US20200308023A1 - Salt recovery solution and processes of use thereof - Google Patents

Salt recovery solution and processes of use thereof Download PDF

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US20200308023A1
US20200308023A1 US16/753,263 US201816753263A US2020308023A1 US 20200308023 A1 US20200308023 A1 US 20200308023A1 US 201816753263 A US201816753263 A US 201816753263A US 2020308023 A1 US2020308023 A1 US 2020308023A1
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salt
solution
salt recovery
recovery solution
alkyl
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Daryl Joseph Briggs
Chaitra PRAKASH
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Aquafortus Technologies Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/04—Chlorides
    • C01D3/06—Preparation by working up brines; seawater or spent lyes
    • 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
    • C02F1/265—Desalination
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • 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
    • 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
    • C02F2103/08—Seawater, e.g. for desalination
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/14—Additives which dissolves or releases substances when predefined environmental conditions are reached, e.g. pH or temperature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • the present disclosure relates to a salt recovery solution and to a process for separating a salt from an aqueous solution.
  • the present disclosure also relates to a salt recovery solution and to its use to concentrate a salt or brine solution by recovering water therefrom.
  • Zero liquid discharge is an ambitious wastewater management strategy that eliminates any liquid waste leaving the plant or facility boundary, with the majority of water being recovered for reuse. Achieving ZLD, however, is generally characterized by intensive use of energy and high cost. As a result, ZLD has long been considered technically but not economically viable and has been applied only in limited cases.
  • RO Reverse osmosis
  • ED electrodialysis
  • FO forward osmosis
  • MD membrane distillation
  • the present invention provides a salt recovery solution suitable for recovering a salt from a first aqueous solution, the salt recovery solution comprising:
  • the salt recovery solution comprises:
  • the salt recovery solution comprises at least one enolisable carbonyl of Formula II,
  • X is a 6-membered aromatic monocyclic.
  • R 4 is a a C 1 -C 7 alkyl optionally substituted with a halo, a hydroxy, a —O—(C 1 -C 7 alkyl) or a C 3 -C 7 monocyclic.
  • the enolisable carbonyl of Formula II is selected from acetophenone and 4-phenyl-2butanone.
  • the present invention provides a process for recovering a salt from a first aqueous solution, the process including the step of
  • the process is a zero-liquid discharge process.
  • the process is a non-membrane process.
  • the present invention provides a process for concentrating a salt containing first aqueous solution, the process comprising the steps of:
  • the precipitated salt forms part of an aqueous layer distinct from the salt recovery solution.
  • the process is a non-membrane process.
  • the process is a non-osmotic process.
  • the process is a non-membrane and non-osmotic process.
  • the process concentrates the first aqueous solution by at least 20%. In other embodiments the process concentrates the first aqueous solution by at least 30%, or by at least 40%, or by at least 50% or by at least 60%, or by at least 70% or by at least 80% or by at least 90%.
  • the process is a minimal discharge process.
  • the process is a zero-liquid discharge process.
  • FIG. 1 shows schematically a salt recovery process of the present invention.
  • FIG. 2 shows gas chromatograms of the additive or regenerant solution overlaid with the additive or regenerant solution which has been used to remove water from a wet salt recovery solution.
  • FIG. 4 shows a calibration curve of NaCl solutions against osmotic pressure measurements.
  • FIG. 6 shows a graph of the osmotic pressure of NaCl solution after concentration using varying ratios of salt recovery solution (TEA:MEK).
  • FIG. 7 shows a bar graph of the concentration of NaCl solution after concentration using varying ratios of N-Ethylpiperidine:Cyclohexanone salt recovery solution.
  • FIG. 8 shows a graph of the osmotic pressure of NaCl solution after concentration using varying ratios of using salt recovery solution (N-Ethylpiperidine:Cyclohexanone).
  • FIG. 10 shows a bar graph of the concentration of NH 4 SO 4 solution after concentration using varying ratios of salt recovery solution (TEA:MEK).
  • the term “about” or “approximately” usually means within 20%, more preferably within 10%, and most preferably still within 5% of a given value or range. Alternatively, the term “about” means within a log (i.e., an order of magnitude) preferably within a factor of two of a given value.
  • additive means an additive that releases water held within the salt recovery solution.
  • a non-limiting example of a suitable additive that has been shown to release water bound within the salt recovery solution is citric acid or a citric acid solution.
  • the word “regenerant” is also used interchangeably with the work “additive”. This is because the additive regenerates the salt recovery solution.
  • brine or “brine solution” as used throughout the specification means an aqueous solution having a concentration of a salt in the water.
  • the salt in the water could include sodium chloride, however, other salt solutions are envisaged, including ammonium sulfate or the like.
  • concentration of the salt in the aqueous solution may range from about 3.5% (typical concentration of seawater) through to much higher concentrations, such as 25%, which would include a salt water solution used for brining foods.
  • Other brine waste water solutions from textile processing, the semiconductor industry or oil and gas industry would also be applicable for use with the current salt recovery solution and processes defined herein.
  • zero liquid discharge means a wastewater treatment process where no effluent, or discharge, is left over.
  • C 1 -C 7 alkyl refers to a fully saturated branched or unbranched hydrocarbon moiety, which may be a straight or a branched chain of a particular range of 1-7 carbons.
  • the alkyl comprises 1 to 7 carbon atoms, or 1 to 4 carbon atoms.
  • C 1 -C 7 alkyl include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, and the like.
  • C 3 -C 7 monocyclic is a 3-, 4-, 5-, 6-, or 7-membered saturated or unsaturated monocyclic ring.
  • Representative C 3 -C 7 monocyclic groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, and cycloheptyl.
  • 3- to 15-membered monocyclic ketone refers to a 3- to 15-membered non-aromatic monocyclic ring system containing a ketone functional group.
  • Representative examples of a 3- to 15-membered monocyclic ketone include, but are not limited to cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, cyclododecanone, cyclotridecanone; cyclotetradecanone and cyclopentadecanone.
  • the 3- to 15-membered monocyclic ketone may be substituted with one or more of the following groups -halo, —OH, —CN, —NO 2 , —C ⁇ CH, —SH, —C 1 -C 7 alkyl, —(C 1 -C 7 alkyl)-OH, —NH 2 , —NH(C 1 -C 7 alkyl), —NH(C 1 -C 7 alkyl) 2 , —O(C 1 -C 7 alkyl), —C(O)—O(—C 1 -C 7 alkyl), —C(O)OH; —C(O)—H, or —C(O)—(C 1 -C 7 alkyl).
  • groups -halo —OH, —CN, —NO 2 , —C ⁇ CH, —SH, —C 1 -C 7 alkyl, —(C 1 -C 7 alkyl)-OH, —NH 2
  • 8-15 membered aromatic system optionally including one or more heteroatoms selected from S, N or O includes naphthaleneone, fluorenone, quinolinone and indanone ring systems, optionally substituted with halo, hydroxy, nitro, —SH, —C 1 -C 7 alkyl and —O(C 1 -C 7 alkyl).
  • Such compounds of Formula I include, without limitation napthalenone, 2,2,4-trichloro-1(2h)-naphthalenone, 4-methyl-1h-naphthalen-2-one, 9-fluorenone, 9-fluorenone oxime, 2-nitro-9-fluorenone, 3-nitro-9-fluorenone, 4-nitro-9-fluorenone, 2,6-dinitro-9-fluorenone, 2,7-dinitro-9-fluorenone, 2,3,7-trinitro-9-fluorenone, 2-fluoro-9-fluorenone, 1-bromo-9-fluorenone, 2-bromo-9-fluorenone, 2,7-dichloro-9-fluorenone, 2,7-dibromo-9-fluorenone, 2-hydroxy-9-fluorenone, 4-hydroxy-9-fluorenone, 1-methylfluoren-9-one, 4-methylfluoren-9-one 11-benzo(a)fluorenone, benzo(b)fluorenone, 1h-
  • 5-8 membered aromatic monocyclic optionally containing a heteroatom includes without limitation 5-membered rings such as pyrrolyl, furanyl, thiophenyl; 6-membered rings such as phenyl, pyridinyl, pyranyl, thiopyranyl and 7-membered rings such as azepinyl, oxepinyl, thiepinyl.
  • 3- to 15-membered monocyclic heterocyclic ketone refers to: (i) a 3- or 4-membered non-aromatic monocyclic cycloalkyl in which 1 of the ring carbon atoms has been replaced with an N, O or S atom; or (ii) a 5- to 15-membered non-aromatic monocyclic cycloalkyl in which 1-4 of the ring carbon atoms have been independently replaced with a N, O or S atom.
  • a 3- to 15-membered monocyclic heterocyclic ketone having one N, O or S atom include, but are not limited to oxiran-2-one, thiiran-2-one, oxetan-2-one, oxetan-3-one, azetidin-3-one, thietan-2-one, thietan-3-one, dihydrofuran-2(3H)-one, dihydrofuran-3(2H)-one, pyrrolidin-3-one, dihydrothiophen-3(2H)-one, dihydrothiophen-2(3H)-one, tetrahydro-2H-pyran-2-one, dihydro-2H-pyran-3(4H)-one, dihydro-2H-pyran-4(3H)-one, piperidin-3-one, piperidin-4-one, tetrahydro-2H-thiopyran-2-one, dihydro-2H-thiopyran-3(4H)-
  • the 3- to 15-membered monocyclic heterocyclic ketone group may be substituted with one or more of the following groups -halo, —OH, —CN, —NO 2 , —C ⁇ CH, —SH, —C 1 -C 6 lower alkyl, —(C 1 -C 7 alkyl)-OH, —NH 2 , —NH(C 1 -C 7 alkyl), —N(C 1 -C 7 alkyl) 2 , —O(C 1 -C 7 alkyl), —C(O)—O(—C 1 -C 7 alkyl), —C(O)OH; —C(O)—H, or —C(O)—(C 1 -C 7 alkyl).
  • the 3-5 membered monocyclic heterocyclic ketone does not include any amide groups where the ketone enolisable carbonyl group is adjacent a N atom in the cyclic structure
  • halo refers to —F, —Cl, —Br or —I.
  • an enolisable carbonyl means a compound that has one or more carbonyl functional groups and wherein at least one of the carbonyl functional groups has alpha hydrogens (H ⁇ ) that may be removed by a base to form an enolate and then an enol as shown in the reaction scheme below.
  • enolisable carbonyl does not include a compound having solely an aldehyde functional group, a compound having solely a carboxylic acid functional group, a compound having solely an amide functional group, a compound having solely an acyl halide functional group or acetylacetone.
  • the enolisable carbonyls of the invention include without limitation those exemplified in the specification and defined by Formulae I and II, and without limitation also include the following enolisable carbonyls: 1-acetonapthone, 2-acetonaphthone, 4-methyl-1-acetonaphthone, 1′-hydroxy-2′-acetonaphthone, 2′-hydroxy-1′-acetonaphthone, 2-methoxy-1-acetonaphthone, 4-fluoro-1-acetonapthone; 2-acetylphenanthrene, 3-acetylphenanthrene, 4-acetylphenanthrene, 9-acetylphenanthrene, 6-bromo-9-acetylphenanthrene, 9-fluoro-10-acetylphenanthrene, 9-fluorenone, 9-fluorenone oxime, 2-nitro-9-fluorenone, 3-nitro-9-fluorenone, 4-nitro-9-flu
  • tertiary amine containing compound preferably means a compound having at least one tertiary amine group, but it is to be appreciated that the compound may have more than one tertiary amine group or further may be a mixture of tertiary amine containing compounds.
  • the tertiary amine containing compound is a base, such as a Lewis base. If the base is a Lewis base, it is envisaged that a Lewis adduct may be formed with the enolisable carbonyl.
  • the tertiary amine containing compound is immiscible with water at or above 20 degrees Celsius under one standard atmosphere of pressure.
  • the solution may include a combination of more than one tertiary amine containing compound.
  • the tertiary amine containing compound may be aliphatic, conjugated, asymmetric or cyclic or a combination thereof.
  • Suitable tertiary amine containing compounds include the following:
  • the tertiary amine containing compound is selected from 1-ethyl pyrrolidine, 2-methylpyridine, N-methylpiperidine and 4-ethylmorpholine.
  • the tertiary amine containing compound is selected from a —N(C 1 -C 7 alkyl) 3 . In another embodiment the tertiary amine containing compound is selected from a —N(C 1 -C 4 alkyl) 3 . In yet a further embodiment the tertiary amine containing compound is —N(C 2 alkyl) 3 (triethylamine).
  • the present invention is directed to a salt recovery solution suitable for recovering a salt from a first aqueous solution, the salt recovery solution comprising:
  • the process is a minimal liquid discharge process.
  • the process includes the further step of adding an additive to the salt recovery solution to further release water held within the salt recovery solution.
  • the additive is citric acid.
  • the citric acid is a concentrated solution of citric acid comprising between about 200-450 gms of citric acid per litre of water.
  • the citric acid is anhydrous citric acid added directly to the salt recovery solution.
  • the molar ratio of the tertiary amine containing compound to the enolisable carbonyl may vary widely and may be from about 1:99 or 99:1; or from about 1:50 or 50:1 or from about 1:10 or 10:1 or from about 1:5 or 5:1 or from about 1:3 or from about 3:1 or from about 1:2 or from about 2:1. In a preferred embodiment the molar ratio is about 1:1.
  • a chemistry technician would be able to routinely determine the most suitable molar ratio depending on the purpose for which the salt recovery solution is to be employed.
  • the first aqueous solution is salt water or a brine solution.
  • a salt recovery solution was prepared using triethylamine (TEA) and methyl ethyl ketone (MEK) in the molar ratio of 0.5:1.
  • TAA triethylamine
  • MEK methyl ethyl ketone
  • a saturated sodium chloride salt solution was introduced to the salt recovery solution—see step 1 of FIG. 1 .
  • the water formed the aqueous layer with salt precipitate at the bottom of the vial.
  • the salt recovery solution along with the aqueous layer was decanted and the salt was then dried. This demonstrated the recovery of salt from a saturated salt solution using a salt recovery solution and with no liquid discharge.
  • the input salt concentrations were measured, and the dry weights of samples recorded containing 0.2 mL, 0.5 mL and 1 mL of both 50 000 ppm NaCl solution and 100 000 ppm NaCl solution respectively.
  • the input salt results are shown in (Table 3) and the percent salt recovery results are shown in Table 4.
  • the output salt concentrations were also determined as follows.
  • Volume Volume Dry weight Salt recovery % of salt of brine of salt Dry weight of recovery solution precipitated* salt output/Dry solution added (output) weight of salt Brine solution (mL) (mL) avg in mg input ⁇ 100 50 000 ppm NaCl 10.0000 0.2000 0.0112 112.0000 solution 50 000 ppm NaCl 15.0000 0.4000 0.0209 104.5000 solution 50 000 ppm NaCl 10.0000 0.2000 0.0107 107.0000 solution 100 000 ppm NaCl 10.0000 0.2000 0.0243 121.5000 solution 100 000 ppm NaCl 10.0000 0.2000 0.0206 103.0000 solution 100 000 ppm NaCl 10.0000 0.4000 0.0507 126.7500 solution *The dry weights are the average values of each set of two trials.
  • Salt recovery From the above results, it can be seen that it is possible to achieve around 100% salt and water recovery from the brine solution when the volume of brine added is just below the maximum absorption capacity of the salt recovery solution. The deviation in salt recoveries can be attributed to the unavoidable error to the small scale of the experiments.
  • the salt rejection percentage was estimated to show that only water was being absorbed by the salt recovery solution from the brine solution and that the salt recovery solution was rejecting substantially all of the salt from the brine.
  • the conductivity of pure water, the neat brine solution and the concentrated salt recovery solution were measured.
  • the salt rejection % was calculated by the following formula:
  • the salt rejection % of over 99 is indicative of the fact that there is complete precipitation of salt from the brine solution and there are no residual salts going into the salt recovery solution.
  • the salt recovery solution can achieve close to 100% salt and water recovery by minimizing the volume of feed solution in a thermo-efficient way unlike the traditional treatment systems.
  • the lab scale results are indicating that there are no salts going into the salt recovery solution during the absorption process and that the purity of absorbed water is relatively high.
  • Brine Sample 1 has the highest capacity at 0.81 mL (+/ ⁇ 0.04) and Brine Sample 2 having the lowest at 0.15 mL (+/ ⁇ 0.03).
  • This reflects the differing salt compositions and concentrations of each of the commercial brine samples and demonstrates the importance of knowing what the composition of the brine is before salt recovery treatment.
  • the salt recovery solution would be diluted and would be unable to absorb water and precipitate salts effectively. It is to be appreciated that for large scale processes, it would be desirable to utilize higher ratios of salt recovery solution relative to the brine solution to ensure a total absorption of water and avoid brine carry-over.
  • the brine and the salt recovery solution were mixed and resulted in the salt precipitating out.
  • the Samples were left for 20 mins to ensure full separation of the solid salts.
  • the now wet salt recovery solution was decanted into a clean vial using a 5 mL syringe to carefully remove the wet salt recovery solution from the precipitated salts without transferring any salts into the fresh vial (approx. 17 mL, measuring the actual quantity in each individual case).
  • the salt slurry left behind was heated at 110° C. for 1 hour to remove the left-over salt recovery material.
  • the dried salt was cooled and then weighed.
  • the weight of the clean vial was deducted to obtain the weight of salt recovered. The results are tabulated in Table 8.
  • the salt recovery percentage was determined by the following formula.
  • Table 8 above details the raw data collected to calculate the percentage of salt recovered.
  • the “salt expected” was calculated by evaporating the same amount of raw brine as was added to each sample, in a heat block at 110° C. This measured how much salt was in each brine sample and allowed for the calculation of what percentage of this initial brine was collected (see Table 9).
  • the decanted and wet salt recovery material was regenerated using a regenerating agent/regenerant (0.3-0.5 mL) using the following method.
  • the regenerating agent which was a concentrated solution of citric acid (412 g/L) or anhydrous citric acid was added to the diluted/wet salt recovery solution from the previous step to separate the water absorbed by the salt recovery solution. It has been found, and gas chromatographic data has shown that some of the salt recovery solution is dissolved into the regenerant. With reference to FIG. 2 , it can be seen that the gas chromatogram of fresh regenerant shows a small peak at 2.8 mins and a larger slightly trailing peak at 3.0 mins. This larger peak is water which is used as the solvent for the regenerant.
  • the tail is caused by the regenerant material bonding with water molecules.
  • the trailing peak at 4.1 mins is highly characteristic of the salt recovery solutions and clearly indicates that some of the salt recovery solution has leached into the regenerant. Because of the trailing shape of this peak and the overlap of the first peaks, it is not possible to accurately quantify the amount of salt recovery solution which has crossed over into the regenerant, however, semi-quantitative analysis of multiple samples has suggested that up to about 15% of the salt recovery solution has crossed over into the regenerant. To minimise this cross over, the amount of regenerating agent used is selected to be as little as possible. In order to determine the amount of water recovered from the process a known volume of regenerating agent was added to the diluted salt recovery solution.
  • the regenerating agent removed the water from the diluted salt recovery solution to leave a concentrated salt recovery solution. Because of the difference in density between the regenerating agent and the concentrated salt recovery solution, the concentrated salt recovery solution (now non-aqueous or dry) rises to the top while the now diluted regenerating agent sinks to the bottom of the vial. The bottom aqueous layer was carefully removed to a measuring cylinder and the volume recovered was recorded in Table 10. The volume of the aqueous layer was measured using the following formula.
  • volume of water recovered (mL) Volume of aqueous phase (mL) ⁇ Volume of regenerant (mL)
  • the water recovery % was calculated by the formula (Table 10):
  • Table 11 shows the average water and salt recoveries across three samples for each of the brines tested. The majority of the salt recoveries are over 100%. This perhaps indicates some interaction between the salts in the brine and the salt recovery solution which results in the salts binding with the salt recovery solution, resulting in an increase in weight compared to when water is removed by evaporation alone.
  • FIG. 3 shows an example gas chromatograph of Brine Sample 1 focusing on the water peak.
  • the black (solid line) trace is the salt recovery solution before the addition of the brine sample.
  • the second trace (long dash line) shows the water content after the brine sample has been added and shows a clear increase in intensity.
  • the third trace (dotted line) shows the water content after the regenerant has been used to release the water from or dry the salt recovery solution, and clearly shows the water content has largely returned to the same prior to brine sample addition. This shows that the salt recovery solution has been regenerated and is ready for reuse.
  • Parameter Setting Injection Volume 1.0 ⁇ L Injection temperature 250° C.
  • Injection mode Split Split ratio 100.0 Carrier gas He Carrier gas pressure 53.1 kPa Column flow 0.93 mL/min Liner velocity 22.0 cm/s Column length 30.0 m Column inner diameter 0.32 Column method Isocratic Column temperature 163.0° C. Total time 9 min Detector TCD TCD sample rate 40 ms TCD current 70 mA Makeup gas He Makeup flow 8.0 mL/min TCD temperature 200° C.
  • Table 12 shows the quantity of brine water (measured by GC) in the salt recovery solution after it has been used to absorb water and the quantity of brine water left in the salt recovery solution after it has been regenerated. This provides a measure of how effective the regenerant has been at removing water from the salt recovery solution. As can be seen from Table 12, the quantity of water remaining in the salt recovery solution after regeneration is very small. This shows that the citric acid regenerant has been very effective in removing most of the brine water from the salt recovery solution.
  • salt recovery solutions were made up with amine(s) and ketone(s) in various specified molar ratios (see Tables 13-17 below).
  • brine 300 000 ppm NaCl was slowly added to 5 mL of the selected salt recovery solution.
  • the brine was absorbed by the salt recovery solution and the salts in the brine precipitated out.
  • the addition of the brine was stopped as soon as a separate phase started to form at the bottom of the vial after shaking. The presence of the separate phase shows that the maximum absorption capacity of the salt recovery solution has been reached. At this point the volume of the brine, which has been added to the salt recovery solution is recorded.
  • Table 13 summarises the maximum absorbing capacity of the salt recovery solution, along with the water recovery and the salts recovery of the different salt recovery solutions containing different amines with 2-butanone. 300 000 ppm NaCl solution was passed through each combination of the salt recovery solution outlined in the following Table 13. The salt and water recovery results listed in this table record one-off tests.
  • the following table 14 summarises the maximum absorbing capacity of the salt recovery solution along with the water recovery and the salts recovery of the different salt recovery solutions containing triethylamine combined with different ketones. 300 000 ppm NaCl solution was passed through each combination of the salt recovery solution outlined in the following table 14. The salt and water recovery results listed in this table record one-off tests.
  • the following table 15 summarises the maximum absorbing capacity of the salt recovery solution along with the water recovery and the salts recovery of the different salt recovery solutions containing up to three different amines combined with cyclohexanone. 300 000 ppm NaCl solution was passed through each combination of the salt recovery solution outlined in the following Table 15. The salt and water recovery results listed in this table record one-off tests.
  • the following table 16 summarises the maximum absorbing capacity of the salt recovery solution along with the water recovery and the salts recovery of the different salt recovery solutions containing up to two different amines combined with up to two different ketones. 300 000 ppm NaCl solution was passed through each combination of the salt recovery solution outlined in the following Table 16. The salt and water recovery results listed in this table record one-off tests.
  • the following table 17 summarises the maximum absorbing capacity of the salt recovery solution along with the water recovery and the salts recovery of the different salt recovery solutions containing up to three different amines combined with up to three different ketones. 300 000 ppm NaCl solution was passed through each combination of the salt recovery solution outlined in the following Table 16. The salt and water recovery results listed in this table record one-off tests.
  • Salt recovery solutions were prepared using: Triethylamine (TEA) and methyl ethyl ketone (MEK), N-Ethylpiperidine and cyclohexanone in the molar ratio of 0.5:1.
  • Example 5 The experiment described in Example 5 was repeated, except the 5% NaCl solution was replaced with a 20% (w/w) ammonium sulfate (NH 4 SO 4 ) solution.
  • Salt recovery solutions were prepared using: Triethylamine (TEA) and methylethylketone (MEK).
  • the results shown in FIG. 10 and Table 20 show that the salt recovery solution (TEA:MEK) is capable of concentrating a salt solution to a higher final concentration. Essentially water has been recovered from the initial NH 4 SO 4 solution and the water has moved into the salt recovery solution effectively leading to the concentration of the initial NH 4 SO 4 solution.

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  • Extraction Or Liquid Replacement (AREA)
  • Hydrogenated Pyridines (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
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CN116282078A (zh) 2023-06-23
KR20200086272A (ko) 2020-07-16
CL2020000891A1 (es) 2020-10-02
JP2020535953A (ja) 2020-12-10
WO2019070134A2 (en) 2019-04-11
BR112020006722A2 (pt) 2020-10-06
WO2019070134A3 (en) 2020-01-02
TW201922681A (zh) 2019-06-16
CN111225875A (zh) 2020-06-02
SA520411670B1 (ar) 2023-12-03
JP7291690B2 (ja) 2023-06-15
IL273653B1 (en) 2024-02-01
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US11987506B2 (en) 2024-05-21
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