EP2948230A1 - Procédés et systèmes de récupération d'eau - Google Patents

Procédés et systèmes de récupération d'eau

Info

Publication number
EP2948230A1
EP2948230A1 EP13872861.3A EP13872861A EP2948230A1 EP 2948230 A1 EP2948230 A1 EP 2948230A1 EP 13872861 A EP13872861 A EP 13872861A EP 2948230 A1 EP2948230 A1 EP 2948230A1
Authority
EP
European Patent Office
Prior art keywords
water
aqueous solution
organic phase
oil
wastewater stream
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13872861.3A
Other languages
German (de)
English (en)
Other versions
EP2948230A4 (fr
Inventor
Aharon Eyal
Carmi Raz
Paul Mcwilliams
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solex Water Ltd
Original Assignee
Solex Water Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Solex Water Ltd filed Critical Solex Water Ltd
Publication of EP2948230A1 publication Critical patent/EP2948230A1/fr
Publication of EP2948230A4 publication Critical patent/EP2948230A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0488—Flow sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0415—Solvent extraction of solutions which are liquid in combination with membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • 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
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits
    • 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
    • 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
    • C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
    • 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
    • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • C02F2103/322—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters from vegetable oil production, e.g. olive oil production
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents

Definitions

  • the invention is in the field of water treatment.
  • Water like many other natural resources, is present on earth in a finite amount. More than 95% of the water on Earth is present as brackish water or sea water containing a salt concentration which renders it unsuitable for many purposes.
  • the bulk of total water consumption in the world is in industrial processes, including use as a cooling medium.
  • Induced hydraulic fracturing for production of natural gas and other petrochemicals from shale also consumes significant amounts of water. It is estimated that 20% to more than 40% of fracking water is recovered either as flow-back water or as produced water. In the state of Pennsylvania alone the amount of high-TDS (total dissolved solids) wastewater produced by fracking and needing disposal was projected to reach to 7300 million gallons per year in 2011 by the natural gas industry. Levels of salt in fracking water can be more than six times higher than in sea water.
  • a broad aspect of the invention relates to separation of usable water from a stream of water containing hydrophilic, or water soluble, contaminants.
  • the stream is an effluent from an industrial process and the usable water is sufficiently purified to be re-used in the same industrial process.
  • bi-directional solvent indicates an organic solvent, which is characterized in that on equilibrating at 20°C with 5% (w/w) NaCl aqueous solution, solvent concentration in the aqueous phase is at least 1% and less than 50% (W/W) and water concentration in the solvent phase is at least 5% and less than 50% (W/W) or a mixture of two or more such solvents.
  • bi-directional solvents include, but are not limited to alcohols of 3 to 6 carbons and/or ketones of 3 to 6 carbons and/or esters of 3 to 6 carbons and/or organic acids of 3 to 6 carbons and amines.
  • the bi-directional solvent includes butanol.
  • butanol is the primary active component in a mixture of bi- directional solvents.
  • butanol serves as the sole active bi-directional solvent.
  • one or more bi-directional solvents comprises one or more members of the group consisting of normal butanol, secondary butanol, isobutanol, tertiary butanol, normal pentanol, secondary pentanol, isopentanol and tertiary pentanol.
  • one or more bi-directional solvents are provided as an extractant.
  • the extractant includes components which are not bi-directional solvents.
  • the extractant comprises water.
  • Another aspect of some embodiments of the invention relates to recovery of usable water from the contaminated wastewater stream without solidification (e.g. precipitation and/or crystallization) of contaminants.
  • a water stream to be treated includes one or more hydrophilic solutes and optionally one or more hydrophobic solutes.
  • hydrophilic solute indicates a solute with a log P ⁇ - 0.5.
  • the log P of the hydrophilic solute is -0.55; -0.6 -0.65; -0.7; -0.75; -0.8 or intermediate or lesser values.
  • hydrophilic solute includes ionic compounds.
  • hydrophobic solute indicates a solute with a log P > 0.0.
  • the log P of the hydrophobic solute is 0.1; 0.15; 0.2; 0.25; 0.3; 0.35 or intermediate or greater values.
  • the term "hydrophobic solute” indicates organic compounds with C:0 atom ratio greater than 3.
  • One aspect of some embodiments of the invention relates to treatment of product process water containing both hydrophilic solutes and hydrophobic solutes.
  • the hydrophobic solutes are crude-oil-associated.
  • said wastewater stream comprises product process water mixture with another stream.
  • said other stream comprises make-up water.
  • said make-up water comprises brackish water or sea water.
  • crude oil indicates materials present in crude oil (i.e. unrefined oil), materials produced during refining of crude oil or chemical conversion of crude oil, materials present in produced gas, materials produced during refining of produced gas or chemical conversion of produced gas.
  • crude oil includes fossil oil and/or vegetable oil (e.g. Palm Oil Mill Effluent - POME).
  • crude-oil-associated hydrophobic solutes are present in the wastewater stream at concentrations of 10 PPM, 25 PPM, 50 PPM 100 PPM, 200 PPM, 300 PPM, 400 PPM or 500 PPM or intermediate or higher concentrations.
  • water-depleted and water-enriched mean containing less water and more water, respectively, compared with the content prior to contacting, in terms of amount or flux or concentration.
  • a method including:
  • water partial vapor pressure at 50°C of the wastewater stream, the water-depleted first aqueous solution, the concentrated aqueous solution and the second aqueous solution are PI, P2, P3 and P4, respectively; and wherein the bi-directional solvent is selected so that P1>P2; P1>P3 and P4>P3.
  • the first contacting is done at temperature higher than 1°C, 10°C, 20°C, 30°C or 40°C and lower than 99°C, 90°C, 80°C, 70°C or 60°C.
  • the second contacting is done at temperature higher than 1°C, 10°C, 20°C, 30°C or 40°C and lower than 99°C, 90°C, 80°C, 70°C or 60°C.
  • the wastewater stream includes one or more crude-oil-associated hydrophobic solutes.
  • the method includes separating at least a portion of the one or more crude-oil- associated hydrophobic solutes from at least a portion of the second organic phase.
  • separating water includes heating the second aqueous solution.
  • the heating separates a gaseous and/or solid compound, and the method comprises contacting the separated gaseous and/or solid compound with a third aqueous solution to form the concentrated aqueous solution.
  • the gaseous or solid compound includes at least one member of the group consisting of NH 3 , CO, C0 2 , CaC12, Ca(N02)3, KBr, KCl, KHC03, K2S04, MgC12, MgS04, NaCl, NaHC03, Na2S04, NH4C1, (NH 4 ) 2 C0 3 , (NH 4 )HC ⁇ 3 ⁇ 4 H2NCOONH4 and (NH4)2S04.
  • the concentrated aqueous solution includes an ammonium compound.
  • the second aqueous solution comprises at least a portion of the bi-directional solvent and the heating separate a third organic phase.
  • separating water includes contacting the second aqueous solution with a membrane to form separated water and a retentate.
  • the method is characterized in that the membrane is a reverse osmosis membrane.
  • the second aqueous solution comprises at least a portion of the bi-directional solvent and the retentate comprises a fourth organic phase.
  • the method includes recycling at least a portion of the third organic phase or at least a portion of the fourth organic phase to the first contacting.
  • the separating water includes heating the second aqueous solution and contacting the second aqueous solution with a membrane.
  • the method is characterized in that the separated water comprises at least 60% of the water in said at least a portion of the wastewater stream.
  • the bi-directional solvent has a greater affinity to monovalent ions compared to divalent ions;
  • the wastewater stream includes at least one multivalent ion and at least one monovalent ion at a multivalent to monovalent ion ratio Rl
  • the first aqueous solution includes at least one multivalent ion and at least one monovalent ion at a multivalent to monovalent ion ratio R2, and R2 is similar to Rl .
  • the wastewater stream includes at least one multivalent ion and at least one monovalent ion at a multivalent to monovalent ion ratio Rl
  • the concentrated aqueous solution includes at least one multivalent ion and at least one monovalent ion at a multivalent to monovalent ion ratio R3, and R3>R1.
  • both the wastewater stream and the concentrates aqueous solution include at least one multivalent ion and the composition of multivalent ions in said wastewater stream is different from the composition of multivalent ions in the concentrated aqueous solution.
  • the method includes contacting at least a fraction of at least one of the first organic phase and the second organic phase with a hydrophobic solvent having a C:0 ratio at least 2 times greater than the C:0 ratio in the bi- directional solvent.
  • the one or more crude-oil- associated hydrophobic solutes include at least one member of the group consisting of naphthenic acid, other organic acids comprising at least 5 carbon atoms, 1,4-dioxane, acetone, bromoform, dibenzo(a,h)anthracene, pyridine, phenols and oil.
  • the second organic phase includes at least 85% of the one or more crude-oil-associated hydrophobic solutes in said wastewater stream.
  • the water-depleted first aqueous solution comprises at least 80% of the one or more hydrophilic solutes in the wastewater stream.
  • the method includes recycling at least 50% of water from the wastewater stream to an industrial process producing the wastewater stream.
  • the wastewater stream includes blowdown of steam generator.
  • the method includes softening said wastewater stream to form a softened feed stream and feeding the softened feed stream to a steam generator to form steam and a blowdown stream.
  • the wastewater stream is produced by an industrial process selected from the group consisting of hydraulic fracturing (fracking), crude oil production from oil sand, steam-assisted gravity drainage (SAGD), petroleum industry processing, enhanced oil recovery (EOR) and vegetable oil production.
  • the wastewater stream is produced by an industrial process selected from the group consisting of recovering crude oil and processing crude oil.
  • the method includes contacting crude oil with the separated water to produce the wastewater stream.
  • the bi-directional solvent includes one or more oxygen-comprising organic molecules with 3 to 6 carbon atoms.
  • the bi-directional solvent includes one or more members of the group consisting of alcohols, ketones, esters, phenols and organic acids.
  • the bi-directional solvent includes one or more members of the group consisting of normal butanol, secondary butanol, isobutanol, tertiary butanol, normal pentanol, secondary pentanol, isopentanol and tertiary pentanol
  • the bidirectional solvent is selected so that the ratio of the one or more hydrophilic solutes to the one or more crude-oil- associated hydrophobic solutes is at least ten times higher in the water-depleted first aqueous solution than in the wastewater stream.
  • the concentration of at least one of the one or more crude-oil-associated hydrophobic solutes in the extractant is at least three times higher than the concentration of the at least one of the one or more crude-oil-associated hydrophobic solutes in the wastewater stream just prior to the first contacting.
  • the separating at least a portion of the one or more crude -oil-associated hydrophobic solutes from the second organic phase includes evaporation.
  • the method includes conducting the first contacting, the second contacting or both in a counter current mode.
  • the method includes conducting the first contacting, the second contacting or both in a counter current mode.
  • between 2 and 20 weight units of the bi-directional solvent are provided for each weight unit of water in the wastewater stream at the first contacting.
  • the bi-directional solvent includes one or more phenols.
  • the one or more crude-oil- associated hydrophobic solutes include one or more oils.
  • a system including:
  • a first extraction module in fluid communication with the extractant source and adapted to contact the extractant with at least a portion of the wastewater stream to form a water-depleted first aqueous solution and a water-enriched first organic phase;
  • a second extraction module adapted to receive the first organic phase and contact the first organic phase with a concentrated aqueous solution, to produce a second organic phase and a second aqueous solution;
  • a pump adapted to route at least a portion of the solute to the second water extraction module as recycled aqueous solution.
  • the system includes a solvent pump directing at least a portion of the second organic phase to the first water extraction module.
  • method refers to manners, means, techniques and procedures for accomplishing a given task including, but not limited to, those manners, means, techniques and procedures either known to, or readily developed from known manners, means, techniques and procedures by practitioners of architecture and/or computer science.
  • Percentages (%) of chemicals and/or contaminants are W/W (weight per weight) unless otherwise indicated. Percentages of solute in solvent (solute concentration) are W/W. In those cases where a portion of a solute precipitates or crystallizes, the weight of solid solute and dissolved solute are both considered in calculating the solute concentration.
  • a proportion of, "a concentration of or "a ratio between” “hydrophobic solute”, “one or more hydrophobic solute”, “at least one of said one or more hydrophobic solute”, “hydrophilic solute”, “one or more hydrophilic solute”, “at least one of said one or more hydrophilic solute”, “monovalent”, “at least one monovalent ion”, “multivalent”, “at least one multivalent ion” and similar phrases are to be taken as specifying a proportion of or a concentration of at least one solute/ion, or the ratio between concentration of a single solute/ion and the concentration of another single solute/ion.
  • Fig. 1 is a schematic flow plan of a water recovery process according to an exemplary embodiment of the invention depicting procedures and streams;
  • Fig. 2 is a schematic flow plan of a water recovery process according to an exemplary embodiment of the invention depicting procedures and streams;
  • Fig. 3 is a schematic flow plan of a water recovery process according to an exemplary embodiment of the invention depicting procedures and streams;
  • Fig. 4 is a schematic representation of a water recovery system according to some exemplary embodiments of the invention.
  • Embodiments of the invention relate to methods and systems for water recovery as well as to various streams produced by the recovery process.
  • some embodiments of the invention can be used to recover wastewater from product process water in an industrial process.
  • Fig. 1, Fig. 2 and Fig. 3 are a schematic flow plan of a water recovery process or methods according to an exemplary embodiments of the invention indicated generally as 100, 200 or 300 respectively.
  • a flow of organic phases is depicted by dashed arrows
  • a flow of aqueous solutions is depicted by solid arrows
  • a flow of gas or solid compound is depicted by dot arrows.
  • At least a portion of a wastewater stream containing one or more hydrophilic solutes 106 is first contacted 110 with an extractant 108 including a bi-directional solvent to form a water-depleted first aqueous solution 116 and a water-enriched first organic phase 118.
  • the first organic phase 118 is second contacted with a concentrated aqueous solution 132 to form a second organic phase 128 and a second aqueous solution 126.
  • water is separated from the second aqueous solution 126 (e.g. by heating 130) to form a gas or solid compounds 134 and separated water 136.
  • gas or solid compounds 134 are contacted with a third aqueous solution to form a concentrated aqueous solution 1321.
  • water is separated from the second aqueous solution 126 (e.g. by Reverse Osmosis 230) to form a concentrated aqueous solution 132 and separated water 136.
  • gas or solid compounds 134 are separated from the second aqueous solution 126 (e.g. by heating 330) and water is separated from the second aqueous solution 126 (e.g. by Reverse Osmosis 331) to form a concentrated aqueous solution 132 and separated water 136.
  • the concentrated aqueous solution 132 is recycled to the second contacting 120.
  • bi-directional solvent is recycled from the second organic phase 128 to the first contacting 110.
  • water partial vapor pressure at 50°C of the wastewater stream 106, the water-depleted first aqueous solution 116, the recycled aqueous solution 132 and the second aqueous solution 126 are PI, P2, P3 and P4, respectively; wherein P1>P2; P1>P3 and P4>P3.
  • the second contacting 120 is conducted between concentrated aqueous solution 132 and at least a fraction of first organic phase 118.
  • the wastewater stream 106 comprises one or more crude -oil-associated hydrophobic solutes.
  • at least a portion of the one or more crude -oil-associated hydrophobic solutes is separated from a portion of the second organic phase 128 (in the depicted exemplary embodiments, by evaporation 150).
  • the separating hydrophobic solutes 152 is conducted prior to the recycling of bi-directional solvent from the second organic phase 128 to the first contacting 110 or simultaneously with it.
  • first aqueous solution 116 is substantially free of organic compounds (crude-oil-associated hydrophobic solutes) other than the bi-directional solvent. These organic compounds (if present) tend to migrate into first organic phase 118. As described below, additional separations by evaporation lead to regeneration of the bi-directional solvent and (optionally) to recovery of desired organic compounds.
  • Depicted exemplary embodiments 100, 200 and 300 employs distillation 140 to recover bi-directional solvent 148 dissolved in first aqueous phase 116.
  • other separation methods are employed, e.g. salting out or using an auxiliary solvent.
  • the amount of solvent 148 to be distilled is relatively small because the majority of bi-directional solvent from extractant 108 is present in first organic phase 118.
  • solvent 148 distills as an azeotrope with water.
  • water in solvent 148 contributes to an increased total water yield as extractant stream 108 is recycled.
  • distillation 140 also produces an impurities- enriched aqueous solution 146.
  • said impurities-enriched solution is characterized by water partial vapor pressure at 50°C of P5 and P5 > PI .
  • said impurities-enriched solution is disposed as such or after further treatment.
  • such further treatment comprises at least one of further concentration, precipitation of at least one component and addition of a chemical compound.
  • the flow rate of said wastewater is Fl
  • the flow rate of said impurities-enriched solution is F2 and F1/F2 is greater than 2, 4, 6, 8, 10 or intermediate of greater ratio.
  • second organic phase 128 (containing some water) is recycled to extractant stream 108 without further separation of water.
  • Separated water 136 is the primary product of methods 100, 200 and 300.
  • the amounts of bi-directional solvent and/or hydrophilic solutes and/or hydrophobic solutes in separated water 136 are sufficiently low at this stage that it can serve as feed water to an industrial process and/or agricultural irrigation water and/or potable water.
  • wastewater stream 106 contains one or more crude-oil-associated hydrophobic solutes. These hydrophobic solutes migrate to the bi-directional solvent and will tend to accumulate there if not removed.
  • evaporation 150 is depicted as separating at least a portion of the one or more hydrophobic solutes 152 from second organic phase 128 prior to the contacting with wastewater stream 106.
  • hydrophobic solutes 152 include organic acids (e.g. naphthenic acid).
  • water separating from second aqueous solution 126 includes at least one of Heating, Evaporation, Reverse Osmosis, Forward Osmosis, Electrodialysis and contacting with a solvent.
  • the separating of water from second aqueous solution 126 includes contacting the second aqueous solution 126 with a membrane 230 (Fig. 2) or 331 (Fig. 3) to form a separated water 136 and a retentate which includes the concentrated aqueous solution 132.
  • the membrane is a reverse osmosis membrane (RO).
  • RO reverse osmosis membrane
  • the membrane is a nano-filtration membrane.
  • second aqueous phase 126 includes the bidirectional solvent.
  • concentration of the bi-directional solvent in second aqueous phase 126 is a function of hydrophilic solutes (e.g. salts) concentration there.
  • the bi-directional solvent is at least partially removed from the second aqueous solution 126 prior to the contacting with the membrane (depicted as separation membrane 230(Fig. 2), or 331 (Fig. 3)), e.g. by distillation.
  • the bi-directional solvent is separated by the contacting with a membrane (e.g. separation membrane 230(Fig. 2), or 331 (Fig. 3)).
  • the bi-directional solvent is rejected by the membrane and is retained in the retentate along with the concentrated aqueous solution.
  • said concentrated aqueous solution 132 is of reduced volume and higher salt concentration compared to said second aqueous solution.
  • the third organic phase 138 is recycled as bi-directional solvent to the first contacting 110.
  • said third organic phase 138 is combined with said second organic phase 128 or introduced separately to said first contacting, e.g. at a point closer to the exit of said first aqueous solution 116.
  • the retentate is included in the concentrated aqueous solution which is at least partially recycled to the second contacting 120 as concentrated aqueous solution 132.
  • the recycling to the second contacting 120 is conducted without prior separation of dissolved bi-directional solvent.
  • the separated water 136 comprises at least 60%, 70%, 80%>, 85%, 90% or at least 95% of the water in the wastewater stream 106.
  • the third organic phase 138 includes the bidirectional solvent and water. According to an embodiment, the third organic phase 138 could be recycled as such to the first contacting in 110.
  • water extraction (first contacting 110) is selective to water over ions.
  • Selectivity is particularly high compared to extraction of divalent ions, including ones contributing to hardness and scale.
  • wastewater stream 106 includes at least one multivalent ion and at least one monovalent ion at a multivalent to monovalent ratio Rl
  • the first aqueous solution 116 includes at least one multivalent ion and at least one monovalent ion at a multivalent to monovalent ratio R2
  • R2 is similar to Rl
  • R2/R1 is in the range between 0.75 and 1.25, between 0.8 and 1.2, between 0.85 and 1.15 or between 0.9 and 1.1.
  • the concentrated aqueous solution 132 includes at least one multivalent ion and at least one monovalent ion at a multivalent to monovalent ratio R3, and R3>R1.
  • R3/R1 is greater than 2, 4, 6, 8 or greater than 10.
  • both the wastewater stream 106 and the concentrated aqueous solution 132 include at least one multivalent ion, and the composition of multivalent ions in the wastewater stream 106 is different from the composition of multivalent ions in the concentrated aqueous solution 132.
  • one of these solutions (132 and 106) contains at least one multivalent ions that do not exist in the other.
  • the concentration of a given multivalent ion in one of these solutions is different from the concentration of the same multivalent ion in the other.
  • the concentrated aqueous solution 132 contains at least one member of: NH 3 , CO, C0 2 , CaC12,
  • exemplary embodiment 100 (Fig. 1)
  • the heating 130 of the second aqueous solution 126 generate the following streams; third organic phase 138, solid or gas compounds 134, a third aqueous solution and separated water 136.
  • Third aqueous solution with said solid or gas compound reforms said concentrated aqueous solution
  • the secondary aqueous solution 126 is heated 330 to separate a solid and/or gas compound 134.
  • the separated compound is selected from a group consisting of NH 3 , CO, C0 2 , CaC12, Ca(N02)3, KBr, KC1, KHC03, K2S04, MgC12, MgS04, NaCl, NaHC03, Na2S04, NH4C1, (NH 4 ) 2 C0 3 , (NH 4 )HC0 3 , H 2 NCOONH 4 and (NH4)2S04.
  • the formed aqueous solution is contacted with a membrane, e.g. a reverse osmosis membrane, to form a retentate, separated water 136 and a fourth organic phase.
  • said separated solid and/or gaseous compound is contacted with said retentate to reform said concentrated aqueous solution 132.
  • the concentrated aqueous solution 132 comprises an ammonium compound.
  • the ammonium compound includes at least one of ammonium bicarbonate, ammonium carbonate, and ammonium carbamate.
  • methods 100, 200 and 300 includes contacting (not depicted) at least a fraction of at least one of first organic phase 118 and second organic phase 128 with a hydrophobic solvent, characterized in that C:0 ratio in the hydrophobic solvent is at least 2 times greater than that ratio in the bi-directional solvent.
  • the contacting induces water rejection from the first organic phase 118 and/or the second organic phase 128.
  • the hydrophobic solvent is separated (e.g. by distillation of one of the two) from the bi-directional solvent in first organic phase 118 and/or second organic phase 128 before the solvent is reused in the contacting 120 and/or 110, respectively.
  • crude-oil-associated hydrophobic solutes 152 include naphthenic acid and/or other organic acids comprising at least 5 carbons, and/or 1,4-dioxane, and/or acetone, and/or bromoform, and/or dibenzo(a,h)anthracene, and/or pyridine, and/or phenols and/or oil (e.g. fossil oil, vegetable oil).
  • soluble crude-oil-associated hydrophobic matter there could be suspended crude-oil-associated hydrophobic matter. Therefore, the amount of the crude-oil-associated hydrophobic matter in 106 may be greater than saturation concentration.
  • one or more of the crude -oil-associated hydrophobic solutes is less volatile than water, and is difficult to separate from the wastewater stream 106 by known methods, such as evaporation. According to some embodiments of the invention, such solutes are efficiently removed at low cost, optionally without their evaporation.
  • second organic phase 128 includes at least 85%, at least 90%, at least 95%, at least 97.5% or at least 99% of the at least one of the one or more crude-oil- associated hydrophobic solutes which were present in the wastewater 106.
  • water-depleted first aqueous solution 116 includes at least 80%, at least 85%, at least 90%, at least 95%, at least 97.5% or at least 99% of the at least one of the one or more hydrophilic solutes (i.e. in case of multiple solutes, this could be true for one of the solutes in some embodiments and more than one of them in other embodiments) in the wastewater stream 106.
  • the method includes recycling at least 50%, at least 55%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95% of water from the wastewater stream 106 to an industrial process producing the wastewater stream.
  • the recycled water is derived from the second aqueous solution 126.
  • the recycled water includes the separated water 136 from the heating 130 (Fig. 1) or Separation membrane 230 (Fig. 2) or 331 (fig.3).
  • the industrial process generates different "product process water" stream (i.e. wastewater stream) and/or consumes water/aqueous solutions in multiple steps.
  • the recycled water results from any stream and is used in any step.
  • the recycled water is at high quality.
  • the recycled water is at quality as required for steam production (including steam required for stripping solvent from exiting streams).
  • the water derived from the second aqueous solution 126 and/or from separated water 136 has alternative outlets (e.g. irrigation, emission to rivers and sewage).
  • wastewater stream 106 is produced by an industrial process selected from the group consisting of induced hydraulic fracturing (fracking), Steam Assisted Gravity drainage (SAGD), crude oil production from oil sand, petroleum industry processing, enhanced oil recovery (EOR) and vegetable oil production.
  • wastewater stream 106 is produced by an industrial process selected from the group consisting of recovering crude oil, recovering gas, and processing crude oil.
  • methods 100, 200 and 300 includes contacting crude oil with separated water 136 derived from second aqueous solution 126 to produce the wastewater stream 106.
  • the bi-directional solvent in extractant 108 includes one or more organic molecules with 3 to 6 carbon atoms.
  • the organic molecules include alcohols and/or ketones and/or esters and/or organic acids.
  • the bi-directional solvent in extractant 108 includes a butanol (e.g. n-butanol or isobutanol).
  • the bi-directional solvent in extractant 108 comprises one or more amines.
  • the one or more amines include one or more members of the group consisting of diethylamine, triethylamine, 1 -methyl piperidine, 4-methyl piperidine di-isopropylamine, ⁇ , ⁇ -dietheylmethylamine, dimethylisopropylamine, ethylisopropylamine, methylethylisopropylamine, methylethyl-n-propylamine, dimethyl-secondary-butylamine, dimethyl-tertiary-butylamine, dimethylisobutylamine, dimethyl-n-butylamine, methyldiethylamine, dimethylallylamine, dimethyl-n-propylamine, diisopropylamine, di-n- propyl amine, di-allylamine, n-methyl-n-amylamine, n-ethyl-n-butylamine, n-ethyl-sec- butylamine, n-e
  • a single amine is employed. In other exemplary embodiments of the invention, a combination of two or more amines is employed. Alternatively or additionally, amines are used in combination with non-amine molecules in some embodiments of the invention.
  • the ratio of at least one of the hydrophilic solutes to at least one of the crude-oil-associated hydrophobic solutes is at least ten times higher (this ratio does not necessarily apply to the ratio between total hydrophilic solutes and total hydrophobic solutes) in the water-depleted first aqueous solution 116 than in the wastewater stream 106.
  • the concentration of at least one of the one or more crude-oil-associated hydrophobic solutes in extractant 108 is at least three times higher than the concentration of the at least one of the one or more crude-oil-associated hydrophobic solutes in the wastewater stream 106 just prior to first contacting 110 (this ratio does not necessarily apply to the total hydrophobic solutes).
  • separating at least a portion of the one or more crude-oil-associated hydrophobic solutes 152 from second organic phase 128 includes evaporation 150.
  • evaporation 150 includes distillation of the solvent from solutes 152.
  • the hydrophobic solute is more volatile than the bi-directional solvent. In that case, the solute is evaporated out. In other cases, the opposite is true and the bi-directional solvent is evaporated. Still there could be both solutes that are more volatile than the bi-directional solvent and ones that are less volatile. In such cases, the more volatile are evaporated first and then the bi-directional solvent is evaporated.
  • only a small fraction of the second organic phase 128 is treated for separation of the hydrophobic solutes 152, e.g. less than 20% of it, less than 15%, less than 10%>, or less than 5%.
  • the one or more crude-oil-associated hydrophobic solutes include one or more phenols.
  • the one or more crude-oil-associated hydrophobic solutes include one or more oils (e.g. fossil oil, vegetable oil).
  • the method includes conducting first contacting 110 and/or second contacting 120 in a counter current mode.
  • the contacting 110 and/or 120 is conducted in 2-20 stages, 3-15 stages, 4-12 stages or 5-10 stages.
  • the weight/weight ratio between the amount of bi-directional solvent in stream 108 and the amount of water in stream 106 is in a range between 2: 1 and 20: 1, between 3: 1 to 17: 1, between 6: 1 to 15: 1, between 2: 1 and 12: 1, between 3: 1 and 11 : 1, between 4: 1 and 10: 1 or in a range between 8: 1 to 12: 1.
  • first contacting 110 is conducted in a continuous mode and this ratio is between the weight fluxes of streams instead of the amounts.
  • stream 106 contains suspended solids. These solids can include, but are not limited to sand or soil particles. According to various embodiments, these solids are removed prior to the first contacting 110. According to various exemplary embodiments of the invention solids removal module includes a settling tank and/or filtration equipment and/or centrifugation equipment (e.g. a flow through centrifuge and/or a cyclonic separator). In some embodiments, removal of solids contributes to mechanical efficiency of downstream processes.
  • a settling tank and/or filtration equipment and/or centrifugation equipment e.g. a flow through centrifuge and/or a cyclonic separator.
  • stream 106 contains one or more dissolved surfactants (e.g. soaps and/or detergents).
  • at least one of the one or more surfactants is removed from and/or inactivated in at least a portion of stream 106 prior to first contacting 110.
  • a surfactant removal and/or inactivation module is positioned upstream of the first contacting 110 to reduce activity of surfactants present in stream 106.
  • the surfactant removal and/or inactivation module employs surface active material (e.g. activated charcoal) and/or pH adjustment and/or addition of multivalent ions.
  • the surfactant removal and/or inactivation module contributes to an efficiency of separation of first aqueous solution 116 from first organic phase 118 and/or to an efficiency of separation of second aqueous solution 126 from second organic phase 128.
  • wastewater stream 106 contains at least 10,000 PPM; at least 20,000 PPM; at least 30,000 PPM or at least 40,000 PPM of total dissolved solids (TDS). In other exemplary embodiments of the invention, stream 106 contains less than 100,000 PPM, less than 90,000 PPM, less than 80,000 PPM, less than 70,000 PPM or less than 50,000 PPM of total dissolved solids (TDS).
  • total dissolved solids (TDS) in said wastewater stream 106 is less than 10,000 ppm; less than 8,000 ppm; less than 6,000 ppm; less than 4,000 ppm or less than 2,000 ppm. Wastewater stream with these relatively low levels of TDS is produced, for example, in cooling towers and/or in the oil industry.
  • the TDS includes barium and/or strontium and/or iron and/or other heavy metals and/or radioactive isotopes and/or cyanides and/or thiocyanates and/or salts of ammonia and/or sulfides and/or sulfates and/or calcium salts and/or silica.
  • Various exemplary embodiments of the invention described herein relate to extraction (110) of water into an extractant comprising bi-directional solvent or back-extraction (120) of water from such extractant.
  • at least one of such extraction and back-extraction is conducted by contacting in a multiple step, counter-current operation.
  • such contacting is conducted in industrially used contactors, e.g. mixer-settlers, extraction columns, centrifugal contactors and raining- bucket contactor.
  • the wastewater comprises suspended solids and/or solids are formed during said first contacting and the used contactor is designed to handle such solids.
  • first organic phase 118 is treated prior to said second contacting, e.g. by adding an organic solvent or contacting with an aqueous solution.
  • first organic phase 118 comprises suspended solids and said treating prior to said second contacting comprises separating such suspended solids, e.g. via extended settling or addition of a coagulant.
  • the bi-directional solvent employed in extractant stream 108 is selected based upon the total dissolved solids (TDS) content of stream 106 and/or the organic compounds (e.g. hydrophobic solutes) content of stream 106 and the cost of available energy.
  • TDS total dissolved solids
  • organic compounds e.g. hydrophobic solutes
  • a known method for treating wastewater involves evaporation of the water. Energy consumption is high due to the required input of latent heat.
  • Major efforts are directed to developing alternatives based on membrane separation (e.g. Reverse Osmosis). Those require several pretreatments (e.g. filtration, adsorption, coagulation and softening) in order to protect the membrane. These pretreatments substantially increase the cost of the membranes-based separation.
  • One exemplary advantage of some embodiments of the invention is that water is separated by the extraction with a bi-directional solvent and recovered from the formed organic phase without the input of latent heat.
  • another exemplary advantage of some embodiments of the invention is that the separation membrane 230 (Fig. 2) and 331 (Fig.3) is not directly contacted with the wastewater stream; therefore less pretreatment stages are required.
  • those portions of the process that optionally employ latent heat are applied to smaller portions of the total mass in the system and directed to evaporation of relatively low latent heat solvent, resulting in significant energy savings.
  • exemplary methods 100, 200 and 300 achieves efficient separation of usable water (separated water 136) from the wastewater (106) forming a reduced- volume, impurities-concentrated stream (impurities-enriched aqueous solution 146), thereby reducing the volume of wastewater to disposal.
  • exemplary methods 100, 200 and 300 achieves good separation of organic matter (hydrophobic solutes 152), which can be used for energy or more specific application.
  • exemplary methods 100,200 and 300 results in a high quality separated water 136, which may be used e.g. for steam, in a relatively low costs compared to alternative treatments.
  • exemplary methods described herein are more suitable for use in handling hard water (at 106) than previously available alternatives.
  • exemplary methods described herein contribute to a reduction in use of chemical reagents.
  • exemplary methods described herein are amenable to integration with other methods, e.g. gravity separation devices such as the API (American
  • Fig. 4 is a schematic representation of a water recovery system indicated generally as 400.
  • a flow of organic phases is depicted by dashed arrows
  • a flow of aqueous solutions is depicted by solid arrows.
  • Depicted exemplary system 400 includes a first water extraction module 410 adapted to contact an extractant comprising a bi-directional solvent 108 with at least a portion of a wastewater stream including one or more hydrophilic solutes 106 to form a water-depleted first aqueous solution 116 and a water-enriched first organic phase 118.
  • system 400 includes a second water extraction module 420 adapted to contact the first organic phase 118 with a concentrated aqueous solution 132, to produce a second organic phase 128 and a second aqueous solution 126.
  • Depicted exemplary system 400 also includes a separation module 430 adapted to separate a concentrated aqueous solution 132, third organic phase 138 and separated water 136 from the second aqueous solution 126.
  • the first contacting 110 at the first water extraction module 410 occurs at a first temperature (Tl) and the second contacting 120 at the second water extraction module 420 occurs at a second temperature (T2).
  • T2 is similar to Tl .
  • T2 is different than Tl .
  • system 400 is configured to allow recycling of at least a portion of the concentrated aqueous solution to the second water extraction module 420.
  • at least a portion of the concentrated aqueous solution 132 is recycled to the second water extraction module 420.
  • system 400 is configured to allow recycling of at least a portion of the second organic phase 128 as bi-directional solvent to the first water extraction module 410.
  • the separation module comprises a membrane adapted to form separated water 136 and a retentate in a retentate compartment and the retentate is included in the concentrated aqueous solution 132.
  • the membrane is a Reverse Osmosis membrane.
  • the system is characterized in that the second aqueous solution 126 includes the bi-directional solvent and in that the retentate compartment is adapted to include a third organic phase 138.
  • system 400 is configured to allow recycling of at least a portion of the third organic phase 138 as bi-directional solvent to the first water extraction module 410.
  • system 400 is characterized in being portable. According to some embodiments, system 400 is mobile, moveable, and can be transported from one place to another (e.g. from one shale oil play to another). According to an embodiment, system 400 is skid mounted.
  • Exemplary use scenario I Induced hydraulic fracturing (fracking)
  • Waste water produced by fracking contains hydrophilic solutes including but not limited to sodium, magnesium and calcium salts, barium, strontium, iron, other heavy metals and radioactive isotopes.
  • Total dissolved solids (TDS) are typically in the range of 5,000 PPM to 100,000 PPM or more.
  • Waste water produced by tracking also contains hydrophobic materials such as oil.
  • fracking serves as industrial process and flowback and/or produced water serve as wastewater stream 106.
  • first aqueous solution 116 During water recovery processes 100, 200 and 300 the bulk of the hydrophilic solutes will separate into first aqueous solution 116 and according to some embodiments, be removed from the system at 146 as described in detail hereinabove.
  • the hydrophobic solutes are selectively and efficiently extracted into the first organic phase 118 in the first contacting 110.
  • the hydrophobic solutes remain practically fully in the extractant during the second contacting, i.e. in the second organic phase 128.
  • a fraction of the hydrophobic solutes arrive at evaporation 150 and is at least partially removed from the system at 152.
  • Separated water 136 becomes feed process water to the industrial process and can be used as part of input water for a subsequent round of fracking.
  • waste water produced by fracking contains a surfactant.
  • surfactant is removed prior to introduction into methods 100, 200 and 300.
  • removal of surfactant contributes to a more efficient partitioning between organic phases and aqueous solutions throughout the process.
  • SAGD Steam Assisted Gravity Drainage
  • two horizontal wells are drilled in the oil sands, one at the bottom of the formation and another about 5 metres above it. These wells are typically drilled in groups off central pads and can extend for miles in all directions.
  • steam is injected into the upper well, the heat melts the bitumen, which allows it to flow into the lower well, where it is pumped to the surface.
  • the steam for the SAGD process can be generated by a once-through steam generator (OTSG).
  • the feed for the OTSG can comprise produced water and optionally also make-up water.
  • the OTSG generate a high quality steam for the well injection and a blowdown stream that can contain dissolve solids, the blowdown stream needs treatment.
  • the produced Synthetic Crude Oil contain water (produces water) that are separated during the processing of the Synthetic Crude Oil, Separated water is recycled to the steam generator.
  • Make-up water is provided from natural sources as rivers or underground wells in some cases the make-up water contains inorganic salts (hydrophilic solutes).
  • Removal of the inorganic salts and organic acids prior to the OTSG can decrease the inorganic salts and organic acids percentage in the blewdown water.
  • blowdown water are wastewater produced during production of synthetic crude oil.
  • Waste water produced during production of synthetic crude oil contains inorganic salts (hydrophilic solutes), and organic acids (hydrophobic solutes).
  • production of synthetic crude oil serves as industrial process and wastewater produced during production of synthetic crude oil serves as wastewater stream 106.
  • the bulk of the hydrophilic inorganic salts will separate into first aqueous solution 116 and according to some embodiments, be removed from the system at 146 as described in detail hereinabove.
  • the hydrophobic solutes (organic acids) are selectively and efficiently extracted into the first organic phase 118 in the first contacting 110.
  • the hydrophobic solutes remain practically fully in the extractant during the second contacting, i.e. in the second organic phase 128.
  • a fraction of the hydrophobic solutes arrive at evaporation 150 and is at least partially removed from the system at 152.
  • Separated water (depicted as permeate 136) becomes feed process water to the industrial process and can be used as part of input water for a subsequent round of production of synthetic crude oil.
  • Exemplary use scenario III Cooling Water
  • Israel water-cooled condensers are estimated to consume some 130 million M 3 of water each year and discharge 35 million M 3 of brines each year.
  • the brines contain about 5.6 tons of chlorides/ M 3 and about tons of 2.6 tons of sodium/ M 3 .
  • cooling water Even larger amounts of cooling water are used in an industrial context. As an example, a single refinery can require about 350 M 3 /hour of cooling water. Of this amount, about 60 to 80% is lost to evaporation in cooling towers and the remaining 20 to 40% is recovered as cooled water which is, at least theoretically, available for recycling. Because minerals do not evaporate, salts are concentrated in the cooling tower by a factor of about 2.5 to 5.
  • cooling in a cooling tower serves as industrial process and the cooled water serves as wastewater stream 106.
  • first aqueous solution 116 the bulk of the hydrophilic inorganic salts will separate into first aqueous solution 116 and according to some embodiments, be removed from the system at 146 as described in detail hereinabove.
  • Separated water 136 becomes feed process water and can be used as part of input water for a subsequent round of cooling.
  • Water recovery processes 100, 200 and 300 are suitable to treat wastewater stream 106 from the oil industry (e.g. refineries) and cooling towers from various industries.
  • an oil refinery includes one or more cooling towers so that there are multiple sources of wastewater. According to various exemplary embodiments of the invention these multiple sources of wastewater are treated according to method 100 either separately or in combination with one another.
  • Exemplary use scenario IV Effluents from Petroleum Industry processing
  • processing includes various treatments (e.g. cracking, which is the process in which heavy hydrocarbons are broken down to lighter hydrocarbons). These processing treatments produce wastewater streams including hydrophilic solutes.
  • hydrophilic solutes can include, but are not limited to cyanide salts, thiocyanate salts, salts of ammonia and sulfides (e.g. H 2 S).
  • the waste can include hydrophobic solutes such as oils and/or phenols.
  • the phenols can include the monohydrics (having one hydroxyl group) such as phenol; o-, m-, and /?-cresols, the various xylenols, and the various ethylphenols.
  • the phenols may also include polyhydrics (having two or more hydroxyl groups) such as catechol and resorcinol which are CeEL ⁇ OH ⁇ isomers.
  • the phenols may include thiophenols such as benzenethiol (or phenyl mercaptan) which is CeH 5 SH and toluenethiols (or tolyl mercaptans) which are CH3C6H4SH isomers.
  • petroleum industry processing wastewater stream can include ⁇ 50 mg cyanides or thiocyanates and/or > 500 mg/L ammonia or ammonium salts and/or > 500 mg/L sulfides as hydrophilic solutes.
  • the same stream may also include 50 to 500 mg/L of phenols and/or 50 to 500 mg/L of oils as hydrophobic solutes.
  • petroleum industry processing serves as industrial process and wastewater produced during the processing serves as wastewater stream 106.
  • first aqueous solution 116 the bulk of the hydrophilic inorganic salts will separate into first aqueous solution 116 and according to some embodiments, be removed from the system at 146 as described in detail hereinabove.
  • the hydrophobic solutes (phenols and/or oils) are selectively and efficiently extracted into the first organic phase 118 in the first contacting 110.
  • the hydrophobic solutes remain practically fully in the extractant during the second contacting, i.e. in the second organic phase 128.
  • a fraction of the hydrophobic solutes arrive at evaporation 150 and is at least partially removed from the system at 152.
  • Separated water 136 becomes feed process water and can be used as part of input water for a subsequent round of any of the processing treatments.
  • Exemplary use scenario V Enhanced oil recovery (EOR)
  • the EOR process is similar production of oil from oil sand (scenario II above) in that it involves pumping water down into a well.
  • EOR liquid water penetrates oil in the bottom of the well and accumulates underneath the oil. As the water accumulates it raises the oil until the oil reaches a level at which it can be pumped from the well.
  • the oil pumped from the well using EOR contains about 20 to 30% water carrying a high concentration of salts which can contain metals and/or radioisotopes. In order to re-use this water it must be separated from the oil and the salt concentration must be reduced.
  • EOR serves as industrial process and water separated from recovered crude oil serves as wastewater stream 106.
  • first aqueous solution 116 the bulk of the hydrophilic inorganic salts, metals and radioisotopes will separate into first aqueous solution 116 and according to some embodiments, be removed from the system at 146 as described in detail hereinabove.
  • the hydrophobic solutes (suspended oil droplets) are selectively and efficiently extracted into the first organic phase 118 in the first contacting 110.
  • the hydrophobic solutes remain practically fully in the extractant during the second contacting, i.e. in the second organic phase 128.
  • a fraction of the hydrophobic solutes arrive at evaporation 150 and is at least partially removed from the system at 152.
  • Separated water 136 becomes feed process water and can be used as part of input water for a subsequent round of EOR.
  • Example 1 Water extraction from a waste stream using recycled n-butanol extractant
  • a flowback waste stream was contacted (extracted) with recycled n-butanol (the bidirectional solvent).
  • the waste stream (Aqueous Feed to extraction) contained 3% total dissolved solutes (TDS), mainly salts (hydrophilic solutes), and about 200ppm oil-related organic matter (crude -oil-associated hydrophobic solutes).
  • the recycled (regenerated) n- butanol (Extractant) contained initially about 11.5% water.
  • the bench scale extraction was conducted at 35°C and simulated counter-currently extraction of 8 stages. Water transferred from the waste stream to the Extractant.
  • the Extractant to Aqueous Feed (O/A) weight/weight ratio was 11.
  • the formed organic phases and aqueous phases were analyzed to determine the time when their composition has reached a steady state.
  • the steady state organic phase (Extract) and the steady state aqueous phase (Raffmate) were analyzed.
  • the TDS of the Raffmate was 12%. Its n-butanol concentration was 2.7% and the concentration of oil-related organic matter was less than 20ppm. The water content if the Extract was 17. These analyses indicate that about 75% of the water and essentially all the oil-related organic matter initially present in the waste stream got extracted into the n- butanol.
  • the formed Raffinate is the water-depleted first aqueous solution and the formed extract is the water-enriched first organic phase.
  • Example 12 Back-extraction of extract formed in Example 1 by means of MgC12 solution
  • the Extract formed in Experiment 1 was contacted (back-extracted) with recycled (regenerated) aqueous 11% MgC12 solution.
  • the bench scale back-extraction was conducted at 35oC and simulated counter-currently extraction of 8 stages.
  • the Extract to Aqueous MgC12 solution (O/A) weight/weight ratio was 5.
  • the formed organic phases and aqueous phases were analyzed to determine the time when their composition has reached a steady state.
  • the steady state organic phase (regenerated Extractant) and the steady state aqueous phase (diluted MgC12 solution) were analyzed.
  • MgC12 concentration in the diluted MgC12 solution was 8.
  • the water content of the regenerated Extract was 11.5%.
  • the water extracted from the waste stream into the extract according to Example 1 transferred from the extract to the recycled MgC12 solution in this back-extraction, regenerating the extractant of Example 1.
  • Examples 13-17 Back-extraction of the extracts formed in Examples 7-11 by means of MgC12 solution
  • Examples 18 Water removal from the diluted MgC12 solution of Example 12 by means of evaporation
  • Examples 19 Water removal from the diluted MgC12 solution of Example 12 by means of reverse osmosis
  • Diluted MgC12 solution formed in Exp. 12 was concentrated in a reverse osmosis cell to reach a concentration of 11%. Water transferred through the membrane, while MgC12 was rejected. The concentration of MgC12 was increased to regenerate the recycled MgC12 solution of Exp. 12. A small organic phase separated from the concentrated MgC12 solution.
  • Example 20 Back-extraction of extract formed in Example 1 by means of ammonium carbonate solution
  • a ammonia and C02 were bubbled through a recycled, dilute aqueous solution of ammonium carbonate to form a concentrated solution of about 20%.
  • the Extract formed in Experiment 1 was contacted (back-extracted) with the concentrated solution.
  • the bench scale back-extraction was conducted at 15oC and simulated counter-currently extraction of 8 stages.
  • the Extract to Aqueous (NH4)2C03 solution (O/A) weight/weight ratio was 5.
  • the formed organic phases and aqueous phases were analyzed to determine the time when their composition has reached a steady state.
  • the steady state organic phase (regenerated Extractant) and the steady state aqueous phase (diluted (NH4)2C03 solution) were analyzed.
  • the water content of the regenerated Extract was 11.5%.
  • features used to describe a method can be used to characterize an apparatus and features used to describe an apparatus can be used to characterize a method.
  • the invention has been described in the context of industrial processes and desalination but might also be used to reduce levels of radioisotopes in water.

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Abstract

La présente invention concerne des procédés et des systèmes de récupération d'eau.
EP13872861.3A 2013-01-28 2013-11-20 Procédés et systèmes de récupération d'eau Withdrawn EP2948230A4 (fr)

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