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WO2025219513A1 - Compositions et procédés d'élimination de métaux lourds de flux contenant de l'acide - Google Patents

Compositions et procédés d'élimination de métaux lourds de flux contenant de l'acide

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Publication number
WO2025219513A1
WO2025219513A1 PCT/EP2025/060636 EP2025060636W WO2025219513A1 WO 2025219513 A1 WO2025219513 A1 WO 2025219513A1 EP 2025060636 W EP2025060636 W EP 2025060636W WO 2025219513 A1 WO2025219513 A1 WO 2025219513A1
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Prior art keywords
acid
compound
composition according
containing stream
dialkyldithiophosphate
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PCT/EP2025/060636
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English (en)
Inventor
Ravi Rajshekar HIREMATH
Lei Zhang
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Cytec Industries Inc
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Cytec Industries Inc
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Publication of WO2025219513A1 publication Critical patent/WO2025219513A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/18—Phosphoric acid
    • C01B25/234—Purification; Stabilisation; Concentration
    • C01B25/237—Selective elimination of impurities
    • C01B25/238—Cationic impurities, e.g. arsenic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
    • C07F9/3873—Polyphosphonic acids containing nitrogen substituent, e.g. N.....H or N-hydrocarbon group which can be substituted by halogen or nitro(so), N.....O, N.....S, N.....C(=X)- (X =O, S), N.....N, N...C(=X)...N (X =O, S)
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C02F1/004—Processes for the treatment of water whereby the filtration technique is of importance using large scale industrial sized filters
    • 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
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • 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
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/04—Surfactants, used as part of a formulation or alone

Definitions

  • the technological concept disclosed herein generally relates to purification of industrial process streams. More particularly, the concept disclosed herein relates to removing heavy metal ions, especially cadmium, arsenic and copper, from acid-containing streams. Background In several sectors, industries are faced with metal impurities which, beyond a certain level, are considered unacceptable, depending on industry specification. Accordingly, the metal impurities have to be either completely removed or their levels have to be significantly reduced.
  • Cd in phosphate fertilizer comes from phosphoric acid, the major raw material used to produce phosphate fertilizer. In fact, the majority of phosphoric acid production is used to produce fertilizer. Cd in phosphoric acid further stems from the phosphate bearing ores. Therefore, Cd can be removed either from the phosphate ore or from the phosphoric acid stream, with the latter being the focus of research in the past decades.
  • Cobalt and nickel metals are extracted from the solid feed material through leaching, that involves transferring a metal of interest from naturally occurring minerals into an aqueous solution, where cobalt and nickel metals may be first subjected to comminution and then contacted with a sulfuric acid leaching reagent which dissolves the metal, transferring it to an aqueous phase as a metal sulfate.
  • leaching involves transferring a metal of interest from naturally occurring minerals into an aqueous solution, where cobalt and nickel metals may be first subjected to comminution and then contacted with a sulfuric acid leaching reagent which dissolves the metal, transferring it to an aqueous phase as a metal sulfate.
  • Cobalt and nickel considered “value metals”, and metal impurities are transferred from the solid feed material to the aqueous phase in varying quantities forming an acidic metal sulfate containing stream.
  • Value metals may be recovered from the aqueous solution as saleable products in subsequent product recovery steps by techniques such as precipitation, electrowinning, or crystallization.
  • cadmium levels in cobalt sulfate heptahydrate and nickel sulfate hexahydrate, produced for the lithium ion battery industry may be ⁇ 5 mg/kg and ⁇ 1 mg/kg respectively.
  • Nickel power may require cadmium levels ⁇ 7 mg/kg.
  • Impurity metal ions in the acidic metal sulfate stream must be reduced with high efficiency and with high selectivity relative to value metals.
  • Iron, aluminum, manganese, and/or copper present in the initial acidic metal sulfate leach solution are commonly removed using precipitation in a multi-stage process by the addition of lime (or an alternative base) and an oxidant such as air, sulfur dioxide or their mixture. Copper may be further reduced using conventional methods such as solvent extraction and/or ion exchange.
  • Minor impurity metal ions, especially cadmium, and also arsenic, lead, mercury, chromium, titanium, and copper may require alternative processing steps to reduce their concentration in the acidic metal sulfate-containing streams.
  • U.S. Patent No. 4,378,340 (1983) describes a method of removing heavy metals, particularly cadmium, from wet process phosphoric acid through partial neutralization of acids with alkali, followed by precipitation with sulfide compounds.
  • U.S. Patent No. 5,431,895 (1995) also discloses using alkali solution and aqueous sulfide solution simultaneously with thorough mixing to remove lead and cadmium from phosphoric acid. The precipitation of metal hydroxides and carbonates is complicated by poor selectivity resulting in the co-precipitation of value metals.
  • cadmium sulfide involves the use of hazardous sulfide precipitating agents (Na 2 S, NaHS, H 2 S).
  • hazardous sulfide precipitating agents Na 2 S, NaHS, H 2 S.
  • Alternative cadmium precipitation methods were proposed by Rickelton (1998) who found a selective method of removing cadmium from zinc, cobalt and nickel by precipitation as its diisobutyldithiophosphinate complex.
  • Dialkyldithiophinates are synthesized using high- pressure phosphine and may be difficult to manufacture industrially.
  • the patent application DE 40 40474 A1 (1990) discloses using dithiophosphorous esters of the formula (R- (OC2H4)x-O)2PS2M where R is C9-C18 alkyl or alkenyl compound, x is an integer from 0 to 6 and M is a cation to remove Zn, Cd, Hg, Cu, Ni or As from crude phosphoric acid or from sulfuric acid (for example, during the treatment of lead-acid batteries). Cadmium is removed using precipitation and flotation in the presence of a foaming agent. Solvent extraction (liquid-liquid) extraction with dithiophosphorous compounds has also been proposed to extract cadmium from phosphoric acid and sulfuric acid based systems.
  • 4,479,924 (1980) proposes a method of extracting metal ions, including cadmium, from an aqueous solution by contact with a reagent mixture including a water insoluble diester of dithiophosphoric acid, a water-insoluble phosphate, and a diluent.
  • a reagent mixture including a water insoluble diester of dithiophosphoric acid, a water-insoluble phosphate, and a diluent.
  • Heavy metal contamination of food especially cadmium that stems from use of phosphoric acid in fertilizer production, continues to be a concern to public health..
  • there has been a recent regulatory push to further limit the Cd level in phosphate fertilizers See European Commission Fact Sheet.
  • compositions and methods presently available for heavy metal removal from acid streams in the production process require further and/or continuous improvement. Since many factors (e.g., ore type, temperature, agitation, reactor design, acid chemistry, foreign ions, organic species, and viscosity of acid medium) can affect the performance of reagents, it is a great challenge to develop high-efficiency reagents useful for removing heavy metals from acid streams. Successful reagents for removing heavy metals in industrial process streams such as wet process phosphoric acid or hydrometallurgical production of cobalt, and nickel metals would be a useful advance in the art and could find rapid acceptance in the industry.
  • the present invention provides compositions for complexing heavy metals ions, especially cadmium and arsenic, from the acid-containing streams, wherein the composition comprises an effective amount of a reagent comprising at least one dialkyldithiophosphate compound, with the alkyl chain length of C2 to C12 and at least one phosphonate compound.
  • the reagent can further comprise at least one surfactant.
  • the reagent can further comprise at least one dialkyldithiophosphinate compound.
  • the invention provides processes for removing heavy metal ions, especially cadmium and arsenic, from a solution containing acid streams, by adding an effective amount of a reagent comprising at least one dialkyldithiophosphate compound, with the alkyl chain length of C2 to C12 and at least one phosphonate compound to the solution to form heavy metal complexes and separating the heavy metal complexes from the solution.
  • the process can further comprise adding an effective amount of at least one surfactant to the solution containing acid streams.
  • the process can further comprise adding an effective amount of at least one dialkyldithiophosphinate compound to the solution containing acid streams.
  • the process can further comprise adding an effective amount of a reducing agent to the solution containing acid streams. In the same or additional embodiments, the process can further comprise adding an effective amount of an adsorbent to the solution containing acid streams.
  • compositions and processes described herein provide improvement and/or an unexpected advantage when compared to compositions and processes of the prior art.
  • the following terms are provided to assist the reader. Unless otherwise defined, all terms of art, notations and other scientific or industrial terms or terminology used herein are intended to have the meanings commonly understood by those of skill in the chemical and/or phosphoric acid production arts.
  • Such heavy metal ions include, for example, one or more of, cadmium, chromium, arsenic, nickel, mercury, zinc, manganese, titanium, copper and lead.
  • cadmium ions are removed from acid-containing streams.
  • arsenic ions are removed from acid-containing streams.
  • the concept of “heavy metal complex” refers to compounds formed by reacting heavy metal ions with chelating agents. Heavy metal complexes can be solid, waxy, or oily in the phosphoric acid solutions. They can precipitate, float, or suspend in the phosphoric acid solutions.
  • the acid-containing streams can be oxyacid containing streams like phosphoric acid, sulfuric acid and acidic metal sulfate containing streams.
  • the acid-containing streams can be phosphoric acid containing streams that, in the context of the invention, may include any acidic solution containing crude phosphoric acid, digestion slurries of phosphoric acid, filtered phosphoric acid, and/or concentrated phosphoric acid.
  • Such phosphoric acid containing streams are typically obtained from industrial phosphoric acid production plant streams.
  • the acid-containing streams can also be acidic metal sulfate containing streams that; in the context of the invention, may include any acidic solution derived from the leaching of a solid feed material with sulfuric acid.
  • Such metal sulfate containing streams are typically obtained from plant streams of hydrometallurgical production of cobalt, and nickel metals.
  • acidic metal sulfate streams can contain cobalt and/or nickel metals.
  • Effective amount means the dosage of any reagents on an active basis (such as the compositions comprising at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 and at least one phosphonate compound described herein) necessary to provide the desired performance in the acid system or circuit being treated (such as the formation of heavy metal complexes) when compared to an untreated control system or system using a reagent product of the prior art.
  • the term “alkyl” is intended to include linear, branched, or cyclic hydrocarbon structures and combinations thereof. Preferred alkyl groups are those of C30 or below. Lower alkyl refers to alkyl groups of from 1 to 6 carbon atoms.
  • lower alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, s-and t-butyl, pentyl, hexyl and the like.
  • Cycloalkyl is a subset of alkyl and includes cyclic hydrocarbon groups having from 3 to 30 carbon atoms, preferably from 3 to 8 carbon atoms as well as polycyclic hydrocarbons having 7 to 10 carbon atoms.
  • aryl refers to cyclic aromatic hydrocarbons that do not contain heteroatoms in the ring. In any or all embodiments, aryl groups contain about 6 to about 14 carbons in the ring portions of the groups.
  • aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups.
  • Aryl groups can be unsubstituted or substituted, as defined herein.
  • substituted aryl groups can be mono-substituted or substituted more than once, such as, but not limited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or 2-8 substituted naphthyl groups, which can be substituted with carbon or non-carbon groups such as those known to persons of skill in the art.
  • Aryl groups of C 6 -C 12 are preferred.
  • alkaryl as used herein is a broad term and is used in its ordinary sense, including, without limitation, to refer to an aryl having at least one aryl hydrogen atom replaced with an alkyl moiety.
  • aralkyl as used herein is a broad term and is used in its ordinary sense, including, without limitation, to refer to an alkyl having at least one alkyl hydrogen atom replaced with an aryl moiety, such as benzyl, –CH2(1 or 2- naphthyl), –(CH2)2phenyl, –(CH2)3phenyl, –CH(phenyl)2, and the like. Particularly preferred are C 7-20 aralkyl groups.
  • any recitation herein of a numerical range by endpoints includes all numbers subsumed within the recited range (including fractions), whether explicitly recited or not, as well as the endpoints of the range and equivalents.
  • the term “et seq.” is sometimes used to denote the numbers subsumed within the recited range without explicitly reciting all the numbers, and should be considered a full disclosure of all the numbers in the range. Disclosure of a narrower range or more specific group in addition to a broader range or larger group is not a disclaimer of the broader range or larger group.
  • the invention embodies compositions for forming complexes with heavy metal ions in an acid-containing stream, wherein the compositions comprise an effective amount of a reagent comprising: at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12; and at least one phosphonate compound.
  • dialkyldithiophosphate compounds with the alkyl chain length of C2 to C12 comprise dialkyldithiophosphoric acid with the alkyl chain length of C2 to C12 and any salts (e.g., calcium, magnesium, potassium, sodium, ammonium salt with the formula NR1R2R3R4 + , where R1, R2, R3, R4 are, equal to or different from each other, independently chosen from hydrogen, alkyl or aryl groups) of any of the foregoing dialkyldithiophosphoric acid with the alkyl chain length of C2 to C12; and mixtures thereof.
  • any salts e.g., calcium, magnesium, potassium, sodium, ammonium salt with the formula NR1R2R3R4 + , where R1, R2, R3, R4 are, equal to or different from each other, independently chosen from hydrogen, alkyl or aryl groups
  • the dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 is selected from the group consisting of dialkyldithiophosphoric acid with the alkyl chain length of C2 to C12 and salts of any of the foregoing dialkyldithiophosphoric acid with the alkyl chain length of C2 to C12 in the form of calcium, magnesium, potassium, sodium salt or ammonium salt with the formula NR 1 R 2 R 3 R 4 + , where R 1 , R 2 , R 3 , R 4 are, equal to or different from each other, independently chosen from hydrogen, alkyl or aryl groups; and mixtures thereof.
  • the alkyl chain of the dialkyldithiophosphate compound according to the invention is a C6 to C12 chain. In some preferred embodiments, the alkyl chain of the dialkyldithiophosphate compound according to the invention is a C8 to C10 chain. Preferably, the alkyl chain of the dialkyldithiophosphate compound according to the invention is a C8 alkyl chain.
  • the dialkyldithiophosphate compound is selected from the group consisting of any salts of di(1,3-dimethylbutyl) dithiophosphoric acid, di(2-ethylhexyl) dithiophosphoric acid, di(3,7-dimethyloctyl) dithiophosphoric acid, di(2-butyloctanol) dithiophosphoric acid; and mixtures thereof, said salts being as defined previously.
  • dialkyldithiophosphate compound is salts of di(2- ethylhexyl) dithiophosphoric acid, di(3,7-dimethyloctyl) dithiophosphoric acid, and di(2- butyloctanol) dithiophosphoric acid, and mixtures thereof.
  • the dialkyldithiophosphate compound is any salts of di(2-ethylhexyl) dithiophosphoric acid.
  • the dialkyldithiophosphate compound is ammonium salt of di(2-ethylhexyl) dithiophosphoric acid.
  • the dialkyldithiophosphate compound is sodium salt of di(2- ethylhexyl) dithiophosphoric acid.
  • the dialkyldithiophosphate compound is selected from the group consisting of di(1,3-dimethylbutyl) dithiophosphate, di(2- ethylhexyl) dithiophosphate, di(3,7-dimethyloctyl) dithiophosphate, di(2-butyloctanol) dithiophosphate; and mixtures thereof.
  • dialkyldithiophosphate compound are di(2-ethylhexyl) dithiophosphate, di(3,7-dimethyloctyl) dithiophosphate, and di(2-butyloctanol) dithiophosphate; and mixtures thereof.
  • the dialkyldithiophosphate compound is di(2-ethylhexyl) dithiophosphate.
  • the dialkyldithiophosphate compound is ammonium di(2- ethylhexyl) dithiophosphate.
  • the dialkyldithiophosphate compound is sodium di(2-ethylhexyl) dithiophosphate.
  • the phosphonate compounds described herein for any or all embodiments comprises the following formula: wherein: R” is an optionally substituted hydrocarbyl radical comprising from about 1 to about 20 carbons; R’ is H, optionally substituted C1-C20 alkyl, optionally substituted C6-C12 aryl, optionally substituted C7-C20 aralkyl, optionally substituted C2-C20 alkenyl, Group I metal ion, Group II metal ion, or NR 1 R 2 R 3 R 4 + , where R 1 , R 2 , R 3 , R 4 are, equal to or different from each other, independently chosen from hydrogen, alkyl, alkenyl, or aryl groups.
  • the phosphate compound is selected from diethylenetriaminepentakis(methylphosphonic acid), nitrilotri(methylphosphonic acid), iminodi(methylphosphonic acid), (aminomethyl)phosphonic acid, N,N- bis(phosphonomethyl)glycine, glyphosate, and mixtures thereof.
  • the phosphate compound is diethylenetriaminepentakis(methylphosphonic acid).
  • the reagent can further comprise at least one surfactant.
  • the reagent can further comprise at least one dialkyldithiophosphinate compound.
  • dialkyldithiophosphinate compound described herein for any or all embodiments comprise dialkyldithiophosphinic acid and any salts (e.g., calcium, magnesium, potassium, sodium, ammonium salt with the formula NR1R2R3R4 + , where R1, R2, R3, R4 are, equal to or different from each other, independently chosen from hydrogen, alkyl or aryl groups) of the foregoing dialkyldithiophosphinic acid; and mixtures thereof.
  • any salts e.g., calcium, magnesium, potassium, sodium, ammonium salt with the formula NR1R2R3R4 + , where R1, R2, R3, R4 are, equal to or different from each other, independently chosen from hydrogen, alkyl or aryl groups
  • the dialkyldithiophosphinate compound is selected from the group consisting of dialkydithiophosphinic acid and any salts (e.g., calcium, magnesium, potassium, sodium) of the foregoing dialkyldithiophosphinic acid in the form of calcium, magnesium, potassium, sodium salt or ammonium salt with the formula NR1R2R3R4 + , where R1, R2, R3, R4 are, equal to or different from each other, independently chosen from hydrogen, alkyl or aryl groups; and mixtures thereof.
  • any salts e.g., calcium, magnesium, potassium, sodium
  • the dialkyldithiophosphinate compound is selected from the group consisting of any salts of diisobutyl dithiophosphinic acid; bis(2,4,4-trimethylpentyl) dithiophosphinic acid; and mixtures thereof, said salts being as defined above.
  • the dialkyldithiophosphinate compound is sodium diisobutyl dithiophosphinate.
  • the surfactant compound can be selected from the group consisting of sulfosuccinates; aryl sulfonates; alkaryl sulfonates; diphenyl sulfonates; olefin sulfonates; sulfonates of ethoxylated alcohols; petroleum sulfonates; sulfosuccinamates; alkoxylated surfactants; ester/amide surfactants; EO/PO block copolymers (ethylene oxide/propylene oxide); and mixtures thereof.
  • the surfactant can be an alkaryl sulfonates.
  • the surfactant can be alkyldiphenyloxide disulfonate. Suitable alkyldiphenyloxide disulfonate compounds include, but are not limited to, DOWFAX® 2A1, DOWFAX® 3B2, DOWFAX® 8390 available from Dow Chemical.
  • the surfactant can be a sulfosuccinate. Suitable sulfosuccinate can be sodium dioctylsulfosuccinate. Suitable sodium dioctylsulfosuccinate compounds include, but are not limited to, AEROSOL® OT-70 PG available from Syensqo S.A.
  • the surfactant can be an alkoxylated surfactant.
  • Suitable alkoxylated surfactants can include, but are not limited to, polyethyleneglycol sorbitan monooleate (such as TWEEN® 80 available from Croda), and polyethyleneglycol sorbitol hexaoleate (such as ATLAS® G1086 available from Croda).
  • the invention embodies processes for removing heavy metal ions from an acid-containing stream, wherein such processes comprise: adding an effective amount of a reagent, comprising a composition for forming complexes with heavy metal ions as disclosed and embodied herein, to the acid-containing stream to form heavy metal ion complexes, and separating the heavy metal ion complexes from the acid-containing stream.
  • a reagent comprising a composition for forming complexes with heavy metal ions as disclosed and embodied herein
  • the dialkyldithiophosphate compound is in a diluted solution when it is added to an acid-containing stream.
  • the diluted solution may include a percent active (of dialkyldithiophosphate compound) having a lower limit of any of greater than 0, 1, 2, 5, or 10% to an upper limit of any of 10, 12, 15, 20 or 35%.
  • the diluted solution may include water.
  • the dialkyldithiophosphate compound prior to adding a dialkyldithiophosphate compound to an acid-containing stream for forming heavy metal ion complexes, the dialkyldithiophosphate compound may be diluted prior to adding a dialkyldithiophosphate compound to an acid-containing stream for forming heavy metal ion complexes.
  • the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12, and the at least one phosphonate compound, and optionally the at least one surfactant and/or the at least one dialkyldithiophosphinate compound can be added to the acid-containing stream to complex the heavy metal ions. Afterwards, heavy metal complexes formed can be separated from the acid-containing stream.
  • the acid-containing stream being phosphoric acid stream, the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12, and the at least one phosphonate compound, and optionally the at least one surfactant and/or the at least one dialkyldithiophosphinate compound can be added to either the crude phosphoric acid or digestion slurries prior to gypsum filtration, or to the filtered phosphoric acid or to the concentrated phosphoric acid to complex the heavy metal ions. Afterwards, heavy metal complexes so formed can be separated from the phosphoric acid or slurry.
  • the acid-containing stream being acidic metal sulfate stream, the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12, and the at least one phosphonate compound, and optionally the at least one surfactant and/or the at least one dialkyldithiophosphinate compound can be added to the acidic metal sulfate containing solution, preferably following the removal of some other metals considering as major impurities, such as iron and copper impurities, using conventional techniques, or any point prior to the recovery of cobalt and/or nickel products. Afterwards, the heavy metal complexes so formed may be separated from the cobalt and/or nickel containing solution.
  • Separation may be carried out via any suitable method known in the art for such separation.
  • the methods of separation include, but are not limited to, filtration, centrifugation, sedimentation, creaming, skimming, flocculation, adsorption, phase separation, and/or flotation.
  • the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12, and the at least one phosphonate compound, and optionally the at least one surfactant and/or the at least one dialkyldithiophosphinate compound can be added to the solution containing acid all in one stage or added in several stages.
  • the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 and the at least one phosphonate compound, and optionally the at least one surfactant and/or the at least one dialkyldithiophosphinate compound is added as a blend, or separately in any order such as concurrently together or sequentially.
  • the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 and the at least one phosphonate compound, and optionally the at least one surfactant and/or the at least one dialkyldithiophosphinate compound is added as a blend.
  • Treatment times in any or all embodiments of the invention can be from a few seconds (i.e., 5 to 10 seconds) to 240 minutes. In those instances where the reagent complexes the heavy metals very rapidly, the preferred treatment times are from about 5 seconds to 5 minutes. Most typically, the treatment times are from 10 seconds to 60 seconds or 120 seconds.
  • the dosage of the reagent for complexing heavy metals and removal efficiency for the various heavy metals will depend on the amount of heavy metal impurities present in the ore and/or acid-containing streams. Generally, the greater the number of heavy metals present and the higher their concentrations, the greater will be the overall dosage of the reagent.
  • the dosages may generally be in the range of from 0.01 to 50 kg (e.g., 0.01, 0.02, 0.03, 0.04, 0.05, et seq. to 0.10, 0.15, 0.20, 0.25, 0.30, et seq.
  • the dosages can be from 0.1 kg to 10 kg (e.g., 0.10, 0.15, 0.20, 0.25, 0.30, et seq. to 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, and 10 kg) of reagent per ton of P2O5.
  • any of the recited dosages can also be recited as “less than” a particular dosage, e.g., less than 50 kg; or that any of the recited dosages (except the highest dosage point) can also be recited as “greater than” a particular dosage, e.g., greater than 0.10 kg.
  • the acid-containing stream being acidic metal sulfate stream
  • the dosages may generally be in the range of from 1 to 10 mole dialkyldithiophosphate per mole of heavy metal, based on the type of heavy metal ions to be removed.
  • the dosages can be from 2 to 4 mole dialkyldithiophosphate per mole of heavy metal ions to be removed. In the case of several heavy metal ions present, the total dose should be the sum of the individual heavy metal dosages.
  • the weight ratio of the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 to the at least one phosphonate compound is from 1000:1 to 5:1. In a preferred embodiment, the weight ratio of the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 to the phosphonate compound is from 100:1 to 10:1, preferably from 70:1 to 30:1.
  • the weight ratio of the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 to the at least one surfactant is from 1000:1 to 5:1. In a preferred embodiment, the weight ratio of the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 to the at least one surfactant is from 100:1 to 10:1, preferably from 70:1 to 30:1. In any or all embodiments, the weight ratio of the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 to the at least one dialkyldithiophosphinate compound is from 100:0 to 1:100.
  • the weight ratio of the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 to the at least one dialkyldithiophosphinate compound is from 1:20 to 20:1, preferably from 1:10 to 10:1.
  • the acid-containing stream being phosphoric acid stream
  • the solution containing phosphoric acid has a P 2 O 5 concentration from 4 wt. % to 70 wt. %, typically from 25 wt. % to 60 wt. %.
  • Specific concentrations of P2O5 contemplated for use with the invention include 25 wt. %, 28 wt. %, 30 wt. %, 42 wt.
  • the acid-containing stream being acidic metal sulfate stream, the solution containing acidic metal sulfates, has a pH from 0 to 6, typically from 1 to 6.
  • the compositions and processes described herewith as the present invention can be used over a wide temperature range. In any or all embodiments, for example, the processes according to the invention can be performed at a temperature from 0 °C to 120 °C, in particular from 0 °C to 80 °C.
  • the temperature is in the range from 20 °C to 80 °C, more preferably from 20 °C to 70 °C, in particular from 20 °C to 60°C.
  • the process can further comprise adding an effective amount of a reducing agent and/or an adsorbent to the solution containing acid.
  • a reducing agent and/or an adsorbent are known to be useful in the field. In certain circumstances one or both of these agents can enhance the activity of the reagent including the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 and the at least one phosphonate compound, and optionally the at least one surfactant and/or the at least one dialkyldithiophosphinate compound.
  • the reducing and/or adsorbent agent can be added to the acid-containing streams all in one stage or added in several stages.
  • the reducing and/or adsorbent agent can be added together as a blend with the reagent including the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 and the at least one phosphonate compound, and optionally the at least one surfactant and/or the at least one dialkyldithiophosphinate compound, or separately in any order with the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 and the at least one phosphonate compound, and optionally the at least one surfactant and/or the at least one dialkyldithiophosphinate compound such as concurrently together or sequentially.
  • Reducing agents useful in any or all processes according to the invention include, but are not limited to, iron powder, zinc, red phosphorus, iron (II) sulfate, sodium hypophosphite, hydrazine, hydroxymethane sulfonate, and mixtures thereof.
  • the process can further comprise adding an effective amount of a reducing agent to the acid-containing stream.
  • the reducing agent is selected from the group consisting of sodium hypophosphite, hydrazine, iron (II) sulfate, iron powder, and mixtures of any of the foregoing.
  • the reducing agent is iron powder and sodium hypophosphite.
  • the reducing agent can be added prior to, or together with, the reagent.
  • the acid-containing stream being phosphoric acid stream the reducing agent is used in an amount from 0.01 kg to 50 kg of reagent per ton of P2O5, based on the type and quantity of the oxidants in the phosphoric acid solution, which can be readily determined by those skilled in the art using no more than routine methods.
  • the amount of reducing agent is from 0.1 kg to 5 kg of reagent per ton of P2O5 of the phosphoric acid solution.
  • Adsorbent agents can be useful in any or all embodiments according to the invention and include, but are not limited to, active charcoal/carbon, carbon black, ground lignite, adsorbents containing silicate (e.g., synthetic silicic acids, zeolites, calcium silicate, bentonite, perlite, diatomaceous earth, and fluorosilicate), calcium sulfate (including gypsum, hemihydrate, and anhydride), oxides or hydroxides of iron, aluminum, copper or manganese, and mixtures thereof.
  • silicate e.g., synthetic silicic acids, zeolites, calcium silicate, bentonite, perlite, diatomaceous earth, and fluorosilicate
  • calcium sulfate including gypsum, hemihydrate, and anhydride
  • oxides or hydroxides of iron, aluminum, copper or manganese and mixtures thereof.
  • the process can further comprise adding an effective amount of an adsorbent to the acid-containing stream.
  • the adsorbent is selected from the group consisting of calcium sulfate, fluorosilicate, activated carbon, oxides or hydroxides of iron, aluminum, copper, or manganese and mixtures of any of the foregoing.
  • the adsorbent is present in an amount from 0.05 wt. % to 50 wt. %, and preferably from 0.1 wt. % to 30 wt. %, based on the quantity of acid in the solution.
  • the process is performed at a temperature from 0 ⁇ C to 120 ⁇ C; preferably from 20 ⁇ C to 80 ⁇ C.
  • the process can comprise the step of filtering the acid-containing streams prior to adding the reagent.
  • the at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 and the at least one phosphonate compound, and optionally the at least one surfactant and/or the at least one dialkyldithiophosphinate compound, of the reagent are added simultaneously, in the form of blend, to the acid-containing stream.
  • the heavy metal ions that are complexed by the reagent and removed by separation are selected from the group consisting of titanium, chromium, cadmium, arsenic, mercury, copper, lead, and mixtures of any of the foregoing.
  • said heavy metal ions are selected from the group consisting of cadmium, copper, arsenic, mercury, lead, and mixtures thereof.
  • the heavy metal ions comprise cadmium and/or arsenic and/or copper.
  • the heavy metal ion is cadmium.
  • the heavy metal ion is arsenic.
  • the performances of blends of at least one dialkyldithiophosphate compound with the alkyl chain length of C2 to C12 and the at least one phosphonate compound, and optionally of the at least one surfactant and/or the at least one dialkyldithiophosphinate compound, to remove heavy metals are evaluated with phosphoric acid and phosphoric acid slurries and with acidic metal sulfate solutions.
  • the phosphoric acids with different P 2 O 5 levels are obtained from industrial phosphoric acid processing plants.
  • the phosphoric acid slurries are generated by mixing plant gypsum solids with plant phosphoric acid. To separate the heavy metal precipitates from the acid, either a syringe filter or a vacuum filtration is used.
  • the filtrate acids are analyzed with ICP (Inductively Coupled Plasma) to determine the level of various heavy metal elements.
  • ICP Inductively Coupled Plasma
  • Phosphonate compound diethylenetriamine penta(methylene phosphonic acid), or DTPMP was purchased from ZSCHIMMER & SCHWARZ Inc. with the product name CUBLEN DNC 450.
  • the sodium diisobutyl dithiophosphinate (“Na-DTPi”), Dioctyldithiophosphinic acid (CYANEX 301), and the sodium dioctylsulfosuccinate (AEROSOL OT70PG – “Surfactant C”) were obtained from Syensqo SA.
  • the alkyldiphenyloxide disulfonate surface active solution (DOWFAX® 8390 – “Surfactant A”) was purchased from Dow Chemicals.
  • the polyethyleneglycol sorbitol hexaoleate (ATLAS® G1086 – “Surfactant B”) was purchased from Croda.
  • the dialkyldithiophosphate compounds with various chain lengths were synthesized in Syensqo laboratories.
  • the blend was prepared by combining the phosphonate compound, and dialkyldithiophosphate compounds with various chain lengths.
  • Some blends further comprise the surfactant and/or the Na-DTPi (Sodium diisobutyl dithiophosphinate) or Dioctyldithiophosphinic acid (CYANEX 301).
  • the dialkyldithiophosphate compounds with various chain lengths were synthesized as explained in Example 1 below.
  • Example 1 Preparation of the dialkyldithiophosphate compounds
  • Example 1-A Synthesis of ammonium di(2-ethylhexyl) dithiophosphate (“C8DTP- NH 4 Salt”) To a 250 ml 3-neck round bottom flask equipped with a heating mantle, magnetic stirring, nitrogen flow and vent to a caustic scrubber was added 155.57 g (1.1946 moles) of 2-ethylhexanol (2mole% excess). After heating to 40 °C, 65.00 g of P2S5 (0.1464 moles) was added in three equal portions over 30 minutes with vigorous stirring. The reaction temperature was then increased to 80 °C where it was held for 4 hours.
  • C8DTP- NH 4 Salt ammonium di(2-ethylhexyl) dithiophosphate
  • reaction product was cooled and filtered to yield a light yellow, low viscosity liquid. ( 31 P NMR ⁇ 85ppm, 85.4%).
  • Example 1-B Synthesis of di(3,7-dimethyloctyl) dithiophosphoric acid (“C10DTP”) To a 250ml 3-neck round bottom flask equipped with a heating mantle, magnetic stirring, nitrogen flow and vent to a caustic scrubber was added 159.99 g (1.0108 moles) of 3,7-dimethyloctanol (2mole% excess). After heating to 40 °C, 80.00 g of P2S5 (0.1239 moles) was added in three equal portions over 30 minutes with vigorous stirring. The reaction temperature was then increased to 80 °C where it was held for 4 hours.
  • C10DTP di(3,7-dimethyloctyl) dithiophosphoric acid
  • Example 2 Process for removing heavy metals from concentrated phosphoric acids from production plants ( ⁇ 57% P2O5) at elevated temperature (65 ⁇ C) 50 g of concentrated phosphoric acid from the plant ( ⁇ 57 % P2O5, collected from the clarification tank after filtration) was transferred into a glass jar with a magnetic stir bar. The acid was heated to 65 °C in a water bath. An effective amount of a reagent of interest (as listed in Table 1) was dosed into acid under agitation at 350 rpm.
  • % gypsum solids ( ⁇ 30 % P 2 O 5 , collected from the stream feeding the gypsum filters) was transferred into a glass jar with a magnetic stir bar. The slurry was heated to 72 °C in a water bath. An effective amount of a reagent of interest (as listed in Table 2) was dosed into the slurry under agitation at 350 rpm. After agitation for 10 minutes, the acid was sampled using a syringe and filtered with a 0.2 ⁇ m polyvinylidene difluoride (PVDF) syringe filter.
  • PVDF polyvinylidene difluoride
  • the acid was heated to 65 °C in a water bath.
  • An effective amount of a reagent of interest (as listed in Table 3) was dosed into acid under agitation at 350 rpm.
  • the acid was sampled using a syringe and filtered with a 0.2 ⁇ m polyvinylidene difluoride (PVDF) syringe filter.
  • PVDF polyvinylidene difluoride
  • Example 5 Process for removing heavy metals from pH 2 sulfuric acid solutions
  • 0.025 g of sodium (meta)arsenite and 0.035 g of cadmium sulfate was added to achieve around 15 ppm of arsenic and 20 ppm of cadmium in the acid solution.
  • 50 g of the prepared acid solution was transferred into a glass jar with a magnetic stir bar.
  • An effective amount of a reagent of interest (as listed in Table 4) was dosed into the acid solution under agitation at 350 rpm.

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Abstract

L'invention concerne des compositions et des procédés permettant d'éliminer/de récupérer des ions métalliques lourds à partir d'un flux contenant de l'acide par ajout de réactifs contenant au moins un composé dialkyldithiophosphate, avec la longueur de chaîne alkyle de C2 à C12, au moins un composé phosphonate, éventuellement au moins un composé dialkyldithiophosphinate, et éventuellement au moins un tensioactif à un flux contenant de l'acide pour former des complexes d'ions métalliques lourds, et de séparer les complexes d'ions métalliques lourds du flux contenant de l'acide.
PCT/EP2025/060636 2024-04-19 2025-04-17 Compositions et procédés d'élimination de métaux lourds de flux contenant de l'acide Pending WO2025219513A1 (fr)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
US4378340A (en) 1979-05-10 1983-03-29 Boliden Aktiebolag Method of purifying phosphoric acid of heavy metals
US4479924A (en) 1982-04-05 1984-10-30 Hoechst Aktiengesellschaft Process for the separation of heavy metal compounds from phosphoric acid
DE4040474A1 (de) 1989-12-23 1991-06-27 Hoechst Ag Neue dithiophosphorsaeureester und deren verwendung zur faellung und flotation von schwermetallen aus mineralsaeuren
US5431895A (en) 1993-08-14 1995-07-11 Hoechst Aktiengesellschaft Process for the removal of lead and cadmium from phosphoric acid
US10865110B2 (en) * 2017-10-08 2020-12-15 Cytec Industries Inc. Compositions and processes for removing heavy metals from phosphoric acid solutions
WO2024047228A1 (fr) * 2022-09-02 2024-03-07 Cytec Industries Inc. Réactifs et procédés d'élimination de métaux lourds de solutions d'acide phosphorique

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US4378340A (en) 1979-05-10 1983-03-29 Boliden Aktiebolag Method of purifying phosphoric acid of heavy metals
US4479924A (en) 1982-04-05 1984-10-30 Hoechst Aktiengesellschaft Process for the separation of heavy metal compounds from phosphoric acid
DE4040474A1 (de) 1989-12-23 1991-06-27 Hoechst Ag Neue dithiophosphorsaeureester und deren verwendung zur faellung und flotation von schwermetallen aus mineralsaeuren
US5431895A (en) 1993-08-14 1995-07-11 Hoechst Aktiengesellschaft Process for the removal of lead and cadmium from phosphoric acid
US10865110B2 (en) * 2017-10-08 2020-12-15 Cytec Industries Inc. Compositions and processes for removing heavy metals from phosphoric acid solutions
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CHILL� DONATELLA ET AL: "Complexation of As(III) by phosphonate ligands in aqueous fluids: Thermodynamic behavior, chemical binding forms and sequestering abilities", JOURNAL OF ENVIRONMENTAL SCIENCES, ELSEVIER BV, NL, vol. 94, 5 May 2020 (2020-05-05), pages 100 - 110, XP086196032, ISSN: 1001-0742, [retrieved on 20200505], DOI: 10.1016/J.JES.2020.03.056 *
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