n‐vinylcaprolactam, n‐vinylimidazole, n‐vinylpyridine, n‐ vinylpyrolidone, acrylamidopropyltrimonium chloride, salts of said acids and the like, or another anionic ethylenically unsaturated compound, and preferably comprises acrylic acid, methacrylic acid, maleic acid monomers, calcium diacrylate, and/or any monomer substituted with a carboxylic acid group or salt thereof, a (meth)acrylamide monomer wherein the amide group has been hydrolyzed to a carboxyl group, monomers comprising sulfonic acids or a sulfonic acid group, or both, 2‐acrylamido‐2‐methylpropane sulfonic acid (“ATBS"), or combinations thereof, and more preferably comprises acrylic acid and/or ATBS. [0065] In some exemplary embodiments the at least one flocculant will comprise an anionic acrylamide copolymer, further optionally a copolymer comprising PAM acrylic acid (AA), and/or ATBS, e.g., an anionic flocculant which comprises greater than 0% or more to about 100 mol% of a charged monomer or from about 20 mol% to about 95 mol% of a charged monomer, or from about 50% or more to about 95% or more mol% of a charged monomer; or comprises an acrylamide flocculant that comprises from greater than 0 mol% or more to about 100 mol% of a charged monomer, such as an anionic monomer, or from about 50% or more to about 95% or more mol% of a charged monomer, such as an anionic monomer or comprises 20‐45 mol% or 50 mol% or more of a charged monomer such as an anionic monomer. [0066] In more preferred embodiments the at least one flocculant will comprise an anionic polymer, typically an anionic polymer flocculant which comprises an acrylamide copolymer, optionally a copolymer comprising PAM acrylic acid (AA), and/or ATBS, or comprises an anionic polymer which comprises a copolymer comprising PAM and acrylic acid (AA), optionally 25‐35 mol% AA, or 15‐40% AA; optionally wherein the anionic polymer flocculant comprises a standard viscosity (SV) ranging from 3‐5, 3.1‐4.1, or 3.2‐4.0. [0067] In some embodiments the molecular weight of the polymer flocculant, e.g., an anionic polymer, optionally an anionic polymer flocculant which comprises an acrylamide copolymer, further optionally a copolymer comprising PAM acrylic acid (AA), and/or ATBS, or an anionic polymer which comprises a copolymer comprising PAM and acrylic acid (AA), optionally 25‐35 mol% AA, or 15‐40% AA; will range from 500 Da to 200,000,000 Da, or from 10,000 Da to 100,000,000 Da, or from 10,000 Da to 50,000,000 Da or from 10,000 Da to 20,000,000 Da, or from 10,000 Da to 10,000,000 Da or from 10,000 Da to 1,000,000 Da or from 10,000 Da to 500,000 Da or from 10,000 Da to 100,000 Da. [0068] In exemplary embodiments the at least one flocculant may comprises a dry polymer, an emulsion or an aqueous solution; e.g., a dry polyacrylamide polymer (DPAM). [0069] The amount of the at least one flocculant added to the tailings will vary dependent on the particular flocculant or flocculants added, and the composition of the treated tailings. In some instances the amount of the at least one flocculant added to the tailings may range from about 50 to about 100000 g/t dry tailings or more typically about 500 to about 10000 g/t dry tailings. [0070] As mentioned earlier, after the addition of the at least one flocculant, at least one process additive is added to the tailings, e.g., a sulfur containing compound or other 16
Docket No.: 1149704.054013 compound which boosts cake solids content in association with the coagulant. Generally the process additive is added from about 10 sec – 10 min after the at least one flocculant, more typically is about 30 ‐ 60 sec after the at least one flocculant or is added after a time sufficient for flocs to form. Preferably the process additive will be added after flocs have formed, and relatively soon thereafter, because if too much time occurs between flocculant addition and the addition of the process additive mixing may result in mechanical breakage or modification of the flocs that form after the addition of the at least one flocculant. [0071] Typically the at least one process additive comprises a sulfur containing compound, and optionally comprises a sulfite or sulfate compound. In some exemplary embodiments the at least one process additive (A) comprises sodium sulfite (RED agent, antioxidant), sodium persulfate (OX agent), sodium sulfate (buffer, weak base), sodium metabisulfate (also referred to as Sodium dithionate, or Na2S2O6). [0072] In some exemplary embodiments the at least one process additive is added in dry form or as an aqueous composition, e.g., a 0.1‐10% aqueous solution (as many of these process additives are highly aqueous soluble), and in a specific exemplary embodiment a 0.2% solution comprising deionized (DI) water. Generally after or concomitant to the addition of the at least one process additive, at least one coagulant is added to the treated tailings stream. The at least one coagulant typically comprises a cationic coagulant or an acidic coagulant. Such coagulants may include organic and inorganic coagulants. [0073] Examples thereof include poly(diallyl dimethyl ammonium chloride) compound; an epi‐polyamine compound; a polymer that contains one or more quaternized ammonium groups, such as acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride, or acrylamidopropyltrimethylammonium chloride; aluminum sulfate, ferric chloride, lime, calcium chloride, magnesium chloride, or another iron or aluminum salts coagulants; gypsum; sulfuric acid or aluminum sulfate (ALS); organic polymeric coagulant, optionally of low MW (e.g., ≈300,000 ‐≈500,000 Da); cationic organic polyamines, polyDADMAC coagulant, optionally of low MW (e.g., ≈300,000 ‐≈500,000 Da). [0074] The at least one cationic coagulant is generally added in liquid form. [0075] The dosage range of the at least one coagulant will vary dependent on the particular coagulant and/or the composition of the treated tailings. A typical dosage may ranges from 200‐8000 ppm or 500‐6000 ppm. [0076] In exemplary embodiments the pH of the tailings is typically around 8 prior to the addition of the at least one flocculant, process additive, and coagulant. By contrast the pH of the tailings after the addition of the coagulant typically is reduced to about 5‐6. Preferably the pH is not reduced so much that it results in the release of Ca into the release water. [0077] In exemplary embodiments the at least one flocculant, process additive, and coagulant are added in line prior to mechanical dewatering. [0078] In exemplary embodiments after the addition of the at least one flocculant, process additive, and coagulant the solids are separated from the tailings stream by one or more of centrifugation, hydrocycloning, decantation, filtration, thickening or another mechanical separation. Preferably mechanical separation is effected by use of centrifugation methods. 17
Docket No.: 1149704.054013 Mechanical methods and apparatus used for separating solids from tailings streams are well known and available. [0079] In some embodiments the process may further comprise a desanding step. [0080] In some embodiments the process may result in one or more of the following benefits: (i) reduction in solids content in tailings; (ii) reduction of turbidity in tailings; (iii) reduced chemical oxygen demand; (iv) improved flocculation at lower flocculant dosages; (v) reduced solids content in treated tailings and changed tailings composition; (vi) improved removal of fine, slow settling clay particles, persistent contaminants, and/or residual bitumen; (vii) reduced formation of non‐segregated tailings; (viii) increased water release; (ix) a desirable degree of floe formation; or (x) a combination of any of the foregoing; as compared to a method wherein the at least one process additive is not added. [0081] Without being bound by this theory it is speculated that the mechanism of action responsible for the surprising results attained by the inventive treatment methods may be because of one or more of the following: (a) The addition of flocculant forms flocs, which may be variable in size. Large flocs are easily separated, but not readily compacted; (b) The addition of the process additive (A) modifies the rheology thereof by reducing floc size to make less bulky, after flocculant (F) addition; e.g., the addition of the process additive (A) may results in floc restructuring resulting in achieve better compaction; (c) If the coagulant C is acidic, the order of addition may be important in order to maintain the pH in optimal range, reason why the coagulant is preferably added last ; and (d) Adding A at end (e.g., F‐C‐A) may result in less optimal results due to pH change (reduction) after addition of an acidic coagulant (C). [0082] In other embodiments the invention provides tailings compositions produced by any of the methods described herein. [0083] In exemplary embodiments the treated tailings composition may be derived from an oil sands separation process. [0084] In other exemplary embodiments the treated tailings composition may be derived from a mining separation process. 18
Docket No.: 1149704.054013 [0085] In some exemplary embodiments, the resulting dewatered solids may be handled or may be processed in any manner as necessary or desired. In some exemplary embodiments, the dewatered solids may be handled in compliance with governmental regulations. In some exemplary embodiments, the resultant solids may be disposed of, may be sent to a tailings pond for additional settling, or when solids may be a concentrated source of minerals, the solids may be used a raw materials or feed to produce compounds for commercial products. In some exemplary embodiments, the separated water may be handled or may be processed in any manner as necessary or desired. In an exemplary embodiment, the separated water may be recycled to the process ("recycled water"). For example, the recycled water may be added to the crushed oil sands ore for bitumen extraction. Recycled water may also be added to the process at any point where water may be added. [0086] Having described the invention in detail the invention is further described in the following examples. While the invention has been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations and substitutions may be applied to the compositions and/or methods described herein without departing from the concept, spirit and scope of the disclosure. Examples MATERIALS & METHODS Materials [0087] Oil Sands Mature Fine Tailings [0088] Oil Sands Mature Fine Tailings (MFT) with solids content of 26% was used. The material was homogenized by overhead mixer before the flocculation tests. [0089] Anionic polymer Flocculant [0090] An anionic flocculant, specifically a polyacrylamide‐Acrylic Acid copolymer (Acrylic Acid %: 27%), was dissolved to a 0.4% solution using CNRL synthetic process water. [0091] Coagulant [0092] Sulfuric acid was used as coagulant. Process additives, such as sodium sulfite, sodium persulfate, sodium sulfate, sodium metabisulfate were prepared as 0.2% solution using DI water. Methods [0093] The MFT sample (500 g) was transferred into a 1L beaker. The sample was first pre‐ mixed at 300 rpm for 2 min with an overhead mixer. The mixing speed was fix at 300 rpm throughout each test. As an example, for one sequence of injection (flocculant‐ process additive ‐coagulant; F‐A‐C) each chemical was added into the MFT and mixed for 1 min followed by the addition of the next chemical defined in the above sequence. [0094] Again the coagulant used is an anionic dry polymer (polyacrylamide‐Acrylic Acid copolymer (Acrylic Acid %: 27%)), was used as the flocculant in all the experiments. The flocculated material was transferred to a 50 ml centrifuge tube and then centrifuged at 910 rcf for 2.5 min. 19
Docket No.: 1149704.054013 [0095] After centrifugation, the solids of the supernatant and centrifuge cake were weighted and then placed in the oven to dry at 100 °C. After drying, the weight was recorded and the solids % was obtained for the supernatant and the centrifuge cake. Example 1: Evaluation of different mixing energies and mixing times on cake solids% at specific F‐C dosages [0096] Mechanical conditioning was evaluated at different mixing energies (impeller speed from overhead mixer). As shown in Table 1 below higher mixing speeds and mixing times were needed to improve the cake solids % at specific F‐C dosages. [0097] Table 1. Coagulant (Anionic polyacrylamide‐Acrylic Acid copolymer; Actual AA%: 27%). dosage: 1100 ppm, sulfuric acid dosage: 3300 ppm Mixing time Mixing Mixing time Centrate (Process Cake solids%
Example 2: Effects of the Addition of Sodium Persulfate or Sodium Sulfate as Process Additive in comparison to “Polymer only” and “Polymer + Coagulant” [0098] Several process additives, in combination with the flocculant and coagulant, were found to be capable of improving the centrifuge cake solids while maintaining or lowering the centrate solids %. When using “polymer only” in the treatment, 43.6% cake solids was achieved. [0099] When adding coagulant after the polymer, cake solids% improved to 48.6% (+5.0% increase). Adding the process additive after polymer addition also provided improvement on the cake solids (~46.8%; +3.2% increase). Additionally, when the process additive was introduced in a F‐A‐C sequence, a surprising further improvement on the cake solids was observed. [0100] This indicates that a synergistic effect is elicited between the coagulant and the process additive. Particularly, as shown in the table, a centrifuge cake with 50.7% solids was obtained when adding 20 ppm sodium sulfite in between the polymer and coagulant (+7.1% increase compared with polymer only treatment). Two different injection sequences, flocculant‐ process additive ‐coagulant (F‐A‐C) and flocculant‐coagulant‐ process additive (F‐ C‐A), were examined. 20
Docket No.: 1149704.054013 [0101] As shown in Table 2 and Table 3 below the results indicate that F‐A‐C provided a superior performance compared to F‐C‐A (see Table 2 and Table 3). Also, the results demonstrate that a low dosage of the process additive is sufficient to improve the cake solids % and that further increasing the dosage of the process additive does not result in a significant effect in further improving cake solids %. [0102] Table 2. Centrifugation results using Sodium Persulfate as Process additive in comparison with “Polymer only” and “Polymer + Coagulant” (anionic polyacrylamide‐ Acrylic Acid Copolymer; actual AA%: 27%) dosage = 1100 ppm) Coagulant Coagulant Process Process Injection Dosage additive Additive Sequence Centrate Cake
er first and then the process additive; F‐C‐A = polymer – coagulant – process additive; F‐A‐C = polymer – process additive – coagulant. [0103] Table 3. Centrifugation results using Sodium Sulfite as Process additive in comparison with “Polymer only” and “Polymer + Coagulant” (anionic polyacrylamide‐ Acrylic Acid copolymer, AA%: 27%) dosage = 1100 ppm for all the tests) 21
Docket No.: 1149704.054013 Coagulant Coagulant Process Process Injection Dosage Additive Additive Sequence Centrate Cake
er first and then process additive; F‐C‐A = polymer – coagulant – process additive; F‐A‐C = polymer – process additive – coagulant. Example 3: Effects of the Addition of Sodium Persulfate or Sodium Sulfate as Process Additive in comparison to “Polymer only” and “Polymer + Coagulant” [0104] Several process additives, in combination with the flocculant and coagulant, were found to be capable of improving the centrifuge cake solids while maintaining or lowering the centrate solids %. [0105] An additional MFT feed was tested which required higher polymer dosage (1200 ppm) to achieve similar results from Table 2 and Table 3 (polymer only data). In this case, for a slightly higher polymer dosage a higher additive dosage was required to achieved improved 22
Docket No.: 1149704.054013 cake solids % compared to F only and F‐C sequence. Additional additives were also successful in increasing cake solids % while maintaining low centrate solids %. [0106] The results of these experiments are summarized in Table 4 below. [0107] Table 4. Centrifugation results by using other Process Additives in comparison with “Polymer only” and “Polymer + Coagulant” (coagulant comprises anionic polyacrylamide‐ Acrylic Acid copolymers (AA%: 27%). dosage = 1200 ppm for all the tests) Process Coagulant Process Additive Injection Centrate Cake
[0108] CONCLUSIONS [0109] The results of the experiments disclosed herein reveal that: (a) The addition of different tested process additives surprisingly boosted cake solids content (≈0.5 % increase) when added after flocculation but before pH adjustment; (b) The addition of F forms flocs, which may be variable in size. Large flocs are easily separated, but not readily compacted; accordingly the addition of the process additive A may modify rheology, e.g., by reducing floc size to make the flocs less bulky after flocculant addition, and/or by causing floc restructuring in order to achieve better compaction; (c) The addition of the coagulant C, if acidic, effected after addition of the process additive A may be important for maintaining the pH in optimal range; i.e., adding 23
Docket No.: 1149704.054013 C last is preferred; and (d) Adding the process additive A at end (e.g., F‐C‐A) was not ideal perhaps due to pH change after addition of C. [0110] The observed benefits are unexpected and significant, i.e., (≈0.5 % increase in solids) given the vast volumes involved when treating tailings streams. [0111] In addition the tailing treatment methods disclosed herein may result in one or more of the following: (i) reduction in solids content in tailings; (ii) reduction of turbidity in tailings; (iii) reduced chemical oxygen demand; (iv) improved flocculation at lower flocculant dosages; (v) reduced solids content in treated tailings and changed tailings composition; (vi) improved removal of fine, slow settling clay particles, persistent contaminants, and/or residual bitumen; (vii) reduced formation of non‐segregated tailings; (viii) increased water release; (ix) a desirable degree of floc formation; (x) improved economics; (xi) improved process efficiency; or (xii) a combination of any of the foregoing; as compared to an otherwise similar tailings treatment method wherein the at least one process additive, e.g., a sulfur containing compound, is not added. [0112] Having described the inventive methods and compositions in terms of preferred embodiments, the invention is further defined by the claims which follow: 24
Claims
Docket No.: 1149704.054013 CLAIMS We claim: 1. A method for treating tailings, wherein said tailings comprise an aqueous phase with suspended solid particulate material, the method comprising (a) contacting tailings which are to be dewatered with at least one flocculant, preferably an anionic, nonionic, and/or cationic flocculant, more preferably an anionic polymer flocculant, and allowing at least a portion of the solids to flocculate; (b) adding at least one process additive, optionally a sulfur containing compound; and (c) adding at least one coagulant, optionally an acidic or cationic coagulant; wherein steps (b) and (c) are performed after step (a), in any order or simultaneously. 2. The method of claim 1, wherein step (b) is effected prior to step (c). 3. The method of claim 1 or 2, wherein the time between step (a) and (b) typically ranges from about 10 sec – 10 min, more typically is about 30 ‐ 60 sec and/or is a time sufficient for flocs to form. 4. The method of claim 1, 2 or 3, wherein the tailings are obtained from an oil sands separation process. 5. The method of claim 1, 2 or 3, wherein the tailings are obtained from a mining separation process. 6. The method of any one of claims 1‐5, wherein: (i) the at least one flocculant comprises an anionic polymer; (ii) the at least one flocculant comprises an anionic polymer which comprises one or more of acrylic acid, sodium acrylate, ammonium acrylate, methacrylic acid, 2‐acrylamido‐2‐methylpropanesulfonic acid (ATBS), vinyl sulfonic acid, styrene sulfonic acid, maleic acid, sulfopropyl acrylate or methacrylate or other water‐soluble forms of these or other polymerizable carboxylic or sulphonic acids, sulfomethylated acrylamide, allyl sulfonate, itaconic acid, acrylamidomethylbutanoic acid, fumaric acid, vinylphosphonic acid, allylphosphonic acid, phosphonomethylated acrylamide, methacrylate, itaconate, 2‐acrylamido 2‐methyl propane sulphonate, sulfoalkyl(meth)acrylic acids, sulfonated styrenes, unsaturated dicarboxylic acids, sulfoalkyl(meth)acrylamides, vinyl acetate, n‐vinylformamide, n‐ vinylacetamide, n‐vinylcaprolactam, n‐vinylimidazole, n‐vinylpyridine, n‐ vinylpyrolidone, acrylamidopropyltrimonium chloride, salts of said acids and the like, or another anionic ethylenically unsaturated compound, and preferably comprises acrylic acid, methacrylic acid, maleic acid monomers, 25
Docket No.: 1149704.054013 calcium diacrylate, and/or any monomer substituted with a carboxylic acid group or salt thereof, a (meth)acrylamide monomer wherein the amide group has been hydrolyzed to a carboxyl group, monomers comprising sulfonic acids or a sulfonic acid group, or both, 2‐acrylamido‐2‐methylpropane sulfonic acid (“ATBS"), or combinations thereof, and more preferably comprises acrylic acid or ATBS; (iii) the at least one flocculant is an anionic polymer which comprises (meth)acrylic acid or a salt thereof, optionally a sodium, calcium, ammonium salt; (iv) the at least one flocculant comprises an anionic polymer flocculant which comprises a nonionic monomer, optionally acrylamide, N‐alkylacrylamides, N,N‐dialkylacrylamides, methacrylamide, N‐vinylmethylacetamide or formamide, vinyl acetate, vinyl pyrrolidone, alkyl methacrylates, acrylonitrile, N‐vinylpyrrolidone other acrylic (or other ethylenically unsaturated) ester or other water insoluble vinyl monomers such as styrene or acrylonitrile and preferably comprises acrylamide; (v) the at least one flocculant comprises an anionic polymer flocculant which comprises an acrylamide copolymer, optionally a copolymer comprising PAM acrylic acid (AA), and/or ATBS; (vi) the at least one flocculant comprises an anionic flocculant which comprises greater than 0% or more to about 100 mol% of a charged monomer or from about 20 mol% to about 95 mol% of a charged monomer, or from about 50% or more to about 95% or more mol% of a charged monomer; (vii) the at least one flocculant comprises an acrylamide flocculant that comprises from greater than 0 mol% or more to about 100 mol% of a charged monomer, such as an anionic monomer, or from about 50% or more to about 95% or more mol% of a charged monomer, such as an anionic monomer or comprises 20‐45 mol% or 50 mol% or more of a charged monomer such as an anionic monomer; (viii) the at least one flocculant comprises an anionic polymer which comprises a copolymer comprising PAM and acrylic acid (AA), optionally 25‐35 mol% AA, or 15‐40% AA; (ix) the at least one flocculant comprises an anionic polymer, wherein the anionic polymer flocculant comprises a standard viscosity (SV) ranging from 3‐5, 3.1‐ 4.1, or 3.2‐4.0; (x) the molecular weight of the polymer flocculant ranges from 500 Da to 200,000,000 Da, or from 10,000 Da to 100,000,000 Da, or from 10,000 Da to 50,000,000 Da or from 10,000 Da to 20,000,000 Da, or from 10,000 Da to 10,000,000 Da or from 10,000 Da to 1,000,000 Da or from 10,000 Da to 500,000 Da or from 10,000 Da to 100,000 Da;
Docket No.: 1149704.054013 (xi) the at least one flocculant comprises a dry polymer, an emulsion or an aqueous solution; (xii) the amount of the at least one flocculant added ranges from 50 to about 100000 g/t dry tailings or from about 500 to about 10000 g/t dry tailings; or (xiii) any combination of the foregoing. 7. The method of any one of claims 1‐6, wherein the at least one process additive comprises a sulfur containing compound, which differs from the added coagulant, and optionally comprises a sulfite or sulfate compound. 8. The method of any one of claims 1‐7, wherein the at least one process additive comprises sodium sulfite (RED agent, antioxidant), sodium persulfate (OX agent), sodium sulfate (buffer, weak base), sodium metabisulfate (alternatively known as sodium dithionate, or Na2S2O6). 9. The method of any one of claims 1‐8, wherein the at least one process additive is added in dry form or as an aqueous composition, optionally a 0.2% solution comprising deionized (DI) water. 10. The method of any one of claims 1‐9, wherein the dosage of the at least one process additive ranges from about 5‐100 g/ton or about 20‐50 g/ton. 11. The method of any one of claims 1‐10, wherein (i) the at least one coagulant comprises a cationic coagulant, and optionally comprises an acidic coagulant; (ii) the at least one coagulant comprises an organic or inorganic coagulant; (iii) the at least one coagulant comprises an inorganic coagulants such as inorganic salts such as aluminum sulfate, polyaluminum chloride, polyaluminum silica sulfate, ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, lime, calcium chloride, calcium sulfate, magnesium chloride, or various commercially available iron or aluminum salts coagulants; (iv) the at least one cationic coagulant is a poly(diallyl dimethyl ammonium chloride) compound; an epi‐polyamine compound; a polymer that contains one or more quaternized ammonium groups, such as acryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride, or acrylamidopropyltrimethylammonium chloride; aluminum sulfate, ferric chloride, lime, calcium chloride, magnesium chloride, or another iron or aluminum salts coagulants; (v) the at least one coagulant comprises gypsum; (vi) the at least one coagulant comprises sulfuric acid or aluminum sulfate (ALS); (vii) the at least one coagulant comprises an organic polymeric coagulant, 27
Docket No.: 1149704.054013 optionally of low MW (e.g., ≈300,000 ‐≈500,000 Da); (viii) the at least one coagulant comprises a cationic organic polyamine, or polyDADMAC coagulant, optionally of low MW (e.g., ≈300,000 ‐≈500,000 Da); (ix) the at least one coagulant is added in liquid form; (x) the dosage range of the at least one coagulant ranges from 200‐8000 ppm or 500‐6000 ppm; or (xi) any combination of the foregoing. 12. The method of any one of claims 1‐11, wherein (i) the pH of the tailings is around 8 prior to the addition of the at least one flocculant, process additive, and coagulant; (ii) the pH of the tailings after the addition of the coagulant typically is reduced to about 5‐6, and preferably is not reduced to a level which results in the release of Ca into release water; (iii) the at least one flocculant, process additive, and coagulant are added in line prior to mechanical dewatering; (iv) the total dosage of the flocculant is about 500 to about 10000 g/t dry tailings; or (v) any combination of the foregoing. 13. The method of any one of claims 1‐12, wherein after the addition of the at least one flocculant, process additive, and coagulant the solids are separated from the tailings stream by one or more of centrifugation, hydrocycloning, decantation, filtration, thickening or another mechanical separation; and optionally further comprises a desanding step. 14. The method of any one of claims 1‐13, which results in one or more of the following; (i) reduction in solids content in tailings; (ii) reduction of turbidity in tailings; (iii) reduced chemical oxygen demand; (iv) improved flocculation at lower flocculant dosages; (v) reduced solids content in treated tailings and changed tailings composition; (vi) improved removal of fine, slow settling clay particles, persistent contaminants, and/or residual bitumen; (vii) reduced formation of non‐segregated tailings; (viii) increased water release; (ix) a desirable degree of floe formation; or (x) a combination of any of the foregoing; as compared to a method wherein the 28
Docket No.: 1149704.054013 at least one process additive is not added. 15. A tailings composition produced by a method according to any one of claims 1‐14, optionally derived from an oil sands or mining separation process. 29
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202263477328P | 2022-12-27 | 2022-12-27 | |
| US63/477,328 | 2022-12-27 | ||
| FI20235309 | 2023-03-16 | ||
| FI20235309 | 2023-03-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024145372A1 true WO2024145372A1 (en) | 2024-07-04 |
Family
ID=91719291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2023/086056 Ceased WO2024145372A1 (en) | 2022-12-27 | 2023-12-27 | Treatment of tailings using synergistic combination of flocculant, coagulant, and 'process additive' |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2024145372A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118772332A (en) * | 2024-07-19 | 2024-10-15 | 安徽理工大学 | A hydrophobic flocculant and its preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012088291A1 (en) * | 2010-12-21 | 2012-06-28 | Kemira Oyj | Processes for flocculating tailings streams of the oil prospection |
| WO2013016821A1 (en) * | 2011-07-29 | 2013-02-07 | Xogen Technologies Inc. | System and method for oil sands tailings treatment |
| US20190152823A1 (en) * | 2016-02-24 | 2019-05-23 | Suncor Energy Inc. | Treatment of thick fine tailings including chemical immobilization, polymer flocculation and dewatering |
| CA3048297A1 (en) * | 2019-07-02 | 2019-09-05 | Imperial Oil Resources Limited | Oil sand tailings treatment using flocculation and treatment with a coagulant and a silicate |
| US20190375994A1 (en) * | 2018-06-12 | 2019-12-12 | Kemira Oyj | Methods of treating tailings |
-
2023
- 2023-12-27 WO PCT/US2023/086056 patent/WO2024145372A1/en not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012088291A1 (en) * | 2010-12-21 | 2012-06-28 | Kemira Oyj | Processes for flocculating tailings streams of the oil prospection |
| WO2013016821A1 (en) * | 2011-07-29 | 2013-02-07 | Xogen Technologies Inc. | System and method for oil sands tailings treatment |
| US20190152823A1 (en) * | 2016-02-24 | 2019-05-23 | Suncor Energy Inc. | Treatment of thick fine tailings including chemical immobilization, polymer flocculation and dewatering |
| US20190375994A1 (en) * | 2018-06-12 | 2019-12-12 | Kemira Oyj | Methods of treating tailings |
| CA3048297A1 (en) * | 2019-07-02 | 2019-09-05 | Imperial Oil Resources Limited | Oil sand tailings treatment using flocculation and treatment with a coagulant and a silicate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118772332A (en) * | 2024-07-19 | 2024-10-15 | 安徽理工大学 | A hydrophobic flocculant and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11560323B2 (en) | Compositions of dry acid polymers and uses thereof | |
| US9540469B2 (en) | Multivalent polymers for clay aggregation | |
| CA2822091C (en) | Processes for flocculating tailings streams of the oil prospection | |
| CA2918391C (en) | Processes for treating tailings streams | |
| CA2909388A1 (en) | Oil sands fluid fine tailings dewatering using additives | |
| US11242492B2 (en) | Methods of treating tailings | |
| US11738292B2 (en) | Terpolymers for oil sands tailings treatment | |
| WO2024145372A1 (en) | Treatment of tailings using synergistic combination of flocculant, coagulant, and 'process additive' | |
| US9487610B2 (en) | Low molecular weight multivalent cation-containing acrylate polymers | |
| AU2013212579B2 (en) | Method for dispersing and aggregating components of mineral slurries | |
| CA2876660C (en) | Processes for treating tailings streams | |
| CA2978248C (en) | Terpolymers for oil sands tailings treatment | |
| CA3010053C (en) | Methods of tailings treatment | |
| WO2024145379A1 (en) | Chemical treatment train for tailings with high solids content | |
| WO2020028824A1 (en) | Systems and methods for treating tailings | |
| CA3013884A1 (en) | Systems and methods for treating tailings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23913666 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 23913666 Country of ref document: EP Kind code of ref document: A1 |



