WO2019207075A1 - Removal of stable metal-cyanide complexes and metallic ions from water stream - Google Patents

Removal of stable metal-cyanide complexes and metallic ions from water stream Download PDF

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Publication number
WO2019207075A1
WO2019207075A1 PCT/EP2019/060683 EP2019060683W WO2019207075A1 WO 2019207075 A1 WO2019207075 A1 WO 2019207075A1 EP 2019060683 W EP2019060683 W EP 2019060683W WO 2019207075 A1 WO2019207075 A1 WO 2019207075A1
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Prior art keywords
hydroxyapatite
cyanide
metal
adsorption
effluent
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PCT/EP2019/060683
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French (fr)
Inventor
Alain Georges BRUHA
Romain DEBORTOLI
Thierry Delplanche
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Solvay Sa
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Priority claimed from EP18187117.9A external-priority patent/EP3604234A1/en
Application filed by Solvay Sa filed Critical Solvay Sa
Publication of WO2019207075A1 publication Critical patent/WO2019207075A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • 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
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/18—Cyanides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/203—Iron or iron compound
    • 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
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/04—Flow arrangements
    • C02F2301/046—Recirculation with an external loop
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a process for treating an effluent contaminated by metallic ions and/or stable metal-cyanide complexes, particularly a water stream generated by an ore mining process.
  • Cyanidation is a process used in the mining industry where metals are leached from ores into a weak solution of cyanide, generally sodium cyanide. Once the metals are leached from the ores, the metals are precipitated and separated from the cyanide solution. Following dissolutions of the metals in the cyanide solution, the process further includes recovery of the metals by cementation, activated carbon or ion exchange resin. A relatively large portion of the cyanide solution is recirculated back to the cyanidation process to take advantage of the leaching potential for the metals. It is, however, necessary to purge a portion of this loaded solution to avoid the build-up of unwanted metals.
  • the purge is sent to a tailings pond or other holding area for removal of metals and cyanide prior to discharge.
  • the purge, pond residues and pond supemate have high concentration of free cyanide as well as metallic cyanide complexes, which give them a high degree of toxicity.
  • Cyanides are harmful for the environment especially in a free
  • cyanide refers to free cyanide (CN, HCN) and complexed cyanides. Cyanides are determined by standard methods. Cyanide may be present in several forms in waste and is classified according to the difficulty of the digestion step in the calorimetric determination method prescribed by the EPA:
  • Simple cyanide compounds including the readily soluble NaCN, KCN, Ca(CN) 2 , Hg(CN) 2 , and relatively insoluble, including Zn(CN) 2 , CuCN, Ni(CN) 2 and AgCN;
  • Weak metal-cyanides including Zn(CN) 4 , Cd(CN) 3 and Cd(CN) 4 ;
  • Moderately strong cyanides including Cu(CN) 2 , Cu(CN) 3 , Ni(CN) 4 and Ag(CN) 2 ; and
  • Strong metal-cyanides such as Fe n (CN) 6 , Fe in (CN) 6 , Co(CN) 6 , AU(CN) 2 and Hg(CN) 4 .
  • Methods for treating cyanide-containing wastes can be divided into two groups: methods that destroy cyanide by breaking the ion to form simpler, non- hazardous compounds (such as carbon dioxide and nitrogen gas) by an oxidation or electrolytic decomposition, and methods that reduce the volume of cyanide waste by evaporation, reverse osmosis or ion exchange.
  • Methods for removing cyanide by destruction include reaction with oxidants such as sulfur dioxide, hydrogen peroxide, sodium hypochlorite and chlorine in various forms, such as under alkaline pH conditions (alkaline chlorination) with the addition of sodium hypochlorite, or through the addition of ozone (ozonation) or hydrogen peroxide (peroxidation) at elevated temperature and pressure.
  • oxidants such as sulfur dioxide, hydrogen peroxide, sodium hypochlorite and chlorine in various forms, such as under alkaline pH conditions (alkaline chlorination) with the addition of sodium hypochlorite, or through the addition of ozone (ozonation) or hydrogen peroxide (peroxidation) at elevated temperature and pressure.
  • the oxidation using hydrogen peroxide (H 2 0 2 ) can be slow, taking days in some processes depending on the forms of cyanides present in the effluent being treating.
  • the time necessary for oxidation with H 2 0 2 can be decreased by using a copper catalyst - see for example U.
  • Electrolytic decomposition involves passing an electric current through the cyanide solution to break the cyanide ion. The process is effective in the destruction of free and complexed forms of cyanide. Electrolytic decomposition, however, is a very expensive process because of the large amounts of electrical energy consumed and is applicable only where the cyanide concentrations are at a relatively high level. High capital equipment costs are also associated with the process.
  • Oxidation is generally the most used in the destruction of cyanides. The process generally is effective in destroying free cyanide and some cyanide complexes. Free cyanide in solution is quite amenable to destruction by oxidation methods. Destruction of complexed forms of cyanide (i.e., "metal- cyanide complexes" or “complexed cyanide") in solution by means of oxidation is highly dependent on the complexing ion associated with the cyanide radical. The relative stability among cyanide complexes varies depending on the complexing ion that is bound to the cyanide radical. It is known that oxidation methods using chlorine or an oxidant like H 2 0 2 are not effective in destroying these strong metal-cyanides in group 5 identified above.
  • the detoxification of a water stream comprising free cyanide and metal- cyanide complexes can proceed as follows: oxidizing free cyanide to cyanate, destroying the weak and moderately strong complexes such as those with zinc, copper and silver, precipitating these metals as hydroxides, and precipitating the strong iron(II) cyanide complex as a heavy metal ferrocyanide or iron ferrocyanide.
  • the detoxification of a water stream comprising free cyanide and iron-cyanide complexes can proceed by removing cyanide from solution and into solid tailings as an iron ferrocyanide precipitate.
  • This can be achieved for example by ferrous sulfate addition.
  • the precipitate that forms in the reaction between excess FeS0 4 and CN comprises mainly insoluble Prussian blue, Fe4[Fe(CN) 6 ] 3 .
  • heavy metals is understood to mean metals whose density is at least equal to 5 g/cm 3 , and also beryllium, arsenic, selenium, and antimony, in accordance with the generally accepted definition (Tchounwou, P. B., Yedjou, C. G., Patlolla, A. K., & Sutton, D. J. (2012). Heavy Metals Toxicity and the Environment. EXS, 101 , p. 133-168. http://doi.org/10.1007/978-3-7643-8340- 4_6). Lead or cadmium are particularly significant examples, given their harmful effect on the human body. Nickel is another example thereof due to its allergenic effect.
  • Hydroxyapatite is an adsorbent which can be used for trapping and immobilizing metals within its structure from contaminated effluents, particularly aqueous effluents. See, for example, WO 2015/173437 by Solvay SA. Hydroxyapatite based adsorption can be used in lieu of ion exchange resins. Cationic species such as zinc, copper, cadmium, and lead are
  • anionic species such as arsenate (As0 4 ),
  • these adsorption-resilient metal-cyanide complexes are in the form of ions in the water stream. Additionally, the metal-cyanide complexes that were not readily captured by this adsorbent were found to be quite stable and resistant to oxidation methods such as those described above. These metal- cyanide complexes which seem to be less amenable to hydroxyapatite adsorption have a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion.
  • Heavy metals are not the only priority of the aqueous environment in terms of legislation and environmental impact; regulations also address many organic compounds, such as polycyclic aromatic hydrocarbons (PAHs), phenolic compounds, and pharmaceutical residues.
  • PAHs polycyclic aromatic hydrocarbons
  • phenolic compounds posed a big threat to aquatic system due to their toxicity and poor biodegradability.
  • Petroleum refinery wastewater usually contains high COD due to the presence of polycyclic aromatic hydrocarbons, phenolic compounds and their derivatives.
  • PAHs priority pollutants with the objective of reducing the release of these compounds to the environment.
  • the widespread occurrence of PAHs is largely due to their formation and release in all processes of incomplete combustion of organic materials.
  • PAHs are particularly found in some industrial water originating from heat treatments (such as from incomplete combustion and pyrolysis of fossil fuels or wood and from the release of petroleum products, wet scrubbers or pyrometallurgy process).
  • PAHs are also found in coal tar, crude oil, creosote and roofing tar and a few are used in medicine or to make dyes, plastics, and pesticides.
  • PAH analysis is restricted to a few compounds— mostly the 16 priority compounds (Naphthalene, Acenaphthylene, Acenaphthene, Fluorene, Phenanthrene, Anthracene, Fluoranthene, Pyrene, Benz[a]anthracene, Chrysene, Benzo[b] fluoranthene, Benzo[k]fluoranthene, Benzo[a]pyrene, Indeno[l,2,3-cd]pyrene, Dibenzo [a, h] anthracene and
  • Solutions for removal of metals may for example include ion-exchange resins.
  • ion-exchange resins cannot address the removal of organics and therefore organics removal requires one or more additional steps.
  • the stable metal-cyanide complexes are generally selected from the group consisting of moderately strong metal-cyanide complexes (‘group 4’ provided above) and strong metal-cyanide complexes (‘group 5’ provided above) - see TABLE 1.
  • cyanide-containing wastewater particularly of water stream containing metallic ions and stable metal-cyanide complexes in the form of soluble anions and optionally also organic contaminants (e.g., PAHs, phenolic compounds, naphtol and derivatives).
  • organic contaminants e.g., PAHs, phenolic compounds, naphtol and derivatives.
  • K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion
  • one aspect of the present invention relates to a process for treating a water stream, preferably originating from an ore mining process, containing cyanide, metallic ions and metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, said method comprising:
  • K is the constant for the equilibrium between the metal- cyanide complex and the free metal ion and cyanide ion.
  • the at least one metal-cyanide complex which undergoes photo dissociation may contain a metal in the complex selected from the group consisting of Fe(II), Fe(III), Co(II), Ni(II), Cu(I), Cu(II), and Hg(II), preferably selected from the group consisting of Fe(II), Fe(III), Co(II), Cu(I), Cu(II), and Ni(II).
  • the metal-cyanide complex which undergoes photo-dissociation may comprise a complex selected from the group consisting of hexacyanoferrate(II), hexacyanoferrate(III), hexacyanocobaltate(III), tetracyanonickelate(II), tetracyanocuprate(II), and combinations thereof.
  • the UV irradiation step further generates bicarbonate and nitrogen gas from cyanates formed by the UV peroxidation of the metal-cyanide complexes.
  • the process for treating a water stream further comprises carrying out the UV irradiation step in the presence of a peroxygen in an UV irradiation unit which is in fluid circulation with a buffer tank. At least a portion of the irradiated effluent flows to the buffer tank and back to the UV irradiation unit. In some embodiments, the at least a portion of the water stream which is to be irradiated with ultraviolet light in the presence of a peroxygen is first fed to the buffer tank before being fed to the UV irradiation unit.
  • the UV irradiation step may be carried out in the presence of a peroxygen in a plurality of UV units operated in series, each UV unit comprising a UV lamp.
  • the process may further comprise carrying out an adsorption step as a pre- treatment prior to the UV irradiation step in order to remove metals, organics and/or color from the at least portion of the water stream prior to being directed to the UV irradiation step.
  • the adsorption step carried out on the at least portion of the irradiated effluent after the UV irradiation step and the adsorption step carried out as a pre-treatment prior to the UV irradiation step are both performed in a same adsorption unit using the solid adsorbent comprising apatite.
  • the solid adsorbent preferably comprises a calcium-deficient
  • hydroxyapatite with a Ca/P ratio more than 1.5 and less than 1.67, preferably wherein the calcium-deficient hydroxyapatite is synthetically made.
  • the solid adsorbent may comprise a synthetic hydroxyapatite composite, said synthetic hydroxyapatite composite comprising a hydroxyapatite and at least one additive which is present during the hydroxyapatite synthesis.
  • the at least one additive in the synthetic hydroxyapatite composite is embedded or incorporated into or coated onto the hydroxyapatite.
  • the at least one additive preferably comprises at least one activated carbon, iron (such as in the form of metal, salt, oxide, oxyhydroxide, or hydroxide), or combinations thereof.
  • the solid adsorbent used in an adsorption unit for both pre-treatment prior to the UV/peroxygen step and adsorption after the UV/peroxygen step preferably comprises a synthetic hydroxyapatite and/or a synthetic hydroxyapatite composite with activated carbon as at least one additive.
  • FIG. 1 is a diagram of a process for treating a water stream, preferably originating from an ore mining process, containing cyanide, metallic ions and metal-cyanide complexes composite, comprising a UV/H2O2 treatment step, an adsorption step and a separation step.
  • FIG. 2 represents another diagram of a process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, comprising a UV/H2O2 treatment step, and separately a combined adsorption / solids separation step.
  • FIG. 3 represents another diagram of a process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, comprising a UV/H2O2 treatment step combined with an adsorption step (for metals/organics removal) carried out into one combined unit and a separation step (for solids removal).
  • FIG. 4 represents another diagram of a process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, comprising a UV/H2O2 treatment step in fluid circulation with a buffer tank, an adsorption step (for metals/organics removal) and a separation step (for solids removal).
  • FIG. 5 represents another diagram of a process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, comprising an adsorption step (pre-treatment for removal of organics, free metals, colored components), a separation step (for solids removal), a UV/H2O2 treatment step in fluid circulation with a buffer tank, wherein at least a portion of the irradiated effluent is sent to the adsorption step (for removal of free metals liberated from cyanide complexes).
  • “Fresh” adsorbent denotes a material which has not been in contact with contaminants
  • “spent” adsorbent denotes a material which has already been in contact with contaminants
  • dry matter refers to a material which has been subjected to drying at a temperature of l05°C for at least 1 hour.
  • the BET specific surface area is determined by gas adsorption on a Micromeritics ASAP2020 machine. The measurement is carried out using nitrogen as adsorbent gas at 77°K via the volumetric method, according to the ISO 9277: 2010 standard (Determination of the specific surface area of solids by gas adsorption - BET method). The BET specific surface area is calculated in a relative pressure (R/R0) range varying from around 0.05 to 0.20.
  • a range of values for a variable defined by a bottom limit, or a top limit, or by a bottom limit and a top limit, also comprises the embodiments in which the variable is chosen, respectively, within the value range : excluding the bottom limit, or excluding the top limit, or excluding the bottom limit and the top limit.
  • the description of several successive ranges of values for the same variable also comprises the description of embodiments where the variable is chosen in any other intermediate range included in the successive ranges.
  • the present description also describes the embodiment where : “the magnitude X is at least 11", or also the embodiment where : “the magnitude X is at least 13.74", etc.; 11 or 13.74 being values included between 10 and 15.
  • One embodiment according to the present invention relates to a process for treating a water stream, preferably originating from an ore processing or metallurgy process, containing cyanide, metallic ions and stable metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion.
  • the water stream may further comprise organics and/or colored species.
  • Such process for treating such water stream includes two main steps:
  • UV peroxidation irradiation of the water stream with ultraviolet light in the presence of a peroxygen to form an irradiated effluent
  • Adsorption contacting the irradiated effluent with a solid adsorbent comprising apatite to form a treated effluent.
  • the UV peroxidation may be also called“UV/peroxygen step” or“UV irradiation with a source of peroxygen” and can be used interchangeably.
  • the first step may be termed for simplification“ UV/H 2 0 2 treatment or step”.
  • the water stream to be subjected to this process may comprise the following metallic contaminants: Al, Ag, Ba, Be, Ce, Co, Cd, Cu, Cr, Fe, Hg, La, Li, Mn, Mg, Mo, Ni, Pb, Pd, Rb, Sb, Sn, Sr, Th, Ti, U, V, Y, Zn and/or non- metallic contaminants such as As, B, F, Se, preferably selected from the group consisting of barium, cadmium, cobalt, copper, iron, magnesium, manganese, nickel, selenium, zinc, and combinations thereof.
  • metallic contaminants selected from the group consisting of Cu, Fe, Ni, and Co.
  • Typical content ranges for these metallic species in the water stream to be subjected to this process may be as follows:
  • the water stream to be subjected to this process also comprises cyanides, in the form of free cyanides and complexed cyanides.
  • Typical content ranges for these cyanides species in the water stream to be subjected to this process may be as follows:
  • Such process for treating the water stream generally includes a separation step to remove solids (such as precipitated material and spent adsorbent) from the treated effluent.
  • the separation of the treated effluent preferably includes settling.
  • the separating may include adding a flocculant to the treated effluent before or during settling.
  • the first step in the present invention relates to the use of UV irradiation in the presence of a peroxygen for removing from a water stream at least a portion of cyanide contaminants, preferably stable metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion.
  • This step may be referred to as“UV/peroxygen step” or“UV peroxidation step”.
  • the peroxygen comprises H 2 0 2
  • this step may be referred to as“UV/H 2 0 2 treatment” or“UV/H 2 0 2 step”.
  • the stable metal-cyanide complexes are generally selected from the group consisting of moderately strong metal-cyanide complexes (‘group 4’ provided above) and strong metal-cyanide complexes (‘group 5’ provided above).
  • the stable metal-cyanide complexes are generally selected from the group consisting of [Co(CN) 6 f ,[Fe(CN) 6 f , [Hg(CN) 4 f, [Fe(CN) 6 ] 4 , [Fe(CN) 6 ] 4 , [Ni(CN) 4 f , [CU(CN) 4 ] 3 ⁇ , [CU(CN)3] 3 , and combinations thereof.
  • the first step in the present invention comprises irradiating the water stream at a alkaline pH greater than 7, preferably greater than 8.0, with ultraviolet light in the presence of a peroxygen at a selected wavelength to form an irradiated effluent, wherein at least one of said metal-cyanide complexes undergoes photo-dissociation and liberates free cyanide from the complex in order for the free cyanide to be converted to cyanate and for the metal from the complex to be converted to an hydroxide form.
  • the at least one metal-cyanide complex which undergoes photo- dissociation during the UV irradiation step with the peroxygen contains a metal in the complex selected from the group consisting of Fe(II), Fe(III), Co(II), Ni(II), Cu(I), Cu(II), and Hg(II), preferably selected from the group consisting of Fe(II), Fe(III), Co(II), Cu(II), and Ni(II).
  • the metal-cyanide complex which undergoes photo-dissociation during the UV irradiation step with the peroxygen may include a complex selected from the group consisting of [Co(CN) 6 ] 3 ,[Fe(CN) 6 ] 3 , [Fe(CN) 6 ] 4 , [Fe(CN) 6 ] 4 ,
  • the pH during the irradiation step is greater than 7, or > 7 and up to 11, preferably from 8 to 11, more preferably from 8.5 to 10.5, yet more preferably from 9 to 10.5, even more preferably from 9.5 to 10.5, yet even more preferably from 10 to 10.5.
  • the pH is generally selected so that no or little HCN gas is liberated from the water stream that is irradiated. For that reason, it may be preferable to select a pH equal to or greater amount of 8.5, preferably at least 9.
  • an optional alkali may be added to increase the pH.
  • Suitable alkali may include NaOH, KOH, Ca(OH) 2 and/or a carbonate solution.
  • the irradiation with ultraviolet light is carried out for at least 4 minutes, or at least 5 minutes, and/or at most 120 min, or at most 90 min, or at most 75 min, or at most 60 min.
  • the ultraviolet light has a wavelength in the region from 200 to 375 nm, preferably from 200 to 350 nm, more preferably from 200 to 300 nm, for the stable metal-cyanide complexes to undergo photo-disassociation and for the peroxygen to form hydroxyl radicals.
  • the ultraviolet lamp preferably emits UV-C light.
  • the irradiation with ultraviolet light is carried out with a Hg lamp with a minimum electric rating of 8 W.
  • the term“pressure” is referred to the mercury pressure present in the lamps.
  • Low-pressure lamps operate with mercury vapor pressure ranging from about 100 to 1000 Pa; a buffer gas supplements the mercury vapor.
  • Medium-pressure lamps operate with mercury vapor pressure of approximately 10 kPa, which enables this type of lamp to reach electrical power levels 100 times higher than low-pressure lamps, i.e. several tens of W/cm.
  • Low and high pressure lamps are monochromatic (254 nm) and medium pressure lamps are polychromatic.
  • the electric rating may be from 8 W to 100 W.
  • Suitable Hg lamps include standard output LP Hg lamps - popularly used UV lamp, whose electric rating is typically 25W, 50W,
  • high output LP Hg lamps whose electric rating is typically 200W, 250W, or 400 W
  • ultra high output LP class lamps whose electric rating is typically 400W.
  • the UV lamp (preferably a Hg lamp) may have a power of at least 55W, preferably of at least 95W.
  • the selection of the wavelength to use for the UV/H2O2 treatment with the Hg lamp should be done to favor decomposition of H2O2 into hydroxyl radical OH ' and for the cyanide complexes to be photo-dissociated.
  • the UV irradiation step with peroxygen may comprise passing water stream through a plurality of UV units, each comprising a UV lamp, preferably a Hg lamp.
  • the plurality of UV units for the UV irradiation step with peroxygen may comprise at least 2, preferably at least 3 UV units, and/or at most 15, preferably at most 12, more preferably at most 10 UV units.
  • the UV units are preferably sized the same so as to accommodate the same incoming flow rate of water to be treated.
  • the plurality of UV units preferably comprises the same type of UV lamp, preferably the same type of Hg lamp, but not necessarily.
  • the peroxygen source is split to feed the plurality of UV units.
  • the plurality of UV units may be operated in parallel, that is to say, wherein a water stream feeding the UV/peroxygen step is split into several feedstreams to feed the plurality of the UV units.
  • the plurality of UV units may be operated in series, that is to say, wherein the irradiated water effluent exiting a UV unit is sent to a subsequent UV unit to get another round of UV treatment.
  • the water stream being fed to the UV/peroxygen step is subjected several times to UV irradiation in the presence of peroxygen.
  • the UV irradiation step with peroxygen may further form particles of metal hydroxides under alkaline condition with the metal liberated from said metal-cyanide complex.
  • the process may further include removing said particles of metal hydroxides from the treated effluent in the separation where the solid adsorbent is separated or removing said particles of metal hydroxides from the irradiated effluent before the contacting step with the solid adsorbent.
  • the conditions for the UV irradiation step with peroxygen include a temperature from 0°C to about 60°C, preferably from 0°C to about 40°C, more preferably from l5°C to about 25°C.
  • the conditions for the adsorption step still more preferably include ambient temperature and atmospheric pressure of the location where the process is operated.
  • the peroxygen used during the UV irradiation step comprises or consists of H 2 0 2 .
  • H 2 0 2 may be in the form of a concentrated H 2 0 2 aqueous solution, such as >20 up to 30 wt% H 2 0 2 , preferably about 30 wt% H 2 0 2 , or a diluted solution comprising from 1 wt% to 20 wt% H 2 0 2 .
  • H 2 0 2 is used in a H 2 0 2 :CN molar ratio of at least 2:1, preferably at least 5:1, more preferably at least 10:1, compared to total cyanide content in the effluent, that is to say, the cyanide which is free and which can be liberated from all metal-cyanide complexes during UV peroxidation.
  • the water stream contains weak metal-cyanide complexes (such as those belonging to ‘group 3’)
  • the cyanide ligand that would be liberated from these weak complexes also need to be taken into account when estimating the amount of H 2 0 2 to add to use the H 2 0 2 :CN ratio equal to or greater than the minimum H 2 0 2 :CN molar ratio.
  • H 2 0 2 One can measure the total amount of cyanide in an effluent sample to do this estimation of how much H 2 0 2 to add for this UV peroxidation.
  • the amount of H 2 0 2 should be sufficient to transform all cyanides (free and liberated ligands) to cyanate and also to oxidize cyanate to N 2 and C0 2 .
  • the H2O2 may be injected periodically into a circulation loop hydraulically connected to a photoreactor where the irradiation takes place or to a tank in such a circulation loop in order for the H2O2 content in the water stream to be treated to be from 10 to 1,000 ppm, preferably from 25 to 750 ppm, preferably from 40 to 500 ppm, yet more preferably from 50 to 400 ppm, most preferably from 100 to 400 ppm.
  • the H2O2 content in the water stream to be treated may be from 10 to 1,000 ppm, preferably from 25 to 750 ppm, preferably from 40 to 500 ppm, yet more preferably from 50 to 400 ppm, most preferably from 100 to 400 ppm.
  • the H2O2 content in the water stream to be treated may be at least 100 ppm.
  • the UV irradiation step further includes formation - see reaction (iv) - of cyanate from cyanide (free and liberated ligand from metal-cyanide complexes) and also further conversion of the cyanate to bicarbonate and nitrogen gas - see reaction (v), according to the following reactions (iv) and (v):
  • the cyanate can also be hydrolysed to carbonate anion and ammonium cation - see reaction (vi):
  • nitrate and nitrite in the irradiated effluent potentially add other compounds which may have to be removed from the water effluent before being discharged.
  • the formation of nitrogen gas from cyanate is therefore preferred, as N 2 gas can be readily liberated from a UV/H 2 0 2 treatment unit where the UV peroxidation takes place.
  • the UV irradiation step further generates bicarbonate and nitrogen gas (as indicated by reaction (v)) from cyanates which are formed (as indicated by reaction (iv)) by the UV peroxidation of the metal- cyanide complexes.
  • the present process further does not include, during or after the UV/peroxygen step, the use of a catalyst which is a metal chelate.
  • a catalyst which is a metal chelate.
  • the present process preferably does not use a phthalocyanine compound (e.g., phthalocyanine of cobalt, vanadium, nickel, or iron, or a sulfonated cobalt phthalocyanine dispersed on carbon, or a water- soluble polysulfonated cobalt phthalocyanine).
  • a phthalocyanine compound e.g., phthalocyanine of cobalt, vanadium, nickel, or iron, or a sulfonated cobalt phthalocyanine dispersed on carbon, or a water- soluble polysulfonated cobalt phthalocyanine.
  • the process may further comprise reducing the pH of the irradiated effluent with an acid, preferably a mineral acid such as sulfuric acid or hydrochloric acid, before contacting with the solid adsorbent.
  • an acid preferably a mineral acid such as sulfuric acid or hydrochloric acid
  • the pH may be reduced to a value from 7 to 9, preferably a pH from 7 to 8.8, more preferably a pH from 7.5 to 8.8, yet more preferably a pH from 7.5 to 8.5.
  • the process may further comprise circulation of at least a portion of the irradiated effluent to flow from the UV/peroxygen step to a buffer tank and flow from the buffer tank back to the UV/peroxygen step.
  • a buffer tank in this process’ embodiment is to permit to hold a large volume of water in that tank for the UV peroxidation, thereby increasing the residence time of the water subjected to this UV peroxidation step.
  • the residence time in the buffer tank may be at least 15 minutes, or at least 30 minutes, or at least 45 minutes, or at least 60 minutes and/or at most
  • the buffer tank may comprise at least one mixed tank in which a stirrer containing one or more impellers stirs its content or at least one tank where its content is recirculated for example by an internal or external pump.
  • UV/peroxygen step The use of the buffer tank circulating at least a portion of the irradiated effluent from and to the UV/peroxygen step thus allows for a lower capital expenditure for the process.
  • the UV/peroxygen step may require 8 to 10 UV units, while in contrast when the process is operated with a buffer tank, the UV/peroxygen step may require 3 to 5 UV units.
  • the second step in the present invention relates to the use of the solid adsorbent comprising apatite, preferably a synthetic hydroxyapatite, for removing at least a portion of one or more contaminants, for example in the form of metals, non-metals, their ions, and/or organics from at least a portion of the water stream, either before UV peroxidation and preferably after UV
  • ación of the irradiated effluent with a solid adsorbent comprising apatite is preferably effective in removing simultaneously a large variety of contaminants such as organics (e.g., PAHs, phenolic compounds, naphtol and derivatives), color, and/or inorganics such as metals and non-metals from a contaminated water stream.
  • organics e.g., PAHs, phenolic compounds, naphtol and derivatives
  • the organic contaminants may be dissolved and/or suspended, and the metal and non-metal contaminants may be in cationic and anionic forms.
  • this contacting step for metal and optionally organics removal may be termed as“adsorption step”.
  • Contacting the water stream with the solid adsorbent comprising apatite is preferably effective in removing at least part of metallic ions containing a metal such as: Al, Ag, Ba, Be, Ce, Co, Cd, Cu, Cr, Fe, Hg, La, Li, Mn, Mg, Mo, Ni,
  • the contacting step with the solid adsorbent comprising apatite may be carried out at a pH of at least 6.5, or at least 7, or at least 7.5, and/or at most 10, or at most 9.5, or at most 9, or at most 8.8, or at most 8.5.
  • the contacting step with the solid adsorbent comprising apatite is preferably carried out at a pH from 7 to 9, preferably a pH from 7 to 8.8, more preferably a pH from 7.5 to 8.8, yet more preferably a pH from 7.5 to 8.5.
  • the contacting step is carried out for at least 5 minutes, or at least 10 minutes, and/or less than 120 min, or less than 60 min, or less than 30 min.
  • the conditions for the adsorption step include a temperature from 0°C to about 60°C, preferably from 0°C to about 40°C, more preferably from l5°C to about 25°C.
  • the conditions for the adsorption step more preferably include ambient temperature and atmospheric pressure of the location where the process is operated.
  • the contacting step with the solid adsorbent and the UV irradiation step with peroxygen may be carried out in different units, alternatively these two steps may be carried out in a same unit, such as a mixed tank or a tank where the water stream is recirculated for example by an internal or external pump.
  • the contacting with the solid adsorbent may be carried out in a mixed tank or a tank where its content is recirculated for example by an internal or external pump, and in such case, the solid adsorbent is in the forms of particles which are suspended in water in the tank.
  • the contacting with the solid adsorbent and the separation step may be carried out in a same unit, preferably wherein the unit is a settler and wherein the solid adsorbent is added to the settler in a zone to allow contact with the irradiated effluent to remove some organics and metallic contaminants and for the solid adsorbent to settle after contact.
  • the contaminated water stream may be an irradiated water effluent containing metallic contaminants, such as: Al, Ag, Ba, Be, Ce, Co, Cd, Cu, Cr, Fe, Hg, La, Li, Mn, Mg, Mo, Ni, Pb, Pd, Rb, Sb, Sn, Sr, Th, Ti, U, V, Y, Zn and/or non- metallic elements such as As, B, F, Se, whether these elements may be in the form of cations and/or anions, such as oxyanions, and optionally colored and/or organic contaminants (e.g., PAHs, phenolic compounds, naphtol and
  • metallic contaminants such as: Al, Ag, Ba, Be, Ce, Co, Cd, Cu, Cr, Fe, Hg, La, Li, Mn, Mg, Mo, Ni, Pb, Pd, Rb, Sb, Sn, Sr, Th, Ti, U, V, Y, Zn and/or non- metallic elements such as As, B
  • the solid adsorbent comprising hydroxyapatite (preferably in suspension form) is mixed into the water stream (preferably wherein a portion of which has been irradiated) for a sufficient time so that the hydroxyapatite adsorbs at least a portion of the contaminants.
  • the so-formed mixture is preferably subjected to a separation (such as settling and/or clarification) in order to produce a treated water which is partially purified of organic, colored, metallic and/or non-metallic contaminants and a spent solid adsorbent loaded with organic, colored, metallic and/or non-metallic
  • the solid adsorbent may be used with the water stream, wherein a portion of which has been irradiated, in a contact reactor, such as a sludge blanket reactor or a fluidized bed.
  • a contact reactor such as a sludge blanket reactor or a fluidized bed.
  • the contact time between the solid adsorbent and the irradiated water effluent is in general at least one minute, advantageously at least 15 minutes, more advantageously at least 30 minutes, even more advantageously at least one hour.
  • the solid adsorbent which is suitable to be used for the adsorption step is described in more detail below.
  • the water stream wherein a portion of which has been irradiated, may be introduced into a sludge blanket contact reactor in which the solid adsorbent is present at a weight concentration from at least 0.5% by weight to in general at most 10% by weight, preferably from 1 to 10 wt%, more preferably from 2 to 5 wt%; a liquid is recovered as overflow from the sludge blanket reactor; a flocculant is added to the recovered liquid in order to form a mixture comprising particles of the solid adsorbent entrained out of the contact reactor and flocculated; said mixture is then introduced into a settling tank where the mixture is separated into:
  • the treated water partially purified of organic, metallic elements and/or of non- metallic elements, and said treated water is recovered as overflow from the settling tank, - and into an underflow from the settling tank comprising flocculated and settled particles of solid adsorbent recovered as underflow from the settling tank; and at least one portion of the underflow from the settling tank containing flocculated and settled particles of adsorbent is recycled to the sludge blanket contact reactor.
  • the effectiveness of the treatment of organics, metallic elements and/or non-metallic elements may be monitored by comparing the concentrations of the elements upstream (in the water stream) and downstream of the treatment (in the partially purified liquid), for example by an automatic analyser or by sampling and analysis.
  • the solid adsorbent charge of the contact reactor is in general regularly renewed in portions. For example, by partial purging of the spent solid adsorbent loaded with organics, metallic and/or non-metallic elements at the underflow from the settling tank, and by adding fresh solid adsorbent to the contact reactor. Such a process thus ensures a "chemical polishing" of the water effluent.
  • the process is particularly advantageous in the case where the treated water partially purified of organics, colored species, metallic and/or non-metallic elements is then treated in a biological treatment plant producing sewage sludges. This makes it possible to reduce the
  • the process may further comprise an adsorption pre-treatment of the water stream prior to being directed to the UV/peroxygen step.
  • the solid adsorbent used in the adsorption pre-treatment is suitable for removing color.
  • Color in the water stream may originate for example from iron species, and may be a yellowish to light brownish color. It is believed that the presence of color in the water stream to be treated may indeed hinder the performance of the UV light in the
  • UV/peroxygen step removing some of the color from the water stream prior to the UV/peroxygen step may be beneficial to maximize the use of the UV light for the photo-disassociation of the metal-cyanide complexes and it would minimize the possible interaction / reaction with UV of the colored species present in the water stream.
  • a spectrophotometric analysis can generate an absorbance spectrum of the water stream sample to be pre-treated to find out a peak or peaks at particular wavelength(s) which is/are representative of the colored species to be removed.
  • the absorbance at the selected wavelength(s) can be measured on unfiltered samples of water streams with a spectrophotometer using a 1 cm path length quartz cell.
  • a wavelength may be selected in the range of 565-590 nm to monitor the removal of yellow-colored species, or a wavelength may be selected in the range of 590-625 nm to monitor the removal of orange-colored species.
  • the data collected represents apparent color.
  • the percent color reduction of the pre-treated samples (after being subjected to the adsorption) are compared to the time-zero samples (before adsorption).
  • the solid adsorbent used in the adsorption pre-treatment is further suitable for removing at least a portion of organics and/or free metallic species such as metallic ions, in particular free species of arsenic, selenium, heavy metals, e.g., iron, copper, cobalt, and/or nickel.
  • the water stream generally contains free metallic species such as metallic ions that are not complexed with cyanide and/or organics.
  • UV/peroxygen step and the adsorption step with the solid adsorption carried out on at least a portion of the irradiated effluent after the UV/peroxygen step are performed in a same adsorption unit in which one or more solid adsorbents comprising apatite can be used.
  • a unit for adsorption can be used prior to and after UV peroxidation step and to this unit is added a solid adsorbent comprising apatite as described herein in the description.
  • a particular preferred solid adsorbent used in this particular adsorption pre-treatment comprises a synthetic hydroxyapatite and/or a synthetic
  • the synthetic hydroxyapatite composite with activated carbon is particularly preferred for removal of free (not-complexed) heavy metals, at least a portion of organics and/or colored species.
  • the solid adsorbent, particularly the solid adsorbent comprising a hydroxyapatite composite, which is suitable to be used for adsorption pre- treatment is described in more detail below.
  • the second step in the present invention relates to the use of a solid adsorbent comprising apatite, preferably an hydroxyapatite, for removing at least a portion of one or more contaminants, for example in the form of organics, metallic and/or non-metallic ions from the irradiated water effluent.
  • a solid adsorbent comprising apatite, preferably an hydroxyapatite
  • apatite denotes a family of mineral compounds, the chemical formula of which can be written in the following general form:
  • Me generally represents a divalent cation (Me 2+ ), X0 4 a trivalent anionic group (X0 4 3 ) and Y a monovalent anion (Y ).
  • Calcium phosphate hydroxyapatite Caio (P0 4 ) 6 (0H) 2 crystallizes in the space group of the hexagonal system.
  • This structure consists of a close-packed quasi-hexagonal stack of X0 4 groups, forming two types of parallel tunnels.
  • Hydroxyapatite should not be confused with tricalcium phosphate (TCP), which has a similar weight composition : Ca 3 (P0 4 ) 2 .
  • the Ca/P molar ratio of TCP is 1.5 whereas the Ca/P molar ratio is 1.67 for hydroxyapatite.
  • Industrial apatites sold as food additives or mineral fillers are, as a general rule, variable mixtures of TCP and hydroxyapatite.
  • hydroxyapatite is more advantageous as it can enclose metals in the form of an insoluble, and therefore relatively inert, matrix.
  • the solid adsorbent may have a particularly high BET specific surface area (at least 110 m 2 /g) and/or a particularly high pore volume (at least 0.3 cm 3 /g) measured after heat treatment of the solid adsorbent at l05°C.
  • Such solid adsorbent particles are composed on their surface of plate-like crystallites, of thickness of a few nano-meters (nm). Particles of solid adsorbent may be covered with plate-like crystallites, having a thickness of at most 25 nm, preferably of at most 20 nm, more preferably of at most 10 nm. The thickness of plate-like crystallites may be at least 1 nm, preferably at least 2 nm, more preferably at least 4 nm.
  • the solid adsorbent used in the present invention may further have a remarkably low solubility of the phosphates contained in the solid adsorbent particles.
  • the adsorbent preferably comprises solid particles with a mean
  • the adsorbent comprises solid particles with a mean diameter D50 from 20 microns to 60 microns, or from 25 microns to 60 microns, or from 30 microns to 60 microns.
  • the mean diameter in question is the D50, that is to say the diameter such that 50 % by weight of the particles have a diameter less than said value.
  • the mean particles size D50 is the diameter such that 50 % by weight of the particles have a diameter less than said value.
  • measurement may be measured using laser diffraction, such as using a
  • Beckman Coulter LS 230 laser diffraction particle size analyser (laser of wavelength 750 nm) on particles suspended in water and using a size distribution calculation based on Fraunhofer diffraction theory (particles greater than 10 pm) and on Mie scattering theory (particles less than 10 pm), the particles being considered to be spherical.
  • the solid adsorbent is inorganic.
  • the solid adsorbent contains less than 1 wt% organics.
  • Solid adsorbent comprising a hydroxyapatite
  • the solid adsorbent comprising apatite preferably comprises an
  • hydroxyapatite preferably a hydroxyapatite which is synthetically made.
  • Suitable hydroxyapatite includes a calcium-deficient hydroxyapatite with a Ca/P ratio more than 1.5 and less than 1.67, preferably with a Ca/P molar ratio more than 1.54 and less than 1.65.
  • the calcium-deficient hydroxyapatite is generally in crystalline form or in vitreous form.
  • the solid adsorbent comprises at least 60 wt % of a calcium-deficient hydroxyapatite.
  • the solid adsorbent may comprise at least 65 wt%, preferably at least 70 wt%, more preferably at least 75 wt%, yet more preferably at least 80 wt%, yet most preferably at least 85 wt%, of the calcium-deficient hydroxyapatite, and/or
  • the solid adsorbent may further include one or more additional components different from the calcium-deficient hydroxyapatite.
  • Calcium may be and is preferably present in another form (other than the calcium-deficient hydroxyapatite) in the solid adsorbent.
  • Calcium carbonate is generally present in the solid adsorbent.
  • the weight ratio of the calcium-deficient hydroxyapatite to calcium carbonate is generally equal to or greater than 3, preferably equal to or greater than 4, more preferably equal to or greater than 5, yet more preferably greater than 7, most preferably equal to or greater than 9.
  • the solid adsorbent generally has a higher Ca/P molar ratio than the calcium-deficient hydroxyapatite present in the solid adsorbent. For that reason, even though the calcium-deficient hydroxyapatite in the solid adsorbent may have a Ca/P molar ratio less than 1.67, the entire solid adsorbent may have a Ca/P molar ratio equal to or more than 1.67.
  • the calcium-deficient hydroxyapatite in the solid adsorbent may have a Ca/P molar ratio of about 1.55-1.59, while the solid adsorbent may have a Ca/P molar ratio of about 1.60-1.67.
  • the solid adsorbent may further comprise calcium carbonate in an amount of less than 20 wt% and more than 0 wt%, preferably from 1 wt% to 19 wt%, more preferably from 2 wt% to 18 wt%, even more preferably from 5 wt% to 15 wt%, yet even more preferably from 7 wt% to 13 wt%, most preferably from 8 wt% to 12 wt%.
  • the solid adsorbent may further comprise less than 1 wt% of calcium dihydroxide Ca(OH) 2 , preferably less than 0.5 wt% calcium dihydroxide
  • the solid adsorbent may further comprise water in an amount of less than 20 wt% and more than 0 wt%, preferably from 1 wt% to 18 wt%, more preferably from 2 wt% to 15 wt%, even more preferably from 4 wt% to 12 wt%, yet even more preferably from 5 wt% to 11 wt% most preferably from 6 wt% to 11 wt%.
  • the solid adsorbent comprises at least 60 wt% of a calcium-deficient hydroxyapatite with a Ca/P ratio more than 1.5 and less than 1.67; calcium carbonate in an amount between 0.5 to 20 wt% and/or contains less than 1 wt% Ca(OH) 2 .
  • the solid adsorbent is substantially free of carbon, i.e., less than 0.5 wt% of carbon.
  • the solid adsorbent may comprise carbon for example in an amount of at least 0.5 wt% carbon but in an amount of less than 7 wt% carbon, preferably less than 6 wt% carbon, more preferably less than 5 wt% carbon or less than 4 wt% carbon.
  • Solid adsorbent comprising a hydroxyapatite composite
  • a hydroxyapatite composite can be effective in trapping simultaneously a large variety of contaminants such as organics (e.g., PAHs, phenolic compounds, naphtol and derivatives) and/or inorganics such as metals and non- metals from a contaminated water stream.
  • organics e.g., PAHs, phenolic compounds, naphtol and derivatives
  • inorganics such as metals and non- metals from a contaminated water stream.
  • the organic contaminants may be dissolved and/or suspended, and the metal and non-metal contaminants may be in cationic and anionic forms.
  • the hydroxyapatite structure can be supplemented or modified by incorporating at least one additive during the synthesis of the hydroxyapatite to yield a hydroxyapatite composite with an improved adsorption affinity and/or efficiency with respect to at least one contaminant, such adsorption affinity and/or efficiency being greater than that of ae hydroxyapatite structure not containing the activated carbon.
  • the additive in the hydroxyapatite composite may be embedded or incorporated into or coated onto the hydroxyapatite structure
  • hydroxyapatite structure or otherwise associated with the hydroxyapatite structure via cohesive forces. Regardless on how the additive is included in the resulting composite, its presence during the hydroxyapatite synthesis results in forming the hydroxyapatite composite.
  • the hydroxyapatite composite is different than a mere physical mixture of a hydroxyapatite and the additive, which in this case would be made after each material (hydroxyapatite and the additive) would be formed separately and then mixed or blended.
  • One advantage of embedding or incorporating the additive into the hydroxyapatite during its synthesis is to provide a much more stable material (compared to a mere physical mixture of a hydroxyapatite and the additive) which does not release the additive when in use, particularly in an aqueous solution when the hydroxyapatite composite is intended to perform as adsorbent for removal of contaminants from water.
  • the additive in the hydroxyapatite composite is a co-sorbent.
  • the additive is preferably selected based on its own particular affinity and/or efficacy to adsorb or trap at least one contaminant that the hydroxyapatite structure (without additive) does not adsorb or weakly adsorbs.
  • the contaminant may be in the form of organics (e.g., PAHs, phenolic compounds, naphtol and derivatives) and/or inorganics such as a metal or a non-metal in the form of a cation or an oxyanion.
  • the additive may be selected based on its own particular affinity and/or efficacy to adsorb organics (e.g., PAHs, phenolic compounds, naphtol and derivatives) or mercury such as in the form of mercury cation, selenium such as in the form of its oxyanions (selenate and/or selenite), arsenic such as in the form of its oxyanions (H 2 As0 4 /HAs0 4 2 ) and uncharged H3ASO3 form of As(III), and/or boron such in the form of borate.
  • organics e.g., PAHs, phenolic compounds, naphtol and derivatives
  • mercury such as in the form of mercury cation
  • selenium such as in the form of its oxyanions (selenate and/or selenite)
  • arsenic such as in the form of its oxyanions (H 2 As0 4 /HAs0 4 2 ) and uncharged H3A
  • the additive may be further selected based on its ability to increase the porosity of the hydroxyapatite structure. For example, it is preferred that the pore volume and/or the BET surface area of the resulting hydroxyapatite composite synthesized with the additive is higher than that of the hydroxyapatite structure synthesized without the additive.
  • One advantage of the present invention is improving the sorption affinity of the hydroxyapatite composite for at least one contaminant that would otherwise not be adsorbed or poorly adsorbed from a contaminated effluent by a hydroxyapatite synthesized without the additive.
  • the at least one contaminant may be an organic compound, or a metal or non-metal in the form of a cation or an oxyanion.
  • Another advantage of a hydroxyapatite composite is improving the sorption capacity of the hydroxyapatite composite, for example by increasing its pore volume and/or BET surface area.
  • the additive can be used as a co-sorbent in powder form for water treatment, the inclusion of the additive powder as co-sorbent in the
  • hydroxyapatite composite provides yet another advantage. While the use of a co-sorbent in a loose powder offers large surface area and high adsorption capacity, a loose powder needs specific and costly equipment to be removed from treated water streams, and solid/liquid separation problems limit reactor configurations that require incorporating large sedimentation basins or filtration. There is therefore a benefit for a powdered co-sorbent to be incorporated into the hydroxyapatite structure to form the composite, so it can be used in practical adsorption processes.
  • the hydroxyapatite synthesis which comprises the presence of the additive powder generates solid particles of larger size than the powder, and these larger particles are easier to separate from a treated water stream, using a solid/liquid separation technique such as by settling.
  • One embodiment according to the present invention relates to the use of a hydroxyapatite composite in the solid adsorbent during the contacting step.
  • a hydroxyapatite composite comprises:
  • At least one additive which is present during the hydroxyapatite synthesis.
  • the at least one additive or a precursor thereof may be added to a vessel where hydroxyapatite synthesis takes place, prior to or during the synthesis of the hydroxyapatite. That is to say, when the synthesis of the hydroxyapatite takes place in a vessel, the additive or a precursor thereof may be added to the vessel before the synthesis is initiated or while the hydroxyapatite structure is synthetized in this vessel.
  • the at least one additive which increases the porosity of the hydroxyapatite.
  • the at least one additive is present while the hydroxyapatite structure is synthetized.
  • the at least one additive may be added to the vessel before the synthesis is initiated or while the hydroxyapatite structure is synthetized in this vessel.
  • the hydroxyapatite composite may have a higher total pore volume and/or a higher BET surface area than a hydroxyapatite material made without the additive.
  • the hydroxyapatite composite according to the present invention is an effective reactant for immobilizing contaminants from water, in particular when employed in dispersed mode in water treatment units.
  • the hydroxyapatite composite may comprise at least 50wt%
  • hydroxyapatite advantageously at least 60wt%, and more advantageously still at least 70wt% hydroxyapatite or at least 75wt% hydroxyapatite, based on the total weight of dry matter.
  • the hydroxyapatite composite may comprise a calcium-deficient hydroxyapatite, preferably with a Ca/P molar ratio more than 1.5 and less than 1.67.
  • the hydroxyapatite composite may comprise a calcium-deficient hydroxyapatite and has an overall Ca/P molar ratio higher than the calcium-deficient hydroxyapatite.
  • the hydroxyapatite composite may further comprise, on the basis of total weight of dry matter,
  • - water of the order of from 1 wt% to 30 wt%, advantageously from 2 wt% to 25 wt%, or from 2 wt% to 20 wt%, or from 3 wt% to l5wt% , and/or
  • - calcium carbonate in an amount of less than 20 wt%, preferably from 1 wt% to 19 wt%, more preferably from 2 wt% to 18 wt%, even preferably from 3 wt% to 15 wt%, yet even more preferably from 4 wt% to 13 wt%, most preferably from 5 wt% to 10 wt%.
  • the hydroxyapatite composite may further comprise, based on the total weight of dry matter, less than 1 wt% of calcium dihydroxide Ca(OH) 2 , preferably less than 0.5 wt% calcium dihydroxide, more preferably less than 0.3 wt% calcium dihydroxide, even more preferably less than 0.2 wt% calcium dihydroxide, or even less than 0.1 wt% Ca(OH) 2 ).
  • the hydroxyapatite composite preferably comprises a weight ratio of hydroxyapatite to additive (HAP:A) of from 1 :0.0l to 1 :0.5. That is to say, when lOOg of hydroxyapatite in the composite, a minimum of 1 g of additive is present and/or a maximum of 50 g is present in the composite.
  • the weight ratio of is preferably at least 1 :0.02 or at least 1 :0.03.
  • the weight ratio of is preferably at most 1 :0.3, more preferably at most 1 :0.25.
  • the hydroxyapatite composite may comprise a weight ratio of hydroxyapatite to additive (HAP: A) of from 1 :0.0l to 1 :0.5, preferably from 1 :0.02 to 1 :0.4 or from 1 :0.03 to 1 :0.4, more preferably from 1 :0.04 to 1 :0.3, yet more preferably from 1 :0.05 to 1 :0.25, yet even more preferably from 1 :0.05 to 1 :0.20.
  • HAP hydroxyapatite to additive
  • a range of 5 to 20 g additive per 100 g of hydroxyapatite is particularly suitable.
  • the hydroxyapatite composite may comprise at least 2 wt%, or at least 3 wt%, or at least 4 wt% of the additive based on the total weight of dry matter.
  • the hydroxyapatite composite may comprise at most 50 wt%, or at most 30 wt%, or at most 20 wt% of the additive based on the total weight of dry matter.
  • the hydroxyapatite composite may further comprise: water, of the order of from 0 to 20 wt%, advantageously from 1 % to 20 wt%, more advantageously from 2 % to 10 wt%, based on the total weight of dry matter.
  • the hydroxyapatite composite may comprise water, of the order of from 5 wt% to 20 wt%, advantageously from 6 wt% to 20 wt%, based on the total weight of dry matter.
  • the hydroxyapatite composite may comprise, based on the total weight of dry matter, less than 5 wt% water, preferably less than 5 wt% and down to 0.1 wt% or even lower
  • the hydroxyapatite composite may further comprise, based on the total weight of dry matter, calcium carbonate in an amount of less than 20 wt% and more than 0 wt%, preferably from 1 wt% to 19 wt%, more preferably from 2 wt% to 18 wt%, even more preferably from 5 wt% to 15 wt%, yet even more preferably from 7 wt% to 13 wt%, most preferably from 8 wt% to 12 wt%.
  • the hydroxyapatite composite may further comprise, based on the total weight of dry matter, calcium dihydroxide Ca(OH) 2 from 0 to 20 %,
  • the hydroxyapatite composite may comprise less than 1 wt% of calcium dihydroxide Ca(OH) 2 , preferably less than 0.5 wt% calcium dihydroxide, more preferably less than 0.3 wt% calcium dihydroxide, even more preferably less than 0.2 wt% calcium dihydroxide. In some embodiments, the hydroxyapatite composite is substantially free of calcium dihydroxide (i.e., less than 0.1 wt% Ca(OH) 2 ).
  • the hydroxyapatite composite may comprise at least 2 wt%, preferably at least 2.5 wt% or at least 3 wt%, more preferably at least 5 wt%, and yet more preferably at least 6 wt% of hydroxide ions.
  • the hydroxyapatite composite may comprise, on the basis of the total weight of dry matter,
  • - water of the order of from 1 wt% to 20 wt%, advantageously from 2 wt% to 20 wt%, or from 2 wt% to 10 wt%, or from 3 wt% to 8 wt% , and/or
  • wt% preferably from 1 wt% to 19 wt%, more preferably from 2 wt% to 18 wt%, even preferably from 3 wt% to 15 wt%, yet even more preferably from 4 wt% to 13 wt%, most preferably from 5 wt% to 10 wt%.
  • the hydroxyapatite composite may be in the form of particles having a specific surface area of at least 110 m 2 /g, preferably of at least 120 m 2 /g, more preferably of at least 130 m 2 /g, yet more preferably of at least 140 m 2 /g.
  • the hydroxyapatite composite may be in the form of particles having a total pore volume of at least 0.3 cm 3 /g, or at least 0.32 cm 3 /g, or at least 0.35 cm 3 /g, or at least 0.4 cm 3 /g.
  • the additive is inorganic.
  • the hydroxyapatite composite may comprise more than one additive.
  • a first additive may serve as support for a second additive.
  • the additive may comprise at least one activated carbon, iron (which may be in the form of metal of oxidation state 0, salt, oxide, oxyhydroxide, or hydroxide, preferably oxyhydroxide or hydroxide), or combinations of two or more thereof.
  • the hydroxyapatite composite may comprise an activated carbon as a first additive and iron (for example in the form of zero- valent metal, salt, oxide, oxyhydroxide, or hydroxide) as a second additive.
  • iron for example in the form of zero- valent metal, salt, oxide, oxyhydroxide, or hydroxide
  • the additive may comprise or consist of at least one activated carbon.
  • Activated carbon may originate from various sources. It can be produced from carbonaceous source materials such as bamboo, coconut husk/shell, willow peat, wood, coir, lignite, coal, petroleum coke, and/or petroleum pitch.
  • the activated carbon used as additive is in a powder form. Its average particle size is generally in size of less than 1 mm.
  • the preferred average particle size for activated carbon may be at most 500 microns, preferably at most 400 microns, or at most 300 microns, or at most 200 microns, or at most 100 microns, or at most 80 microns, or at most 60 microns.
  • the average particle size for activated carbon may be at least 5 microns, or at least 10 microns.
  • the average particle size for activated carbon is preferably within +/- 50% of the average particle size of the hydroxyapatite which is to be synthesized in the presence of this activated carbon.
  • the average particle size for activated carbon is preferably less than the average particle size of the hydroxyapatite which is to be synthesized in the presence of this activated carbon.
  • the activated carbon may be selected based at least on the following criteria: the activated carbon yields a pH of at least 5 when dispersed in a suspension at 0.3 wt% in deionized water for 5 hours.
  • the additive comprises an activated carbon or blend of two or more activated carbons
  • the activated carbon or blend of two or more activated carbons is selected so that a 0.3 wt% dispersion of the activated carbon(s) in deionized water provides a pH of 5 or more.
  • a blend with another more-alkaline activated carbon may be used in the additive to provide a pH of 5 or more.
  • the activated carbon may comprise a pore volume of at least 0.25 cm 3 /g, preferably of at least 0.35 cm 3 /g, more preferably of at least 0.4 cm 3 /g.
  • the activated carbon may have a BET surface are of at least 500 m 2 /g, preferably of at least 750 m 2 /g.
  • the activated carbon may have a unique distribution of pore sizes that contributes to the ability of the composite to remove specific contaminants from aqueous systems.
  • the activated carbon has a porosity of at least about 0.25 cm 3 /g.
  • the pores diameter of the activated carbon may be at least about 10 and at most about 500 A (Hg intrusion porosimetry, such as using a Micromeritics model AutoPore-II 9220 porosimeter).
  • the activated carbon has a porosity of at least about 0.4 cm 3 /g in pores diameter of at least about 10 and at most about 500 A.
  • the activated carbon has been subjected to a treatment prior to being used into the hydroxyapatite composite synthesis. Such treatment may enhance the sorption capability of the activated carbon and/or modify the porosity of the activated carbon.
  • the activated carbon may be impregnated by sulfur to enhance the sorption of mercury cations.
  • sulfur- impregnated activated carbon is MerSorb® from NUCON International.
  • the activated carbon may be subjected to an acid treatment such as with nitric acid.
  • the activated carbon may be subjected to steam, generally to impact its porosity.
  • the activated carbon is not treated with acid prior to being used into the hydroxyapatite composite synthesis.
  • the additive may exclude activated carbon.
  • the additive may comprise or consist of an iron-containing additive, preferably in the form of metal of oxidation state 0, salt, oxide, oxyhydroxide, or hydroxide, preferably in the form of metal of oxidation state 0, oxide, oxyhydroxide, or hydroxide.
  • the iron in the additive may be of oxidation state 0, 2 or 3.
  • the iron-containing additive is preferably inorganic. If the additive comprises an iron salt, the iron salt is preferably inorganic.
  • the additive may comprise or consist of an iron oxide.
  • the iron oxide may be iron(III) oxide or ferric oxide of formula Fe 2 0 3 , iron(II) oxide (FeO), or iron(II,III) oxide (Fe 3 0 4 ).
  • the additive may comprise or consist of Fe 3 0 4 .
  • Fe 3 0 4 can occur naturally as the mineral magnetite or may be synthesized, for example in the form of nanoparticles. Examples of synthesis of Fe 3 0 4 nanoparticles can be found in Gonzales et al., 2012, Journal of Hazard Materials, vol. 211-212, pg.
  • the additive when the additive comprises iron, the additive more preferably comprises iron(III) hydroxide, and/or iron(III) oxyhydroxide; more preferably comprises iron(III) oxyhydroxide.
  • Iron(III) hydroxide has the chemical formula Fe(OH)3.
  • Iron(III) oxyhydroxide has the chemical formula FeOOH. It can be obtained for example by reacting ferric chloride with sodium hydroxide.
  • iron(II) may be oxidized to iron(III) by hydrogen peroxide in the presence of an acid.
  • ferric hydroxide can be prepared as described in W02003/053560 or can be prepared as described in [0045] of
  • iron(III) oxide-hydroxide occurs in anhydrous and hydrated forms.
  • Ferrihydrite FeOOH 0.4H 2 O
  • FeOOH 0.4H 2 O is a hydrous ferric oxyhydroxide mineral which is also suitable for use as additive.
  • iron(III) oxyhydroxide occurs in four different polymorphic forms, known as alpha-, beta-, gamma- and delta- FeOOH. All these forms may be used in the present invention.
  • Goethite is a widespread mineral of formula -FeO(OH) and lepidocrocite is a less common mineral of formula y-FeO(OH) with the same chemical composition as goethite but with a different crystal structure.
  • the iron(III) oxyhydroxide particles may have a median particle size in the range of from about 1 to about 3,000 nm, preferably about 5 to about 2,000 nm, more preferably from about 10 to about 700 nm, even more preferably from about 50 to about 500 nm, such as in the range of from about 100 to about 400 nm.
  • the iron(III) oxyhydroxide may be formed in situ during the synthesis of the hydroxyapatite by adding the Fe precursor and adding a base to form the FeOOH, or FeOOH may be added as an aqueous slurry or solution comprising from at least 1 wt% to at most 20 wt% FeOOH, or from at least 2 wt% to at most 15 wt% FeOOH, or from at least 2 wt% to at most 10 wt% FeOOH.
  • the iron may be added during the synthesis of the hydroxyapatite in the form of an iron precursor such as a salt.
  • a suitable precursor of iron may be iron chloride, iron nitrate, iron sulfate, or any combination thereof.
  • a base (source of OH ) is generally added to this iron precursor to generate iron(III) hydroxide or oxyhydroxide.
  • the additive may exclude iron.
  • the adsorbent material used for removal of contaminants from the water stream may comprise one of the following materials:
  • - one synthetic hydroxyapatite made without additive
  • hydroxyapatite composites wherein the additives in the hydroxyapatite composites are different; preferably wherein at least one of the additives in a first hydroxyapatite composite comprises an activated carbon or blend of two or more activated carbons, and wherein at least one of the additives in a second hydroxyapatite composite comprises iron (such as in the form of metal, salt, hydroxide,
  • an adsorption pre-treatment step can be carried out to remove at least a portion of one or more contaminants from the water stream prior to
  • UV/peroxygen step for example organic contaminants (e.g., PAHs, phenolic compounds, naphtol and derivatives), colored species, and/or inorganic contaminants in the form of metals, non-metals, their cations and/or oxyanions, particularly Hg or its cation, As, B, and/or Se, or their respective oxyanions.
  • the adsorption pre-treatment step preferably comprises contacting the water stream to be treated with a synthetic hydroxyapatite and/or a hydroxyapatite composite.
  • the contacting step can remove at least a portion of one or more contaminants from the water stream, for example organic contaminants
  • the contacting step preferably comprises contacting the water stream, at least a portion of which being irradiated in the UV/peroxygen step, with a hydroxyapatite composite or the adsorbent material comprising at least one hydroxyapatite composite.
  • a hydroxyapatite composite comprising at least one activated carbon.
  • a hydroxyapatite composite comprising at least one activated carbon, at least one iron (such as in the form of iron(III) hydroxide and/or iron(III) oxyhydroxide), or combination thereof
  • hydroxyapatite composite comprising activated carbon, iron in the form of iron(III) hydroxide and/or iron(III) oxyhydroxide, or combination thereof or
  • hydroxyapatite composite comprising activated carbon, iron in the form of iron(III) hydroxide and/or iron(III) oxyhydroxide, or combination thereof or
  • a portion of metallic cations from the water stream prior to and/or after the UV/peroxygen step such as cations of Al, Ag, Ba, Be, Ce, Co, Cd, Cu, Cr, Fe, La, Li, Mn, Mg, Mo, Ni, Pb, Pd, Rb, Sb, Sn, Sr, Th, Ti, U, V, Y, and/or Zn, and particularly Fe, Ni, Co, and/or Cu
  • a synthetic hydroxyapatite and/or a hydroxyapatite composite comprising at least one activated carbon, at least one iron (such as in the form of iron(III) hydroxide and/or iron(III) oxyhydroxide), or combination thereof
  • the solid adsorbent may be made by a process comprising:
  • a source of calcium and a source of phosphate ions are mixed in water in a molar ratio that is adjusted to obtain a Ca/P molar ratio of between 0.5 and 1.6, preferably between 0.7 and 1.3, and reacting the source of calcium with the phosphate ions at a pH of between 2 and 8, in order to obtain a suspension (A) of calcium phosphate,
  • a second step adding to the suspension (A) an alkaline compound comprising hydroxide ions in order to set a pH of at least 7.5, preferably at least 8, or at least 8.5, or at least 9, or of at least 10; further adding an additional source of calcium in order to obtain a suspension (B) of composite having a Ca/P molar ratio of greater than 1.6, preferably greater than 1.65 to form a hydroxyapatite structure.
  • the source of calcium advantageously comprises calcium carbonate, or calcium oxide, or calcium hydroxide, or calcium chloride, or calcium nitrate, or calcium acetate.
  • the source of calcium is more advantageously a limestone, or a mixture of limestone and calcium oxide or hydroxide. More advantageously, the source of calcium is in the form of powder or aqueous suspension of powder and the powder is selected from: calcium carbonate, calcium oxide, calcium hydroxide, or a mixture thereof, and the powder has a mean particle size of less than 300 pm.
  • the source of calcium selected from calcium carbonate, calcium oxide, calcium hydroxide or mixtures thereof is in the form of a powder or aqueous suspension of powder, and to have a small particle size.
  • the mean diameter of the particles of the powder is less than 300 pm, advantageously less than 200 pm and preferably less than 100 pm.
  • the mean diameter in question is the D50, that is to say the diameter such that 50% by weight of the particles have a diameter less than said value.
  • various sources of phosphate ions may be used, in particular:
  • a dihydrogen phosphate salt such as a sodium, potassium or ammonium dihydrogen phosphate salt, preferably a sodium dihydrogen phosphate salt,
  • a monohydrogen phosphate salt such as a sodium, potassium or ammonium monohydrogen phosphate salt, preferably a sodium monohydrogen phosphate salt.
  • phosphoric acid is preferred due to its greater availability and lower cost compared to dihydrogen and monohydrogen phosphate salts.
  • the suspended solids density of the suspension (A) in the first step is in general at most 20% by weight.
  • the suspended solids density of the suspension (B) in the second step is in general at most 25% by weight.
  • a preferred range of suspended solids density of the suspension (B) in the second step is from 16 wt% to 24 wt%. It has been indeed observed that a too low density of suspension decreases the efficacy of the produced reactant particles in heavy metal adsorption. Moreover a too low density of suspension induces longer time of water separation when decantation or filtration is used in the process.
  • the stirring of the suspension during the first and second steps corresponds generally to a stirring dissipated energy in the reactors volume of at least 0.2 and at most 1.5 kW/ m 3 , preferably at least 0.5 and at most 1.0 kW/ m 3 .
  • the first step is preferably carried out at a temperature of less than 50°C, preferably at a temperature of at most 45°C, or at a temperature of at most 40°C, more preferably at a temperature of at most 35°C. This makes it possible to obtain an adsorbent at the end of the second step in the form of particles of large to medium particle size and having a high specific surface area.
  • An embodiment of the present invention further relates to the use of particles of hydroxyapatite adsorbent,
  • - having a mean size of at least 20 pm, or of at least 25 pm, or of at least 30 pm; - having a specific surface area of at least 110 m 2 /g, or of at least 120 m 2 /g, or of at least 130 m 2 /g, or of at least 140 m 2 /g; and/or
  • the second step is advantageous for the second step to be carried out at a temperature of at least 45°C, preferably of at least 50°C, more preferably of at least 55°C, or of at least 60°C, or of at least 80°C.
  • this makes it possible to rapidly convert the calcium phosphate compound of low Ca/P ratio (such as brushite) from the first step into the adsorbent comprising a hydroxyapatite of higher Ca/P ratio, with a good fixation of the hydroxide ions at the core and at the surface of the adsorbent, and to more rapidly consume the phosphates from the solution of the suspension (B).
  • the second step is carried out for a duration of at least 0.5 hour.
  • the method takes place in two steps, a first step called “acid attack” and a second step, called “lime maturation”.
  • the first step includes the decarbonation of calcium carbonate (as source of calcium) by the addition of phosphoric acid (as source of phosphate ions). Carbonic acid formed by this acid attack decomposes into water and carbon dioxide, as soon as the maximum solubility of C0 2 in the aqueous phase is reached.
  • Calcium hydrogenphosphate (CaHP0 4 .2H 2 0, also known as brushite) formed in the first step has a Ca/P molar ratio of 1. However, the Ca/P molar ratio of a
  • stoichiometric hydroxyapatite is 1.67. So there is a calcium deficit that has to be filled by the second step.
  • the addition of lime (Ca(OH) 2 ) as an additional source of calcium to the brushite contributes the calcium necessary to approach a stoichiometric hydroxyapatite.
  • this addition of lime also allows the addition of hydroxide anions necessary for the structure of the hydroxyapatite and the neutralization of H + hydrogenphosphate.
  • This method has the advantage that it allows the synthesis of hydroxyapatite from relatively inexpensive reagents, compared to other methods, and uses relatively mild conditions of synthesis (temperature and pH).
  • the synthetized hydroxyapatite in the adsorbent approaches the molar Ca/P hydroxyapatite stoichiometry of 1.67 but generally comprises a Ca/P more than 1.5 and less than 1.67, that is to say, the synthetized hydroxyapatite in the adsorbent is deficient in calcium compared to the stoichiometry.
  • Some of the calcium source e.g., calcium carbonate when it is used in the first step
  • the calcium source which is not utilized in the hydroxyapatite would remain inside the hydroxyapatite adsorbent composition.
  • the first step is to attack limestone with phosphoric acid at a temperature of from 20 to 25°C to make a brushite type structure.
  • the second step is initiated by heating the mixture up to at least 50°C.
  • a suspension of Ca(OH) 2 (such as 25 wt%) is then added to maintain the pH of the suspension at a maximum 8.9.
  • the second step preferably uses an overall Ca/P molar ratio of about 1.67.
  • the goal of this second step is to convert the brushite type structure created in the first step to a hydroxyapatite structure in the second step.
  • the suspension (B) may be left to cool for 1 to 24 hours, preferably at least 10 hours, down to ambient temperature (generally 20-25°C). This makes it possible to mature the adsorbent and to reduce the residues of MCP/DCP or brushite, or of octacalcium (precipitated during the first step), into
  • the suspension (B) comprises an aqueous solution (C) and composite particles, and
  • a portion of the aqueous solution (C) is separated from the suspension (B) in order to obtain an aqueous suspension (D) comprising at least 18% and at most 50% of adsorbent particles, or in order to obtain a wet solid (D') comprising at least 50% and at most 80% of composite particles, or a pulverulent solid (D") comprising at least 80% and at most 95% of adsorbent particles and at least 5% and at most 20% of water.
  • the separation may comprise a dewatering step which increases the solids content.
  • the separation may comprise for example a filter, such as a filter press. This type of separation may provide an aqueous suspension (D) or a wet solid (D') of higher solids content than the
  • the method for making the hydroxyapatite adsorbent particles may further comprise drying the suspension (B) or aqueous suspension (D) or wet solid (D') at a temperature between 50 to l80°C, preferably from 80 to 130 °C, or more preferably from 90 to 120 °C, most preferably from 95 to 115 °C. Drying may comprise any suitable technique suitable for decreasing the water content of the suspension (B) or aqueous suspension (D) or wet solid (D'), such as, but not limited to, spray drying, flash drying, and/or drying in a fluidized bed.
  • the method for making the hydroxyapatite adsorbent particles may comprise spray drying the suspension (B) or aqueous suspension (D) to provide a pulverulent solid (D").
  • the present invention also relates to the use of an aqueous suspension (D) comprising at least 25%, preferably at least 40% and at most 50% of adsorbent particles, or to a wet solid (D') comprising at least 50% and at most 80% of adsorbent particles, or a pulverulent solid (D") comprising at least 70%, preferably at least 80%, and at most 95% of adsorbent particles and at least 5% and at most 20% of water.
  • D aqueous suspension
  • D' comprising at least 50% and at most 80% of adsorbent particles
  • a pulverulent solid (D") comprising at least 70%, preferably at least 80%, and at most 95% of adsorbent particles and at least 5% and at most 20% of water.
  • the adsorbent obtained according to such method is effective for treating the irradiated water stream contaminated by metallic ions.
  • the process for producing a hydroxyapatite composite may comprise the following step:
  • a source of calcium and a source of phosphate ions are mixed in water in a molar ratio that is adjusted to obtain a Ca/P molar ratio of between 0.5 and 1.6, preferably between 0.7 and 1.3, and reacting the source of calcium with the phosphate ions at a pH of between 2 and 8, in order to obtain a suspension (A) of calcium phosphate,
  • a second step adding to the suspension (A) an alkaline compound comprising hydroxide ions in order to set a pH of at least 7.5, preferably at least 8, or at least 8.5, or at least 9, or of at least 10; further adding an additional source of calcium in order to obtain a suspension (B) of composite having a Ca/P molar ratio of greater than 1.6, preferably greater than 1.65 to form a hydroxyapatite structure; and
  • the additive or precursor thereof When the additive or precursor thereof is added in the first step, it may be added at the beginning of the first step before the reaction takes place, during the reaction, or after the reaction is completed in the first step (this being preferred). It is envisioned that the additive or precursor thereof may be added not all at once, for example in at least two portions, for example a first portion in the first step and another portion in the second step.
  • additives or precursors thereof may be added.
  • a first additive or precursor thereof is added in the first step and a second additive or precursor thereof is added in the second step.
  • first and second additives or precursors thereof may be added in the first step or in the second step.
  • additives or precursors thereof that may be added in the first step include activated carbon and/or chloride salts of iron.
  • a particular embodiment of the present invention relates to a process for producing the hydroxyapatite composite, comprising:
  • a source of calcium and a source of phosphate ions are mixed in water in a molar ratio that is adjusted to obtain a Ca/P molar ratio of between 0.5 and 1.6, preferably between 0.7 and 1.3, and reacting the source of calcium with the phosphate ions at a pH of between 2 and 8, in order to obtain a suspension (A) of calcium phosphate, and
  • An alternate embodiment of the present invention relates to a process for producing the hydroxyapatite composite, comprising:
  • a source of calcium and a source of phosphate ions are mixed in water in a molar ratio that is adjusted to obtain a Ca/P molar ratio of between 0.5 and 1.6, preferably between 0.7 and 1.3, and reacting the source of calcium with the phosphate ions at a pH of between 2 and 8, in order to obtain a suspension (A) of calcium phosphate,
  • additives or precursors thereof that may be added in the first step include activated carbon and/or chloride salts of iron.
  • the additive may be added as a precursor of the additive, and this precursor is converted to the form of the additive during the synthesis of the composite in order for the additive to be present in the final composition of the composite.
  • a precursor of the additive may be a salt of iron, and during the synthesis of the composite, the salt of iron is converted to iron hydroxide or oxyhydroxide to generate the additive in the final composition of the hydroxyapatite composite.
  • the additive or precursor thereof may be in the form of a solution or a slurry before it is added to at least one of the first and second steps of the method of making the composite.
  • the additive is preferably incorporated or embedded into or coated onto the hydroxyapatite structure, or otherwise associated with the hydroxyapatite structure via cohesive forces.
  • the additive or precursor thereof may be in the form of a solid before it is added to at least one of the first and second steps.
  • the method of making the composite may further include sieving the powder of the additive or precursor thereof to remove large particles, such as those exceeding a size of 100 microns, or exceeding a size of 90 microns.
  • the powder of the additive or precursor thereof which passes through a sieve No. 170 (under ASTM El l) equivalent to a size of less than 90 microns, or through a sieve No. 200 (under ASTM El 1) equivalent to a size of less than 75 microns, or through a sieve No.
  • the plateau is where the additive is preferably added out at one time, although the addition of additive may be carried out in several increments.
  • the addition of the additive in the second step may be carried out during the same period of time when the hydroxide ions are added (that is to say, before the pH plateau is reached), such as a one-time addition, in several increments, or in a continuous manner.
  • the additive needs to be present during the hydroxyapatite synthesis but its addition does not have to necessarily take place at the time of the hydroxyapatite synthesis.
  • the additive or a precursor thereof may be added before the addition of the hydroxide ions is initiated in the second step.
  • the additive or a precursor thereof may be added even during the first step, parti cul arly if the additive or precursor thereof is compatible with the pH condition of the first step, which is generally less than 7, or less than 6.5, or even less than 6.“Compatible” here means that the additive or precursor thereof added in the first step is not degraded/reacted or otherwise rendered ineffective as an additive for making a hydroxyapatite composite in the second step.
  • FIG. 1 to 5 represent various embodiments of simplified process flow diagrams for carrying out the process according to the present invention.
  • a UV/H2O2 unit 10 there is a mention of a UV/H2O2 unit 10, and it should be understood that any suitable UV/peroxygen unit is suitable in these embodiments.
  • FIG. 1 represents a schematic process flow diagram of an embodiment of the process according to the invention for treating a water stream, for example originating from an ore mining process, containing cyanide, metallic ions (such as barium, cadmium, cobalt, copper, iron, manganese, nickel, lead, zinc) and metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion (such as hexacyanoferrate(II), hexacyanoferrate(III), hexacyanocobaltate(III), tetracyanonickelate(II), tetracyanocuprate(II), or combinations thereof).
  • the water stream may also comprise organic species and/or colored species.
  • This process includes a UV/H2O2 unit 10, an adsorption unit 20 (for metals/organics removal), and a separation unit 30 (for solids removal).
  • a H2O2 source 50 is fed to the UV/H2O2 unit 10 which comprises a UV lamp (UV light source), preferably emiting UV-C, preferably with a wavelength from 200 to 290 nm.
  • a water feedstream 40 to be treated enters the UV/H2O2 unit 10 under suitable peroxidation conditions as described herein to form an irradiated effluent 60.
  • the irradiated effluent 60 in part or in totality, is directed to the adsorption unit 20 while fresh solid adsorbent 70 comprising apatite (preferably hydroxyapatite, more preferably a synthetic hydroxyapatite) is fed to this adsorption unit 20 in order for contaminants, such as free metallic species, to be removed from the irradiated effluent.
  • fresh solid adsorbent 70 comprising apatite (preferably hydroxyapatite, more preferably a synthetic hydroxyapatite) is fed to this adsorption unit 20 in order for contaminants, such as free metallic species, to be removed from the irradiated effluent.
  • the treated effluent 80 which is contacted with the solid adsorbent exiting the adsorption unit 20 is fed to the separation unit 30 where the solids are separated from the liquid phase (water).
  • the entry point of the recycled solids into the adsorption unit 20 may be the same as the fresh adsorbent 70 (not illustrated), or may be different (as illustrated in FIG. 1).
  • An optional pH adjustment step may be done on at least a portion of the irradiated effluent 60 before entering the adsorption unit 20.
  • An optional addition of an acid 115 may be carried out in order to reduce the pH of at least a portion of the irradiated effluent 60 to a value from 7 to 9, preferably from 7.5 to 8.8, yet more preferably from 7.5 to
  • FIG. 2 represents another schematic process flow diagram of an embodiment of the process according to the invention for treating a water stream originating from an ore processing process, containing cyanide, metallic ions (such as barium, cadmium, cobalt, copper, iron, nickel, manganese, lead, zinc) and metal- cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion (such as hexacyanoferrate(II),
  • the water stream may also comprise organic species and/or colored species.
  • This embodiment of the process illustrated in FIG. 2 is similar to what is shown in FIG. 1 except that the adsorption (e.g., for metals/organics removal) and the separation are combined into one single unit 120.
  • the UV/H2O2 treatment proceeds as previously described in FIG. 1 in the UV/H2O2 unit 10 and the irradiated effluent 60 is directed to this adsorption + separation unit 120.
  • the unit 120 includes a settler, where fresh solid adsorbent 70 is fed generally in a zone of the settler which allows sufficient time of contact of the apatite with the metallic ions and optionally organic contaminants. It is preferred that the addition of the fresh adsorbent 70 is carried out away from the treated water outlet of the unit 120 in order to avoid bypass of the fresh solids into the treated water 90.
  • the separation in unit 120 is effective in settling the solids originating from the spent adsorbent and also the particles of metal hydroxides that may form from the metal(s) extracted from the metal-cyanide complexes during the UV/H2O2 treatment in the UV/H2O2 unit 10.
  • the stream 100 containing separated solids can be directed at least in part back to the adsorption + separation unit 120 (spent adsorbent recycle), while a portion 110 of the stream 100 containing separated solids is purged out of the process.
  • the entry point of the recycled solids to unit 120 may be the same as the entry point of fresh adsorbent 70 (not illustrated), or may be different (as illustrated in FIG. 2).
  • the UV/H2O2 unit 10 may comprise a plurality of UV units, each comprising a UV lamp, and the H2O2 source 50 may be split to be fed to the plurality of these UV units.
  • the plurality of UV units may be operated in parallel or in series (preferred). For example, FIG. 4
  • FIG. 4 illustrates two (2) UV units lOa, lOb operated in series, and the H2O2 source 50 is split into two streams 50a and 50b, which are fed respectively to the 2 UV units lOa and lOb.
  • Any embodiment described with respect to the plurality of the UV units concerning FIG. 4 is equally applicable for the UV/H2O2 unit 10 of FIG. 1 & 2.
  • FIG. 3 represents another schematic process flow diagram of an embodiment of the process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, and optionally organics.
  • This process is similar to what is shown in FIG. 1 except that the UV/H2O2 step and the adsorption step (for metals/organics removal) are carried out into one combined unit 210.
  • the UV/H2O2 treatment step and the adsorption step proceed as previously described in FIG. 1 except that these two steps are done in the same unit 210.
  • the pH selected for this UV peroxidation in unit 210 must be compatible with the operational pH of the metals/organics removal step.
  • the separation in unit 30 is effective in settling the solids originating from the adsorbent and also the particles of metal hydroxides that may form from the metal(s) extracted from the metal-cyanide complexes during the UV/H2O2 treatment step in combined unit 210.
  • the stream 100 containing separated solids exiting the separation unit 30 can be directed at least in part back to the combined unit 210 (spent adsorbent recycle), while a portion 110 of the stream 100 containing separated solids is purged out of the process.
  • the entry point of the recycled solids to combined unit 210 may be the same as the fresh adsorbent 70 (not illustrated), or may be different (as illustrated in FIG. 3).
  • pH adjustment on the water feedstream 40 before entering the combined UV/H2O2 + adsorption unit 210 by an optional addition of acid 215 in order for the pH of the water feedstream 40 entering the unit 210 to be a value from 8 to 11, preferably from 8.5 to 10 suitable for both UV peroxidation and adsorption of metals and optionally organics on the solid adsorbent comprising apatite in the combined unit 210.
  • FIG. 4 represents another schematic process flow diagram of an embodiment of the process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, comprising a UV/H2O2 treatment step in a UV/H2O2 unit 10, a buffer tank 220, an adsorption step (for metals/organics removal) in an adsorption unit 20 and a separation step (for solids removal) in a separation unit 30.
  • This process is similar to what is shown in FIG. 1 except that the UV/H2O2 unit 10 is in fluid circulation with the buffer tank 220.
  • the UV/H2O2 unit 10 comprises a plurality of UV units and the peroxygen source is fed to the plurality of UV units.
  • Each of the UV units comprises a UV lamp, preferably a Hg lamp.
  • the plurality of UV units may comprise at least 2, preferably at least 3 UV units, and/or at most 15, preferably at most 12, more preferably at most 10 UV units.
  • the UV units are preferably sized the same so as to accommodate the same incoming flow rate of water stream to be treated.
  • the plurality of UV units preferably comprises the same type of UV lamp, preferably the same type of Hg lamp, but not necessarily.
  • the plurality of UV units may be operated in series, that is to say, wherein the irradiated water effluent exiting a UV unit is sent to a subsequent UV unit to get another round of UV treatment. In this manner, the water effluent being fed to the UV/H2O2 step is subjected several times to UV irradiation in the presence of peroxygen.
  • FIG. 4 illustrates two (2) UV units lOa, lOb operated in series, and the H2O2 source 50 is split into two streams 50a and 50b, which are fed respectively to UV units lOa and lOb.
  • FIG.4 illustrates two UV units operated in series, it is to be understood that the plurality of UV units may be operated in parallel, that is to say, wherein a water stream feeding the UV/H2O2 step is split into several feedstreams to feed the plurality of the UV units.
  • At least some or all of the UV lamps in the plurality of UV units preferably emit UV-C, preferably with a wavelength from 200 to 290 nm.
  • the water feedstream 40 to be treated by the process is fed to the buffer tank 220.
  • At least a portion of the tank content represented by water effluent 170 exiting the buffer tank 220 is directed to the UV/H2O2 unit 10 where the water is irradiated under suitable peroxidation conditions as described herein to form an irradiated effluent 60 that exists the UV/H2O2 unit 10.
  • the irradiated effluent 60 is then sent back to the buffer tank 220.
  • the stream 170 exiting the buffer tank 220 and entering the UV/H2O2 unit 10 and the irradiated effluent 60 exiting the UV/H2O2 unit 10 and entering the buffer tank 220 thus create a fluid circulation between the UV/H2O2 unit 10 and the buffer tank 220.
  • volumetric flow rates of incoming stream 60 and exiting stream 170 in the buffer tank 220 are preferably about the same. Additionally, the volumetric flow rates of the incoming water feedstream 40 and of the exiting effluent 160 in the buffer tank 220 are also preferably about the same. This permits the maintenance of the hydraulic balance in the buffer tank 220 between the incoming streams (40, 60) and exiting streams (160, 170).
  • the effluent stream 160 (at least a portion of which has been irradiated) which exits the buffer tank 220 and which is directed to the adsorption unit 20 may be withdrawn from the buffer tank 220 by way of an overflow. This would permit to maintain the contents’ level in the buffer tank 220 at a constant value.
  • the volumetric capacity of the buffer tank 220 may be sized to be at least 2 times greater, preferably at least 5 times greater, more preferably at least 10 times greater, yet more preferably at least 15 times greater, or at least 20 times greater, than the volumetric capacity of the UV unit(s).
  • the buffer tank 220 may be sized to be at least 20 m 3 , preferably at least 30 m 3 , more preferably at least 40 m 3 .
  • the residence time in the buffer tank 220 may be at least 15 minutes, or at least 30 minutes, or at least 45 minutes, or at least 60 minutes and/or at most 180 minutes, or at most 150 minutes, or at most 120 minutes.
  • the buffer tank 220 may comprise at least one mixed tank in which a stirrer containing one or more impellers stirs its content or at least one tank where its content is circulated for example by an internal or external pump.
  • At least a portion of the effluent 160 (at least a portion of which has been irradiated) exiting the buffer tank 220 is directed to the adsorption unit 20 in order for free metallic ions to be removed. At least a portion of this effluent is contacted with the solid adsorbent and exits the adsorption unit 20 as treated effluent 80.
  • the treated effluent 80 is fed to the separation unit 30 where the solids are separated from the liquid phase (water).
  • a stream 100 containing separated solids and exiting the separation unit 30 can be directed at least in part back to the adsorption unit 20 (solid adsorbent recycle), while a portion 110 of the stream 100 containing separated solids is purged out of the process.
  • the entry point of the recycled solids into the adsorption unit 20 may be the same as the fresh adsorbent 70, or may be different (illustrated with different entry points for fresh and spent recycled adsorbents in FIG. 4).
  • An optional pH adjustment step may be carried out on at least a portion of the effluent 160 (at least a portion of which has been irradiated) exiting the buffer tank 220 before entering the adsorption unit 20.
  • an optional addition of an acid 115 may be carried out in order to reduce the pH of the effluent 160 to a value from 7 to 9, preferably from 7.5 to 8.8, yet more preferably from 7.5 to 8.5.
  • FIG. 5 represents another schematic process flow diagram of an embodiment of the process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, comprising an adsorption step (pre-treatment for removal of organics, free metals, and/or colored species), a separation step (for solids removal), a UV/H2O2 treatment step in fluid circulation with a buffer tank, wherein at least a portion of the irradiated effluent is sent to an adsorption step (for removal of free metals liberated from cyanide complexes), wherein the adsorption step prior to irradiation and the adsorption step after irradiation are preferably carried out in a same unit (unit 20).
  • This process includes a UV/H2O2 unit 10, a buffer tank 220, an adsorption unit 20 (for metals/organics/ color removal), and a separation unit 30 (for solids removal).
  • This process is similar to what is shown in FIG. 4 in that the UV/H2O2 step is in fluid circulation with the buffer tank 220, but the adsorption unit 20 in this process is used for an adsorption pre-treatment of the water feedstream prior to being directed to the UV/H2O2 unit 10 and also used for an adsorption of at least a portion of the irradiated effluent which exits either the UV/H2O2 unit 10 (not illustrated) or the buffer tank 220 in fluid circulation with the UV/H2O2 unit 10 (as illustrated in FIG. 5).
  • the water feedstream 40 is fed to the adsorption unit 20 which serves as a pretretament step for the removal of organics, free metallic species and/or color.
  • the solid adsorbent 70 is added to the adsorption unit 20.
  • the solid adsorbent 70 used in the adsorption unit 20 is suitable for removing color.
  • the presence of color in the water feedstream 40 to be treated may indeed hinder the performance of the UV in the UV/H2O2 step.
  • removing some of the color of the water feedstream prior to the UV/H2O2 step may be beneficial to maximize the use of the UV light for the photo-disassociation of the metal-cyanide complexes and not for the treatment of colored species in the water stream.
  • the solid adsorbent 70 used in the adsorption unit 20 is further suitable for removing at least a portion of organics and free metallic species such as ions, in particular free species of heavy metals, arsenic, selenium, ....
  • the water feedstream 40 generally contains free metallic species such as metallic ions that are not complexed with cyanide and/or organics. Therefore the adsorption unit 20 used in FIG. 5 for adsorption prior to and after irradiation step preferably uses a solid adsorbent 70 comprising apatite as described herein in the description.
  • a particular preferred solid adsorbent used in this particular adsorption unit comprises a synthetic hydroxyapatite and/or a synthetic hydroxyapatite composite with activated carbon.
  • the synthetic hydroxyapatite composite with activated carbon is particularly preferred for removal of free (not-complexed) heavy metals, at least a portion of organics and colored species.
  • An effluent 80 exiting the adsorption unit 20 is directed to the separation unit 30 in which the solids are separated from the liquid phase (water).
  • the entry point of the recycled solids into the adsorption unit 20 may be the same as the fresh adsorbent 70, or may be different.
  • the pre-treated water 180 is directed to the buffer tank 220.
  • a water effluent 170 exiting the buffer tank 220 which is to be treated enters the UV/H2O2 unit 10 under suitable peroxidation conditions as described herein to form an irradiated effluent 60 that exists the UV/H2O2 unit 10.
  • the irradiated effluent 60 is then sent back to the buffer tank 220.
  • a treated water 190 is withdrawn from the buffer tank 220 and exits the process.
  • the stream 170 exiting the buffer tank 220 and entering the UV/H2O2 unit 10 and the irradiated effluent 60 exiting the UV/H2O2 unit 10 and entering the buffer tank 220 thus create a fluid circulation between the UV/H2O2 unit 10 and the buffer tank 220.
  • the volumetric flow rates of incoming stream 60 and exiting stream 170 are preferably about the same.
  • the volumetric flow rates of feedstream 180 and of effluents 190 and 160 are also preferably about the same. This allows to maintain hydraulic balance in the buffer tank 220 between the incoming streams (180, 60) and exiting
  • At least a portion of the irradiated effluent 160 exiting the buffer tank 220 is directed to the adsorption unit 20 in order for free metallic ions to be removed from the irradiated effluent. At least a portion of this irradiated effluent is contacted with the solid adsorbent and exits the adsorption unit 20 as treated effluent 80.
  • the effluent stream 160 which exits the buffer tank 220 and which is directed to the adsorption unit 20 may be withdrawn from the buffer tank 220 by way of an overflow. This would permit to maintain the contents’ level in the buffer tank 220 at a constant value.
  • the UV/H2O2 unit 10 comprises a plurality of UV units comprising UV lamps and the peroxygen source is fed to the plurality of UV units.
  • FIG. 5 illustrates two (2) UV units lOa, lOb operated in series, and the H2O2 source 50 is split into two streams 50a and 50b, which are fed respectively to the 2 UV units lOa and lOb. Any embodiment described with respect to the plurality of the UV units concerning FIG. 4 is equally applicable for FIG. 5.
  • the volumetric capacity of the buffer tank 220 may be sized to be at least 2 times greater, preferably at least 5 times greater, more preferably at least 10 times greater, yet more preferably at least 15 times greater, or at least 20 times greater, than the volumetric capacity of the UV unit(s).
  • the buffer tank 220 may be sized to be at least 20 m 3 , preferably at least 30 m 3 , more preferably at least 40 m 3 .
  • the residence time in the buffer tank 220 may be at least 15 minutes, or at least 30 minutes, or at least 45 minutes, or at least 60 minutes and/or at most 180 minutes, or at most 150 minutes, or at most 120 minutes.
  • the buffer tank 220 may comprise at least one mixed tank in which a stirrer containing one or more impellers stirs its content or at least one tank where its content is circulated for example by an internal or external pump.
  • An optional pH adjustment step may be carried out on at least a portion of the water feedstream 40 entering the adsorption unit 20 for pre-treatment in order to remove at least a portion of organics, free metallic species (e.g., metals in the forms of ions and not complexed), and/or color.
  • an optional addition of an acid 215 may be carried out in order to reduce the pH of the water feedstream 40 to a value from 7 to 9, preferably from 7.5 to 8.8, yet more preferably from 7.5 to 8.5.
  • An optional pH adjustment step may be carried out on at least a portion of the irradiated effluent 160 exiting the buffer tank 220 before entering the adsorption unit 20 on on at least a portion of the irradiated effluent 60 exiting the UV/H202 unit 10 before entering the buffer tank 220.
  • an optional addition of an acid 115 may be carried out in order to reduce the pH of the effluent 60 or effluent 160 to a value from 7 to 9, preferably from 7.5 to 8.8, yet more preferably from 7.5 to 8.5.
  • ITEM 1 A process for treating a water stream, preferably originating from a ore mining process, containing cyanide, metallic ions and metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion, said method comprising:
  • ITEM 2 The process of ITEM 1, wherein the pH during irradiation is greater than 7 and up to 11, preferably from 8 to 11, more preferably from 8.5 to 10.5, yet more preferably from 9 to 10.5, even more preferably from 9.5 to 10.5, most preferably from 10 to 10.5.
  • the at least one metal-cyanide complex which undergoes photo-dissociation contains a metal in the complex selected from the group consisting of Fe(II), Fe(III), Co(II), Ni(II), Cu(I), Cu(II), and Hg(II), preferably selected from the group consisting of Fe(II), Fe(III), Co(II), Cu(I), Cu(II), and Ni(II).
  • ITEM 4 The process of any of the preceding ITEMS, wherein said metal- cyanide complex which undergoes photo-dissociation is selected from the group consisting of hexacyanoferrate(II), hexacyanoferrate(III),
  • the ultraviolet light has a wavelength in the region from 200 to 375 nm, preferably from 200 to 350 nm, more preferably from 200 to 300 nm, most preferably at 254 nm, or the ultraviolet light is emits by a UV-C lamp, preferably with a wavelength from 200 to 290 nm, preferably in order for the metal-cyanide complexes to undergo photo-disassociation and for the peroxygen to form hydroxyl radicals.
  • ITEM 6 The process of any of the preceding ITEMS, wherein the irradiation with ultraviolet light is carried out for at least 5 minutes and preferably less than 30 min.
  • ITEM 7 The process of any of the preceding ITEMS, wherein the irradiation with ultraviolet light is carried out with a Hg lamp with a minimum electric rating of 8 W, preferably a low pressure UV Hg lamp with an electric rating from 8 to 100 W.
  • ITEM 8 The process of any of the preceding ITEMS, wherein the UV irradiation step with peroxygen further forms particles of metal hydroxides with the metal liberated from said metal-cyanide complex, and wherein the process further includes removing said particles of metal hydroxides from the treated effluent in said separating step or removing said particles of metal hydroxides from the irradiated effluent in a different separation step prior to contacting with the solid adsorbent.
  • ITEM 9 The process of any of the preceding ITEMS, wherein the peroxygen used during the irradiation step comprises or consists of H 2 0 2 , and wherein H 2 0 2 is used in a H 2 0 2 :CN molar ratio of at least 2:1, preferably at least 5:1, more preferably at least 10:1, compared to cyanide in the effluent which is free and which can be liberated from one or more of said metal-cyanide complexes during UV irradiation.
  • ITEM 10 The process of any of the preceding ITEMS, wherein the adsorbent comprises a calcium-deficient hydroxyapatite with a Ca/P ratio more than 1.5 and less than 1.67, preferably wherein the calcium- deficient hydroxyapatite is synthetically made.
  • ITEM 11 The process of ITEM 10, wherein the adsorbent further comprises calcium carbonate in an amount between 0.5 to 20 wt% and/or contains less than 1 wt% Ca(OH) 2 .
  • the solid adsorbent comprises a synthetic hydroxyapatite composite, said synthetic hydroxyapatite composite comprising a hydroxyapatite and at least one additive which is present during the hydroxyapatite synthesis.
  • ITEM 13 The process of ITEM 12, wherein the at least one additive in the synthetic hydroxyapatite composite is embedded or incorporated into or coated onto the hydroxyapatite.
  • ITEM 14 The process of ITEM 12 or 13, wherein the at least one additive comprises at least one activated carbon, iron (such as in the form of metal, salt, oxide, oxyhydroxide, or hydroxide), or combinations thereof.
  • the at least one additive comprises at least one activated carbon, iron (such as in the form of metal, salt, oxide, oxyhydroxide, or hydroxide), or combinations thereof.
  • ITEM 15 The process of any of ITEM 12-14, wherein the solid adsorbent comprises:
  • the additives in the synthetic hydroxyapatite composites are different; preferably wherein at least one of the additives in a first synthetic hydroxyapatite composite comprises an activated carbon or blend of two or more activated carbons, and another additive in a second synthetic
  • hydroxyapatite composite comprises iron (such as in the form of metal, salt, oxide, oxyhydroxide, or hydroxide); or
  • the at least one additive in the synthetic hydroxyapatite composite comprises at least one activated carbon, iron (such as in the form of metal, salt, oxide, oxyhydroxide, or hydroxide), or combinations thereof.
  • ITEM 16 The process of any of the preceding ITEMS, wherein the contacting step with the solid adsorbent comprising apatite is carried out at a pH from 6.5 to 10, preferably a pH from 7 to 9.5, more preferably a pH from 7 to 9, yet more preferably a pH from 7.2 to 8.8, still more preferably a pH from 7.5 to 8.8, yet still more preferably a pH from 7.5 to 8.5.
  • ITEM 17 The process of any of the preceding ITEMS, wherein the contacting step with the solid adsorbent comprising apatite is carried out by mixing the solid adsorbent in the irradiated effluent with a content from 1 to 10 wt% of solid adsorbent, preferably from 2 to 5 wt% of solid adsorbent.
  • ITEM 18 The process of any of the preceding ITEMS, further comprising reducing the pH of at least a portion of the irradiated effluent with an acid (such as sulfuric acid or hydrochloric acid) before contacting with the solid adsorbent.
  • ITEM 19 The process of any of the preceding ITEMS, wherein the contacting with the adsorbent is carried out in a mixed tank or a tank where its content is recirculated, and wherein the solid adsorbent is in the forms of particles which are suspended in water in the tank.
  • ITEM 20 The process of any of ITEMS 1-19, wherein the contacting with the solid adsorbent and the irradiation step are carried out in different units.
  • ITEM 21 The process of any of ITEMS 1-19, wherein the contacting with the adsorbent (adsorption) and the irradiation step are carried out in a same unit.
  • ITEM 22 The process of ITEM 21, wherein the combined UV irradiation step with peroxygen and the contacting step with solid adsorbent (adsorption) are carried out at a pH from 7 to 10 or from 7.5 to 10, or from 8 to 10, preferably a pH from 8to 9.5 or from 8.5 to 9.5, more preferably a pH from 8.5 to 9.
  • ITEM 23 The process of any of ITEMS 1-19, wherein the contacting step with the adsorbent (adsorption step) and the separation step are carried out in a same unit, preferably wherein the unit is a settler, and wherein the solid adsorbent is added to the settler in a zone to allow contact with the treated effluent to remove the metallic ions and for the solid adsorbent to settle after contact.
  • ITEM 24 The process of any of the preceding ITEMS, wherein contacting at least a portion of the irradiated effluent (adsorption step) with a solid adsorbent comprising apatite is effective to remove at least part of said metallic ions containing one or more metals selected from the group consisting of Al, Ag, Ba, Be, Ce, Co, Cd, Cu, Cr, Fe, Hg, La, Li, Mn, Mg, Mo, Ni, Pb, Pd, Rb, Sb, Sn, Sr, Th, Ti, U, V, Y, Zn, As, B, F, Se, and combinations thereof.
  • metals selected from the group consisting of Al, Ag, Ba, Be, Ce, Co, Cd, Cu, Cr, Fe, Hg, La, Li, Mn, Mg, Mo, Ni, Pb, Pd, Rb, Sb, Sn, Sr, Th, Ti, U, V, Y, Zn, As, B, F, Se, and
  • ITEM 25 The process of any of the preceding ITEMS, wherein the water stream further comprises organic contaminants, particularly those of PAHs, phenolic compound, naphtol and derivatives, and wherein the contacting step (adsorption step) removes at least a portion of said organic contaminants.
  • ITEM 26 The process of any of the preceding ITEMS, wherein separating the treated effluent includes settling.
  • ITEM 27 The process of any of the preceding ITEMS, wherein separating the treated effluent includes adding a flocculant to the treated effluent before or during settling.
  • ITEM 28 The process of any of the preceding ITEMS, wherein the peroxygen used during the irradiation step comprises or consists of H 2 0 2 , and wherein the H 2 0 2 content in the effluent is from 10 to 1,000 ppm, preferably from 25 to 750 ppm, preferably from 40 to 500 ppm, yet more preferably from 50 to 400 ppm, most preferably from 100 to 400 ppm.
  • ITEM 29 is preferably from 10 to 1,000 ppm, preferably from 25 to 750 ppm, preferably from 40 to 500 ppm, yet more preferably from 50 to 400 ppm, most preferably from 100 to 400 ppm.
  • H 2 0 2 is injected periodically into a circulation loop hydraulically connected to a photoreactor where the irradiation takes place or to a tank in such a circulation loop in order for H 2 0 2 content in the effluent to be from 10 to 1,000 ppm, preferably from 25 to 750 ppm, preferably from 40 to 500 ppm, yet more preferably from 50 to 400 ppm, most preferably from 100 to 400 ppm.
  • ITEM 30 The process of any of the preceding ITEMS, further comprising carrying out the UV irradiation step in the presence of a peroxygen in an UV irradiation unit which is in fluid circulation with a buffer tank, wherein at least a portion of the irradiated effluent flows to the buffer tank and back to the UV irradiation unit.
  • ITEM 31 The process of ITEM 30, wherein the at least a portion of the water stream which is to be irradiated with ultraviolet light in the presence of a peroxygen is first fed to the buffer tank before being fed to the UV irradiation unit.
  • ITEM 32 The process of any of the preceding ITEMS, wherein the UV irradiation step is carried out in the presence of peroxygen in a plurality of UV units operated in series, each UV unit comprising a UV lamp.
  • ITEM 33 The process of any of the preceding ITEMS, further comprising carrying out an adsorption step as a pre-treatment prior to the UV irradiation step in order to remove metals, organics and/or colored species from the at least portion of the water feedstream prior to being directed to the UV irradiation step.
  • ITEM 34 The process of ITEM 33, wherein the adsorption step carried out on the at least portion of the irradiated effluent after the UV irradiation step and the adsorption step carried out as a pre-treatment prior to the UV irradiation step are both performed in a same adsorption unit using the solid adsorbent comprising apatite.
  • ITEM 35 The process of ITEM 34, wherein the solid adsorbent used in the adsorption unit comprises a synthetic hydroxyapatite composite with activated carbon.
  • ITEM 36 The process of any of the preceding ITEMS, wherein the UV irradiation step further generates bicarbonate and nitrogen gas from cyanates formed by the UV peroxidation of the metal-cyanide complexes.
  • ITEM 37 The process of any of the preceding ITEMS, wherein the irradiation with ultraviolet light is carried out with a UV lamp, preferably a Hg lamp, having a power of at least 55W, preferably of at least 95W.
  • ITEM 38 The process of any of the preceding ITEMS, wherein the peroxygen used during the irradiation step comprises or consists of H 2 0 2 , and wherein the H 2 0 2 content in the water stream to be treated is at least 100 ppm.
  • the pH measurements were made using a WTW Sentix 41 electrode (pH 0-14, temperature: 0 °C-80 °C), a pH meter WTW pH3l 10.
  • the calibration of the equipment was made using three buffer solutions: at pH 4.0 (batch Dulco test-0032) Prominent, a WTW pH 7.0 (WTW D-82362) and at pH 10.01 Hach (cat 27702). Note: If multiple sample measurements were to be made with the same electrode, the electrode was rinsed with deionized water between each measurement.
  • the particle size measurement was carried out on a Beckman Coulter LS 230 laser diffraction particle size analyser (laser of wavelength 750 nm) on particles suspended in water and using a size distribution calculation based on Fraunhofer diffraction theory (particles greater than 10 pm) and on Mie scattering theory (particles less than 10 pm), the particles being considered to be spherical.
  • the BET specific surface area was determined by gas adsorption on a Micromeritics ASAP2020 machine. Before the analysis, the samples (0.7 to 1 g) are pretreated under vacuum at 250°C until a stable vacuum of 4-5 pbar has been achieved. The measurements were carried out using nitrogen as adsorbent gas at 77°K via the volumetric method, according to the ISO 9277: 2010 standard (Determination of the specific surface area of solids by gas adsorption - BET method). The BET specific surface area was calculated in a relative pressure (R/R0) range varying from around 0.05 to 0.20.
  • ICP-MS Inductively Coupled Plasma Mass Spectrometry
  • a hydroxyapatite material was made under similar conditions as those described in example lb of WO2015/173437 patent application by SOLVAY SA.
  • This hydroxyapatite (to be used as adsorbent) is labelled“HAPi”.
  • the process used two steps. In the first step, limestone was dispersed in water at 20-25°C in a 5-liter reactor (with baffles). Then H 3 PO 4 (75%) was added to this suspension and the mixture was stirred at 700 rpm. The first step used an overall Ca/P molar ratio of about 1. The goal of this first step was to attack the limestone to make a brushite type structure. At the end of the addition of acid, the second step was initiated by heating the mixture up to about 50°C.
  • a 25 wt% suspension of Ca(OH) 2 was then added to maintain the pH of the suspension at a maximum 8.9.
  • the second step used an overall Ca/P molar ratio of about 1.67.
  • the goal of this second step was to convert the brushite type structure created in the first step to a hydroxyapatite structure in the second step.
  • the reaction time was 120 minutes (2 hrs). After the reaction time, the suspension was continually stirred at half the stirring speed than was used in the first step to allow it to cool down to 20-25°C.
  • a hydroxyapatite composite with activated carbon was made using Pulsorb C from Chemviron as the source of activated carbon.
  • the content of activated carbon in the hydroxyapatite composite was about 10% by weight.
  • This hydroxyapatite composite (to be used as adsorbent) is labelled“BHAPi”.
  • the preparation of the composite with activated carbon was carried out in a similar manner as in the Example l.a., except that the activated carbon was added during the synthesis of the hydroxyapatite during the lime addition step (2 nd step) after the pH had risen to about 8-9 and after the reaction medium was heated to +/- 50 °C.
  • the activated carbon was added in the form of a powder.
  • the reactor used for this synthesis was a baffled 200-L reactor. No significant change during the synthesis of the composite (compared to the synthesis as described in Example l.a.) is noted apart from this addition of activated carbon during the pH plateau in the 2 nd step.
  • the solid portion of the suspension in the second step remained the same, at about 18wt% by weight.
  • the pH used for the making of the composite was similar to that of hydroxyapatite without additive, namely a range between pH 6.5 and 12, and preferred being maintained between 8 and 9.
  • the temperature for the first step was 20°C and the temperature for the second step was maintained at 50°C. l.c. Porosity and particle size
  • the tests were carried out in a method similar to what is illustrated in FIG.l.
  • About 1.5 liters of a water stream (WW1 or WW2) was placed in a UV/H2O2 reactor at a pH of about 9.5. This alkaline pH was selected to avoid the release of HCN gas during this UV/H2O2 treatment.
  • the mixing in this reactor was done by recirculating a portion of the effluent with an external pump in order to homogenize the reactor content.
  • the UV/H2O2 treatment was carried out for 1 hour residence time using a low pressure UV Hg light operated at 95W and at a wavelength of 254 nm.
  • Two H 2 0 2 :CN molar ratios were tested at 5:1 and 10:1.
  • a portion (1 liter) of the irradiated water was extracted from the initial 1.5 L.
  • the pH of this l-L irradiated water was adjusted to 7.6 by addition of hydrochloric acid (1 N).
  • a first portion (400 ml) of this pH-adjusted effluent was used for carrying out the adsorption test with 2 wt% of the solid adsorbent HAPi, and another portion (400 ml) of this pH-adjusted effluent was used for carrying out the adsorption test with 2 wt% of the solid BHAPi adsorbent (hydroxyapatite composite).
  • the pH at the end of these two adsorption steps was about 8.1-8.2.
  • WW1 had an initial free CN content of 5.8 mg/l and an initial pH of 9.4.
  • WW2 had an initial free CN content of 8 mg/l and an initial pH of 9.6.
  • the % removal in TABLES 4 & 5 was calculated based on the difference of the measured value (2) of the metal content after the UV/H 2 0 2 treatment and the value measured after the adsorption test (3 for HAPi) or (4 with BHAPi) divided by the same measured value (2).
  • the % removal was high in the 95-96 % with the BHAPi (composite) adsorption and with HAPi adsorption.
  • the % removal was high in the 97 % with the BHAPi (composite) adsorption but the % removal was poor (15% & 21%) with HAPi adsorption.
  • the % removal was high in the 98 % for either of BHAPi (composite) and HAPi adsorptions.
  • the % removal was high in the 92-98 % for either of BHAPi (composite) and HAPi adsorptions.
  • the % removal was high in the 93 % with the BHAPi (composite) adsorption, but there was no removal (0%) with HAPi adsorption.
  • the % removal was moderately low in the 62-65% with the BHAPi (composite) adsorption but the % removal was lower (42-46 %) with HAPi adsorption.
  • the % removal was high in the 92-93 % with the BHAPi (composite) adsorption and with HAPi adsorption.
  • the % removal was high in the 89-96 % with the BHAPi (composite) adsorption and with HAPi adsorption.
  • the % removal was moderate in the 54-55 % with the BHAPi adsorption but the % removal was very poor (11% & 9%) with HAPi adsorption.
  • the % removal was moderate in the 41-42 % with the BHAPi adsorption but the % removal was very poor (26-27%) with HAPi.
  • the % removal was high in the 87-90 % with the BHAPi (composite) adsorption and with HAPi adsorption.
  • the % removal was high in the 85-90 % with the BHAPi adsorption but the % removal was poor (5%) with HAPi adsorption.
  • the % removal was moderately low in the 33-46% with the BHAPi and HAPi adsorption.
  • the % removal was very high in the 99-100 % with the BHAPi (composite) adsorption and with HAPi adsorption.
  • HAP 2 Another hydroxyapatite material labelled“HAP 2 ” was made in the similar manner as previously described for Example l.a, except that the synthesis was arried out in a 200-L vessel, the same vessel as described in Example l.b.
  • the adsorption step was carried out as follows. In a 200-ml water sample, 7 g HAP 2 (or 7.1 g BHAP 2 ) were mixed for 1 hour at 10 rpm at a pH of 8.8 (corresponding to an equivalent loading of 20 g of dry matter/L) following by decantation for 10 minutes, and the supemate water was filtered using a 45-mih syringe filter before measuring the metal contents.
  • the hydroxyapatite HAP 2 had very limited activity because it only treats significantly the Fe with removal of 74%. A Cu reduction of 5% was also observed but remained low in comparison with the amount of Cu present in the water sample WW3.
  • the hydroxyapatite composite BHAP 2 had better processing capabilities for Ni, Cu and Fe present in the water sample WW3 with respectively 100%, 93% and 74% removal, respectively.
  • BHAP 2 resulted in a removal of 96% for Cu and 73% for Ni from WW4, and these removals were similarly (albeit slightly lower) for Cu and Ni compared to the WW3, to what was observed with HAP 2 .
  • the improved efficiency of removal for Ni and Cu from WW4 and the inefficacy for Fe from WW4 may be due to a change in the balance of complexation of these metallic elements.
  • Tests were carried out in a 3l6-stainless steel 1.7- liter photoreactor in which a UV-C lamp was inserted.
  • the UV lamp used in the photoreactor was a Philips 95W UV-C lamp (with a UV-C power of 27W), respectively.
  • the UV lamp was protected from the water stream by a quartz sheath.
  • the reactor was equipped with a jacket to regulate the temperature of the water stream inside the photoreactor.
  • a 30 wt% FI 2 0 2 solution was injected into the buffer tank to achieve a certain concentration of H 2 0 2 in the effluent entering the photoreactor, and the H 2 0 2 was mixed for about 1 minute in the tank before the recirculation pump was started.
  • a final water aliquot after the adsorption step was filtered using a 0.45 pm syringe filter for analysis of metals via ICP-MS.
  • the % removal in TABLES 9 & 10 was calculated based on the difference of the initial value of the various metal contents measured by ICP-MS in the ore processing water stream WW3 prior to any treatment and the final value obtained after the adsorption (TABLE 9 with HAP 2 & TABLE 10 with BHAP 2 ) divided by the same initial value.
  • the UV peroxidation step in this example lasted 240 minutes (4 hours).
  • Example 6 Tests were carried out as similarly described in Example 6. The concentration in H 2 0 2 was varied from 0 to 400 ppm; the UV lamp was a Philips 95W UV-C lamp; the recirculation flow rate was 30 L/hr and the injection frequency of the H 2 0 2 into the buffer tank was 20 minutes.
  • the % removal of targeted metals (Co, Cu, Fe, Ni) in TABLES 11 & 12 was calculated based on the difference of the initial value of the various metal contents measured by ICP-MS in the ore processing water stream prior to any treatment and the final value obtained after the adsorption (TABLE 11 with HAP 2 & TABLE 12 with BHAP 2 ) divided by the same initial value.
  • the UV peroxidation step lasted 240 minutes (4 hours), except for the UV peroxidation step with 50 ppm H 2 0 2 which was carried out for 180 min (3 hours).
  • UV lamps used in the UV/H2O2 step were Philips UV-C lamps with either 55W power or 95 W power (equivalent in UV-C power of 17W or 27 W).
  • the recirculation flow rate was 30 L/hr ; the injection frequency of the H2O2 into the buffer tank was 20 minutes; and the concentration in FLO2 was 200 ppm .
  • the UV peroxidation step using the recirculation loop lasted 240 minutes (4 hours).
  • the % removal in TABLES 13 & 14 was calculated based on the difference of the initial value of the various metal contents measured by ICP-MS in the ore processing water stream prior to any treatment and the final value obtained after the adsorption (TABLE 13 with HAP 2 & TABLE 14 with BHAP 2 ) divided by the same initial value.
  • the impact of the UV-C lamp power was significant for the most stable metal complexes such as those with Co. Indeed, in increasing the power of the lamp from 55 W to 95 W (with equivalent UV-C power of 17W to 27W), the removal of Co increased from 24% to 50%.
  • Tests were carried out as similarly described in Example 7 with either 150 ppm or 200 ppm H2O2 over a time period for the UV/H2O2 treatment from 60 minutes to 240 minutes, while keeping the adsorption step identical
  • the UV lamp was a Philips 95W UV-C lamp (eq. power 27W for UV-C); the recirculation flow rate was 30 L/hr and the injection frequency of the H2O2 into the buffer tank was 20 minutes.
  • TABLE 15 Treatment with 150 ppm H 2 0 2 over UV/H 2 0 2 pretreatment time

Abstract

A process for treating a water stream, preferably originating from a ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, such as one or more cyanide complexes comprising iron, cobalt, nickel, and/or copper, including two main steps: irradiating with UV light in the presence of a peroxygen, preferably comprising Η202, to form an irradiated effluent, and contacting the irradiated effluent with a solid adsorbent comprising apatite to form a treated effluent. The irradiation step is carried out under alkaline pH with UV light having a wavelength from 200 to 375 nm, preferably UV-C light from 200 to 290 nm, for photo-disassociation of the complexes and forming hydroxyl radicals. The solid adsorbent preferably comprises a synthetic hydroxyapatite, preferably calcium-deficient. The synthetic hydroxyapatite may be a composite made with an additive which preferably contains activated carbon and/or iron.

Description

Removal of stable metal-cyanide complexes and metallic ions from water stream
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. provisional application
No. 62/662734 filed April 25, 2018 and to European application No. 18187117.9 filed August 2, 2018, the whole content of each of these applications being incorporated herein by reference for all purposes.
TECHNICAL FIELD
The invention relates to a process for treating an effluent contaminated by metallic ions and/or stable metal-cyanide complexes, particularly a water stream generated by an ore mining process.
BACKGROUND ART
Cyanidation is a process used in the mining industry where metals are leached from ores into a weak solution of cyanide, generally sodium cyanide. Once the metals are leached from the ores, the metals are precipitated and separated from the cyanide solution. Following dissolutions of the metals in the cyanide solution, the process further includes recovery of the metals by cementation, activated carbon or ion exchange resin. A relatively large portion of the cyanide solution is recirculated back to the cyanidation process to take advantage of the leaching potential for the metals. It is, however, necessary to purge a portion of this loaded solution to avoid the build-up of unwanted metals. Eventually the purge is sent to a tailings pond or other holding area for removal of metals and cyanide prior to discharge. The purge, pond residues and pond supemate have high concentration of free cyanide as well as metallic cyanide complexes, which give them a high degree of toxicity.
Cyanides are harmful for the environment especially in a free,
uncomplexed form. The problems posed by the impact of heavy metals in the environment are well known. Because of the cyanide content and its high concentration of metallic compounds, the purge and holding pond residues can present a potential environmental hazard for the mining industry. It is therefore common to treat these various wastes from ore processing processes in order to remove cyanides and metallic contaminants. As used herein, "cyanide" refers to free cyanide (CN, HCN) and complexed cyanides. Cyanides are determined by standard methods. Cyanide may be present in several forms in waste and is classified according to the difficulty of the digestion step in the calorimetric determination method prescribed by the EPA:
1. Free cyanide CN, HCN;
2. Simple cyanide compounds, including the readily soluble NaCN, KCN, Ca(CN)2, Hg(CN)2, and relatively insoluble, including Zn(CN)2, CuCN, Ni(CN)2 and AgCN;
3. Weak metal-cyanides, including Zn(CN)4, Cd(CN)3 and Cd(CN)4;
4. Moderately strong cyanides, including Cu(CN)2, Cu(CN)3, Ni(CN)4 and Ag(CN)2; and
5. Strong metal-cyanides, such as Fen(CN) 6, Fein(CN) 6, Co(CN) 6, AU(CN)2 and Hg(CN)4.
The metal-cyanide complexes can be characterized in strength by a stability constant in terms of log K, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion (for ferrocyanide for example: K = [(Fe(CN)6)4 ]/ [Fe2+] / [CN-]6) - see TABLE 1 provided in Thomas & Rohrer, Themo Fisher Scientific Inc, Application update 147“Direct Determination of Metal Cyanides by Ion
Chromatography with UV Absorbance Detection” available online at https://assets.thermofisher.com/TFS-Assets/CMD/Application-Notes/AU-l47-
IC-Metal-Cyanides-AU7l360-EN.pdf.
TABLE 1
Figure imgf000005_0001
* n/a : not available
Methods for treating cyanide-containing wastes can be divided into two groups: methods that destroy cyanide by breaking the ion to form simpler, non- hazardous compounds (such as carbon dioxide and nitrogen gas) by an oxidation or electrolytic decomposition, and methods that reduce the volume of cyanide waste by evaporation, reverse osmosis or ion exchange.
Methods for removing cyanide by destruction include reaction with oxidants such as sulfur dioxide, hydrogen peroxide, sodium hypochlorite and chlorine in various forms, such as under alkaline pH conditions (alkaline chlorination) with the addition of sodium hypochlorite, or through the addition of ozone (ozonation) or hydrogen peroxide (peroxidation) at elevated temperature and pressure. The oxidation using hydrogen peroxide (H202) can be slow, taking days in some processes depending on the forms of cyanides present in the effluent being treating. The time necessary for oxidation with H202 can be decreased by using a copper catalyst - see for example U.S. Patent
No. 3617567. These processes involve handling large volumes of chemicals and generally are not effective on wastes that contain complexed cyanides, such as the cyanides present in purges generated by many mining and metallurgic processes. Other techniques available for removing cyanide by destruction include reaction with metal salts such as copper sulfate, ferrous and ferric salts, and the like, singly or in combination. See, for example, U.S. Patent
Nos. 5015396; 4622149; 4851129 and 4312760.
Electrolytic decomposition involves passing an electric current through the cyanide solution to break the cyanide ion. The process is effective in the destruction of free and complexed forms of cyanide. Electrolytic decomposition, however, is a very expensive process because of the large amounts of electrical energy consumed and is applicable only where the cyanide concentrations are at a relatively high level. High capital equipment costs are also associated with the process.
Oxidation is generally the most used in the destruction of cyanides. The process generally is effective in destroying free cyanide and some cyanide complexes. Free cyanide in solution is quite amenable to destruction by oxidation methods. Destruction of complexed forms of cyanide (i.e., "metal- cyanide complexes" or "complexed cyanide") in solution by means of oxidation is highly dependent on the complexing ion associated with the cyanide radical. The relative stability among cyanide complexes varies depending on the complexing ion that is bound to the cyanide radical. It is known that oxidation methods using chlorine or an oxidant like H202 are not effective in destroying these strong metal-cyanides in group 5 identified above.
The detoxification of a water stream comprising free cyanide and metal- cyanide complexes can proceed as follows: oxidizing free cyanide to cyanate, destroying the weak and moderately strong complexes such as those with zinc, copper and silver, precipitating these metals as hydroxides, and precipitating the strong iron(II) cyanide complex as a heavy metal ferrocyanide or iron ferrocyanide.
As an alternative, the detoxification of a water stream comprising free cyanide and iron-cyanide complexes can proceed by removing cyanide from solution and into solid tailings as an iron ferrocyanide precipitate. This can be achieved for example by ferrous sulfate addition. The precipitate that forms in the reaction between excess FeS04 and CN comprises mainly insoluble Prussian blue, Fe4[Fe(CN)6]3. The Prussian blue precipitate is stable over a pH range of 1 to 7, but is unstable in alkaline solution, decomposing rapidly to form Fe(CN6)4 in solution. It forms various insoluble iron oxides, Fe203.n H20 (n = 1-3), at pH values above 7. See M.D. Adams, 1992, Journal of South African Institute of Mining and Metallurgy, vol 92, no. 1, pp. 17-25. In this technique, the addition of FeS04 can generate stable ferrocyanide anions at a pH>7 that can be found in soluble form in an alkaline effluent. Such presence can create issues in ultimate disposal of the effluent as the total cyanide content may exceed the regulation limit even though the free cyanide content may be below its acceptable limit. Moreover stable ferrocyanide anions may pose problems in downstream processes such as ion exchange resin or activated carbon.
For methods for treating metals-containing wastes, numerous industrial processes release liquid or gaseous effluents that are heavily loaded with heavy metals, in particular heavy metal soluble salts, such as cationic form salts. The expression "heavy metals" is understood to mean metals whose density is at least equal to 5 g/cm3, and also beryllium, arsenic, selenium, and antimony, in accordance with the generally accepted definition (Tchounwou, P. B., Yedjou, C. G., Patlolla, A. K., & Sutton, D. J. (2012). Heavy Metals Toxicity and the Environment. EXS, 101 , p. 133-168. http://doi.org/10.1007/978-3-7643-8340- 4_6). Lead or cadmium are particularly significant examples, given their harmful effect on the human body. Nickel is another example thereof due to its allergenic effect.
Hydroxyapatite is an adsorbent which can be used for trapping and immobilizing metals within its structure from contaminated effluents, particularly aqueous effluents. See, for example, WO 2015/173437 by Solvay SA. Hydroxyapatite based adsorption can be used in lieu of ion exchange resins. Cationic species such as zinc, copper, cadmium, and lead are
preferentially trapped over anionic species such as arsenate (As04),
selenite (Se04), or molybdate (Mo04).
In the context of a cyanide-containing water stream from an ore processing plant, while certain metals like cadmium, lead, chromium, zinc in the forms of cations were removed very efficiently with a hydroxyapatite adsorbent, it was observed that certain metals such as cobalt, iron, nickel, and copper present in such water stream were not removed efficiently, even though they are generally well captured by such hydroxyapatite. Even when their removal efficiency is generally very high - well above 90% - when these metals are in the form of cations, it was found that metals in the water stream form metal-cyanide complexes that were not readily captured by this adsorbent with efficiency of less than 50%. Since the adsorption typically takes place at an alkaline pH, it is premised that these adsorption-resilient metal-cyanide complexes are in the form of ions in the water stream. Additionally, the metal-cyanide complexes that were not readily captured by this adsorbent were found to be quite stable and resistant to oxidation methods such as those described above. These metal- cyanide complexes which seem to be less amenable to hydroxyapatite adsorption have a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion.
Without wishing to be bound by this theory, it is thought that because these metal-cyanide ions present in the water stream are negatively charged and are quite stable under alkaline conditions, the hydroxyapatite in the solid adsorbent was much less efficient in capturing these anionic complexes.
Hence the problem posited by the stability of the metal-cyanides complexes and their inability to bind efficiently an hydroxyapatite-containing adsorbent is that the removal of metals from these water stream is rather difficult.
Thus in order to use effectively a metal removal technique using an hydroxyapatite-based adsorbent from a water stream containing cyanides in free and complexed forms, there is a need to first decompose these stable metal- cyanide anions by removing away the cyanide ligands from the complexes and recover metallic ions (central ions in these complexes) that are in a form
(cations) which are far more readily amenable to adsorption by hydroxyapatite.
Heavy metals are not the only priority of the aqueous environment in terms of legislation and environmental impact; regulations also address many organic compounds, such as polycyclic aromatic hydrocarbons (PAHs), phenolic compounds, and pharmaceutical residues. In many industries wastewater such as petrochemical industry, pesticides and insecticides, phenolic compounds posed a big threat to aquatic system due to their toxicity and poor biodegradability.
Petroleum refinery wastewater usually contains high COD due to the presence of polycyclic aromatic hydrocarbons, phenolic compounds and their derivatives.
The United States Environmental Protection Agency and the European Commission have listed PAHs as priority pollutants with the objective of reducing the release of these compounds to the environment. The widespread occurrence of PAHs is largely due to their formation and release in all processes of incomplete combustion of organic materials. PAHs are particularly found in some industrial water originating from heat treatments (such as from incomplete combustion and pyrolysis of fossil fuels or wood and from the release of petroleum products, wet scrubbers or pyrometallurgy process). PAHs are also found in coal tar, crude oil, creosote and roofing tar and a few are used in medicine or to make dyes, plastics, and pesticides. There are thousands of PAH compounds in the environment but in practice PAH analysis is restricted to a few compounds— mostly the 16 priority compounds (Naphthalene, Acenaphthylene, Acenaphthene, Fluorene, Phenanthrene, Anthracene, Fluoranthene, Pyrene, Benz[a]anthracene, Chrysene, Benzo[b] fluoranthene, Benzo[k]fluoranthene, Benzo[a]pyrene, Indeno[l,2,3-cd]pyrene, Dibenzo [a, h] anthracene and
Benzo[ghi]perylene) listed by US EPA as potentially toxic.
Solutions for removal of metals may for example include ion-exchange resins. However these techniques cannot address the removal of organics and therefore organics removal requires one or more additional steps.
There is a need for a process for treatment of water stream containing both metal ions and metal cyanide complexes and optionally also organics which includes using an hydroxyapatite based adsorbent effective on water streams to remove cyanide and metal contaminants and optionally also organic
contaminants. This is also applicable to water purification in general to remove water-soluble metallic ions as well as anionic metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion. The stable metal-cyanide complexes are generally selected from the group consisting of moderately strong metal-cyanide complexes (‘group 4’ provided above) and strong metal-cyanide complexes (‘group 5’ provided above) - see TABLE 1.
Hence, there is still a need to develop a method for treatment of a water stream from the ore mining industry to produce a treated water that is suitable for discharge according to environmental regulations.
Accordingly, it is an object herein to provide methods for treatment of cyanide-containing wastewater, particularly of water stream containing metallic ions and stable metal-cyanide complexes in the form of soluble anions and optionally also organic contaminants (e.g., PAHs, phenolic compounds, naphtol and derivatives).
It is another object herein to provide a method for removal from a water stream, such as a liquid purge/effluent from a mining / metallurgy operation, of metallic ions and stable metal-cyanide complexes in the form of anions, which includes the destruction of metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35 (where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion) and also the removal of metallic ions and optionally also organic contaminants by contact by a solid adsorbent containing apatite.
SUMMARY OF INVENTION
Accordingly, one aspect of the present invention relates to a process for treating a water stream, preferably originating from an ore mining process, containing cyanide, metallic ions and metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, said method comprising:
- irradiating at least a portion of the water stream at a pH greater than 7.0 with ultraviolet light in the presence of a peroxygen at a selected wavelength to form an irradiated effluent, wherein at least one of said metal-cyanide complexes undergoes photo-dissociation and liberates free cyanide from the complex in order for the free cyanide to be converted to cyanate;
- contacting at least a portion of the irradiated effluent with a solid adsorbent comprising apatite to remove from the irradiated effluent at least part of said metallic ions to form a treated effluent; and
- separating the treated effluent from the solid adsorbent.
In the logK, K is the constant for the equilibrium between the metal- cyanide complex and the free metal ion and cyanide ion.
The at least one metal-cyanide complex which undergoes photo dissociation may contain a metal in the complex selected from the group consisting of Fe(II), Fe(III), Co(II), Ni(II), Cu(I), Cu(II), and Hg(II), preferably selected from the group consisting of Fe(II), Fe(III), Co(II), Cu(I), Cu(II), and Ni(II).
The metal-cyanide complex which undergoes photo-dissociation may comprise a complex selected from the group consisting of hexacyanoferrate(II), hexacyanoferrate(III), hexacyanocobaltate(III), tetracyanonickelate(II), tetracyanocuprate(II), and combinations thereof.
In preferred embodiments, the UV irradiation step further generates bicarbonate and nitrogen gas from cyanates formed by the UV peroxidation of the metal-cyanide complexes.
In some embodiments, the process for treating a water stream further comprises carrying out the UV irradiation step in the presence of a peroxygen in an UV irradiation unit which is in fluid circulation with a buffer tank. At least a portion of the irradiated effluent flows to the buffer tank and back to the UV irradiation unit. In some embodiments, the at least a portion of the water stream which is to be irradiated with ultraviolet light in the presence of a peroxygen is first fed to the buffer tank before being fed to the UV irradiation unit.
The UV irradiation step may be carried out in the presence of a peroxygen in a plurality of UV units operated in series, each UV unit comprising a UV lamp.
The process may further comprise carrying out an adsorption step as a pre- treatment prior to the UV irradiation step in order to remove metals, organics and/or color from the at least portion of the water stream prior to being directed to the UV irradiation step. In some preferred embodiments, the adsorption step carried out on the at least portion of the irradiated effluent after the UV irradiation step and the adsorption step carried out as a pre-treatment prior to the UV irradiation step are both performed in a same adsorption unit using the solid adsorbent comprising apatite.
The solid adsorbent preferably comprises a calcium-deficient
hydroxyapatite with a Ca/P ratio more than 1.5 and less than 1.67, preferably wherein the calcium-deficient hydroxyapatite is synthetically made.
The solid adsorbent may comprise a synthetic hydroxyapatite composite, said synthetic hydroxyapatite composite comprising a hydroxyapatite and at least one additive which is present during the hydroxyapatite synthesis. The at least one additive in the synthetic hydroxyapatite composite is embedded or incorporated into or coated onto the hydroxyapatite. The at least one additive preferably comprises at least one activated carbon, iron (such as in the form of metal, salt, oxide, oxyhydroxide, or hydroxide), or combinations thereof.
The solid adsorbent used in an adsorption unit for both pre-treatment prior to the UV/peroxygen step and adsorption after the UV/peroxygen step preferably comprises a synthetic hydroxyapatite and/or a synthetic hydroxyapatite composite with activated carbon as at least one additive.
BRIEF DESCRIPTION OF FIGURES
FIG. 1 is a diagram of a process for treating a water stream, preferably originating from an ore mining process, containing cyanide, metallic ions and metal-cyanide complexes composite, comprising a UV/H2O2 treatment step, an adsorption step and a separation step. FIG. 2 represents another diagram of a process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, comprising a UV/H2O2 treatment step, and separately a combined adsorption / solids separation step.
FIG. 3 represents another diagram of a process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, comprising a UV/H2O2 treatment step combined with an adsorption step (for metals/organics removal) carried out into one combined unit and a separation step (for solids removal).
FIG. 4 represents another diagram of a process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, comprising a UV/H2O2 treatment step in fluid circulation with a buffer tank, an adsorption step (for metals/organics removal) and a separation step (for solids removal).
FIG. 5 represents another diagram of a process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, comprising an adsorption step (pre-treatment for removal of organics, free metals, colored components), a separation step (for solids removal), a UV/H2O2 treatment step in fluid circulation with a buffer tank, wherein at least a portion of the irradiated effluent is sent to the adsorption step (for removal of free metals liberated from cyanide complexes).
DEFINITIONS
“Fresh” adsorbent denotes a material which has not been in contact with contaminants, whereas“spent” adsorbent denotes a material which has already been in contact with contaminants.
As used herein, the terms“% by weight”,“wt%”,“wt. %”,“weight percentage”, or“percentage by weight” are used interchangeably.
As used herein, the term“dry matter” refers to a material which has been subjected to drying at a temperature of l05°C for at least 1 hour.
As used herein, the BET specific surface area is determined by gas adsorption on a Micromeritics ASAP2020 machine. The measurement is carried out using nitrogen as adsorbent gas at 77°K via the volumetric method, according to the ISO 9277: 2010 standard (Determination of the specific surface area of solids by gas adsorption - BET method). The BET specific surface area is calculated in a relative pressure (R/R0) range varying from around 0.05 to 0.20.
In the present specification, the choice of an element from a group of elements also explicitly describes :
- the choice of two or the choice of several elements from the group,
- the choice of an element from a subgroup of elements consisting of the group of elements from which one or more elements have been removed.
In addition, it should be understood that the elements and/or the
characteristics of a composition, a method, a process or a use, described in the present specification, can be combined in all ways possible with the other elements and/or characteristics of the composition, method, process, or use, explicitly or implicitly, this being without departing from the context of the present specification.
In the passages of the present specification that will follow, various embodiments or items of implementation are defined in greater detail. Each embodiment or item of implementation thus defined can be combined with another embodiment or with another item of implementation, this being for each mode or item unless otherwise indicated or clearly incompatible when the range of the same parameter of value is not connected. In particular, any variant indicated as being preferred or advantageous can be combined with another variant or with the other variants indicated as being preferred or advantageous.
In the present specification, the description of a range of values for a variable, defined by a bottom limit, or a top limit, or by a bottom limit and a top limit, also comprises the embodiments in which the variable is chosen, respectively, within the value range : excluding the bottom limit, or excluding the top limit, or excluding the bottom limit and the top limit.
In the present specification, the description of several successive ranges of values for the same variable also comprises the description of embodiments where the variable is chosen in any other intermediate range included in the successive ranges. Thus, for example, when it is indicated that "the magnitude X is generally at least 10, advantageously at least 15", the present description also describes the embodiment where : "the magnitude X is at least 11", or also the embodiment where : "the magnitude X is at least 13.74", etc.; 11 or 13.74 being values included between 10 and 15.
The term "comprising" includes "consisting essentially of' and also "consisting of'. In the present specification, the use of "a" in the singular also comprises the plural ("some"), and vice versa, unless the context clearly indicates the contrary. By way of example, "a mineral" denotes one mineral or more than one mineral.
If the term "approximately" or“about” is used before a quantitative value, this corresponds to a variation of ± 10 % of the nominal quantitative value, unless otherwise indicated.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
One embodiment according to the present invention relates to a process for treating a water stream, preferably originating from an ore processing or metallurgy process, containing cyanide, metallic ions and stable metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion. The water stream may further comprise organics and/or colored species.
Such process for treating such water stream includes two main steps:
UV peroxidation: irradiation of the water stream with ultraviolet light in the presence of a peroxygen to form an irradiated effluent, and Adsorption: contacting the irradiated effluent with a solid adsorbent comprising apatite to form a treated effluent.
The UV peroxidation may be also called“UV/peroxygen step” or“UV irradiation with a source of peroxygen” and can be used interchangeably.
When the peroxygen comprises H202, the first step may be termed for simplification“ UV/H202 treatment or step”.
The water stream to be subjected to this process may comprise the following metallic contaminants: Al, Ag, Ba, Be, Ce, Co, Cd, Cu, Cr, Fe, Hg, La, Li, Mn, Mg, Mo, Ni, Pb, Pd, Rb, Sb, Sn, Sr, Th, Ti, U, V, Y, Zn and/or non- metallic contaminants such as As, B, F, Se, preferably selected from the group consisting of barium, cadmium, cobalt, copper, iron, magnesium, manganese, nickel, selenium, zinc, and combinations thereof. Of particular interest in this process are the metallic contaminants selected from the group consisting of Cu, Fe, Ni, and Co.
Typical content ranges for these metallic species in the water stream to be subjected to this process may be as follows:
Cu : up to 10 mg/liter, Fe : up to 60 mg/liter,
- Ni : up to 4 mg/liter,
Co : up to 3 mg/liter.
The water stream to be subjected to this process also comprises cyanides, in the form of free cyanides and complexed cyanides.
Typical content ranges for these cyanides species in the water stream to be subjected to this process may be as follows:
- total cyanides : up to 60 mg/liter,
free cyanides: up to 10 mg/liter.
Such process for treating the water stream generally includes a separation step to remove solids (such as precipitated material and spent adsorbent) from the treated effluent.
The separation of the treated effluent preferably includes settling.
The separating may include adding a flocculant to the treated effluent before or during settling.
PEROXIDATION STEP WITH UV IRRADIATION
The first step in the present invention relates to the use of UV irradiation in the presence of a peroxygen for removing from a water stream at least a portion of cyanide contaminants, preferably stable metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion. This step may be referred to as“UV/peroxygen step” or“UV peroxidation step”. When the peroxygen comprises H202, this step may be referred to as“UV/H202 treatment” or“UV/H202 step”.
The stable metal-cyanide complexes are generally selected from the group consisting of moderately strong metal-cyanide complexes (‘group 4’ provided above) and strong metal-cyanide complexes (‘group 5’ provided above). The stable metal-cyanide complexes are generally selected from the group consisting of [Co(CN)6f ,[Fe(CN)6f , [Hg(CN)4f, [Fe(CN)6]4 , [Fe(CN)6]4 , [Ni(CN)4f , [CU(CN)4]3~ , [CU(CN)3]3 , and combinations thereof.
The first step in the present invention comprises irradiating the water stream at a alkaline pH greater than 7, preferably greater than 8.0, with ultraviolet light in the presence of a peroxygen at a selected wavelength to form an irradiated effluent, wherein at least one of said metal-cyanide complexes undergoes photo-dissociation and liberates free cyanide from the complex in order for the free cyanide to be converted to cyanate and for the metal from the complex to be converted to an hydroxide form.
The at least one metal-cyanide complex which undergoes photo- dissociation during the UV irradiation step with the peroxygen contains a metal in the complex selected from the group consisting of Fe(II), Fe(III), Co(II), Ni(II), Cu(I), Cu(II), and Hg(II), preferably selected from the group consisting of Fe(II), Fe(III), Co(II), Cu(II), and Ni(II).
The metal-cyanide complex which undergoes photo-dissociation during the UV irradiation step with the peroxygen may include a complex selected from the group consisting of [Co(CN)6]3 ,[Fe(CN)6]3 , [Fe(CN)6]4 , [Fe(CN)6]4 ,
[Ni(CN)4]2 , [Cu(CN)4]3 , [CU(CN)3]2 , and combinations thereof; preferably selected from the group consisting of hexacyanoferrate(II),
hexacyanoferrate(III), hexacyanocobaltate(III), tetracyanocuprate(II), tetracyanonickelate(II), and combinations thereof
The pH during the irradiation step is greater than 7, or > 7 and up to 11, preferably from 8 to 11, more preferably from 8.5 to 10.5, yet more preferably from 9 to 10.5, even more preferably from 9.5 to 10.5, yet even more preferably from 10 to 10.5.
The pH is generally selected so that no or little HCN gas is liberated from the water stream that is irradiated. For that reason, it may be preferable to select a pH equal to or greater amount of 8.5, preferably at least 9.
If the water stream to be treated is not at a pH within the preferred pH range for the irradiation step (that is to say too acidic for the avoidance of HCN volatilisation, and preferably at a pH less than 8.5), an optional alkali may be added to increase the pH. Suitable alkali may include NaOH, KOH, Ca(OH)2 and/or a carbonate solution.
The irradiation with ultraviolet light is carried out for at least 4 minutes, or at least 5 minutes, and/or at most 120 min, or at most 90 min, or at most 75 min, or at most 60 min.
During irradiation, the ultraviolet light has a wavelength in the region from 200 to 375 nm, preferably from 200 to 350 nm, more preferably from 200 to 300 nm, for the stable metal-cyanide complexes to undergo photo-disassociation and for the peroxygen to form hydroxyl radicals.
The ultraviolet lamp preferably emits UV-C light.
The irradiation with ultraviolet light is carried out with a Hg lamp with a minimum electric rating of 8 W. The term“pressure” is referred to the mercury pressure present in the lamps. Low-pressure lamps operate with mercury vapor pressure ranging from about 100 to 1000 Pa; a buffer gas supplements the mercury vapor. Medium-pressure lamps operate with mercury vapor pressure of approximately 10 kPa, which enables this type of lamp to reach electrical power levels 100 times higher than low-pressure lamps, i.e. several tens of W/cm. Low and high pressure lamps are monochromatic (254 nm) and medium pressure lamps are polychromatic. For a low pressure (LP) Hg lamp, the electric rating may be from 8 W to 100 W. Suitable Hg lamps include standard output LP Hg lamps - popularly used UV lamp, whose electric rating is typically 25W, 50W,
65 W, or 95 W; high output LP Hg lamps, whose electric rating is typically 200W, 250W, or 400 W; or ultra high output LP class lamps, whose electric rating is typically 400W.
In particular embodiments, the UV lamp (preferably a Hg lamp) may have a power of at least 55W, preferably of at least 95W.
The selection of the wavelength to use for the UV/H2O2 treatment with the Hg lamp should be done to favor decomposition of H2O2 into hydroxyl radical OH' and for the cyanide complexes to be photo-dissociated.
In preferred embodiments, the UV irradiation step with peroxygen may comprise passing water stream through a plurality of UV units, each comprising a UV lamp, preferably a Hg lamp. The plurality of UV units for the UV irradiation step with peroxygen may comprise at least 2, preferably at least 3 UV units, and/or at most 15, preferably at most 12, more preferably at most 10 UV units. The UV units are preferably sized the same so as to accommodate the same incoming flow rate of water to be treated. The plurality of UV units preferably comprises the same type of UV lamp, preferably the same type of Hg lamp, but not necessarily.
In such instance, the peroxygen source is split to feed the plurality of UV units.
The plurality of UV units may be operated in parallel, that is to say, wherein a water stream feeding the UV/peroxygen step is split into several feedstreams to feed the plurality of the UV units.
In preferred embodiments however, the plurality of UV units may be operated in series, that is to say, wherein the irradiated water effluent exiting a UV unit is sent to a subsequent UV unit to get another round of UV treatment. In this manner, the water stream being fed to the UV/peroxygen step is subjected several times to UV irradiation in the presence of peroxygen. The UV irradiation step with peroxygen may further form particles of metal hydroxides under alkaline condition with the metal liberated from said metal-cyanide complex. The process may further include removing said particles of metal hydroxides from the treated effluent in the separation where the solid adsorbent is separated or removing said particles of metal hydroxides from the irradiated effluent before the contacting step with the solid adsorbent.
The conditions for the UV irradiation step with peroxygen include a temperature from 0°C to about 60°C, preferably from 0°C to about 40°C, more preferably from l5°C to about 25°C. The conditions for the adsorption step still more preferably include ambient temperature and atmospheric pressure of the location where the process is operated.
In preferred embodiments, the peroxygen used during the UV irradiation step comprises or consists of H202.
H202 may be in the form of a concentrated H202 aqueous solution, such as >20 up to 30 wt% H202, preferably about 30 wt% H202, or a diluted solution comprising from 1 wt% to 20 wt% H202.
H202 is used in a H202:CN molar ratio of at least 2:1, preferably at least 5:1, more preferably at least 10:1, compared to total cyanide content in the effluent, that is to say, the cyanide which is free and which can be liberated from all metal-cyanide complexes during UV peroxidation. For example, if the water stream contains weak metal-cyanide complexes (such as those belonging to ‘group 3’), the cyanide ligand that would be liberated from these weak complexes also need to be taken into account when estimating the amount of H202 to add to use the H202:CN ratio equal to or greater than the minimum H202:CN molar ratio. One can measure the total amount of cyanide in an effluent sample to do this estimation of how much H202 to add for this UV peroxidation. The amount of H202 should be sufficient to transform all cyanides (free and liberated ligands) to cyanate and also to oxidize cyanate to N2 and C02.
The total quantity of H202 may be added to the UV/H202 treatment at once to satisfy the desired H202:CN molar ratio, or H202:CN may be added in two or more portions after several time intervals, such as time 0, time=l5 min and times =30 min, or may be added continuously or continually to the UV/H202 treatment until the total quantity of H202 (necessary to transform all cyanides -free and liberated ligands- to cyanate and also to oxidize cyanate to N2 and C02) is delivered to the UV/H202 treatment. The H2O2 may be injected periodically into a circulation loop hydraulically connected to a photoreactor where the irradiation takes place or to a tank in such a circulation loop in order for the H2O2 content in the water stream to be treated to be from 10 to 1,000 ppm, preferably from 25 to 750 ppm, preferably from 40 to 500 ppm, yet more preferably from 50 to 400 ppm, most preferably from 100 to 400 ppm.
When the peroxygen used during the irradiation step comprises or consists of H2O2, the H2O2 content in the water stream to be treated may be from 10 to 1,000 ppm, preferably from 25 to 750 ppm, preferably from 40 to 500 ppm, yet more preferably from 50 to 400 ppm, most preferably from 100 to 400 ppm.
In preferred embodiments when the peroxygen used during the irradiation step comprises or consists of H2O2, the H2O2 content in the water stream to be treated may be at least 100 ppm.
Under the alkaline condition and the above-mentioned fUCUCN molar ratio, at least one of said metal-cyanide complexes undergoes photo-dissociation and liberates free cyanide ligands from the complex. The removal of a first ligand CN from the complex is the most difficult step in this reaction, and once the first ligand CN is removed from the stable metal-cyanide complex, it becomes much easier to remove the remaining CN ligands. As an example, the UV irradiation of the hexaferrocyanate proceeds as follows:
Fe(CN)6 3 + H2O [Fe(CN)5H20]2 + CN (i)
[Fe(CN)5H20]2- + 2H2O Fe(OH)3(s) + 5CN + 3H+(ii)
hv
H2O2
Figure imgf000019_0001
20H ' (iii)
The UV irradiation step further includes formation - see reaction (iv) - of cyanate from cyanide (free and liberated ligand from metal-cyanide complexes) and also further conversion of the cyanate to bicarbonate and nitrogen gas - see reaction (v), according to the following reactions (iv) and (v):
Figure imgf000019_0003
The cyanate can also be hydrolysed to carbonate anion and ammonium cation - see reaction (vi):
Figure imgf000019_0002
Care must be given to avoiding an excess of H202 during the UV irradiation, as there is a risk of generating extra hydroxyl radicals which then can react with cyanate (CNO ) to generate nitrate and nitrite, according to the following reactions (vii) and (viii):
(vii)
Figure imgf000020_0001
(viii)
The formation of nitrate and nitrite in the irradiated effluent potentially add other compounds which may have to be removed from the water effluent before being discharged. The formation of nitrogen gas from cyanate is therefore preferred, as N2 gas can be readily liberated from a UV/H202 treatment unit where the UV peroxidation takes place.
Thus in preferred embodiments, the UV irradiation step further generates bicarbonate and nitrogen gas (as indicated by reaction (v)) from cyanates which are formed (as indicated by reaction (iv)) by the UV peroxidation of the metal- cyanide complexes.
Additonally in preferred embodiments, the present process further does not include, during or after the UV/peroxygen step, the use of a catalyst which is a metal chelate. For example, the present process preferably does not use a phthalocyanine compound (e.g., phthalocyanine of cobalt, vanadium, nickel, or iron, or a sulfonated cobalt phthalocyanine dispersed on carbon, or a water- soluble polysulfonated cobalt phthalocyanine).
The process may further comprise reducing the pH of the irradiated effluent with an acid, preferably a mineral acid such as sulfuric acid or hydrochloric acid, before contacting with the solid adsorbent. Since the irradiation step is preferably carried out at a pH of 9 up to 11, the pH may be reduced to a value from 7 to 9, preferably a pH from 7 to 8.8, more preferably a pH from 7.5 to 8.8, yet more preferably a pH from 7.5 to 8.5.
PEROXIDATION STEP WITH UV IRRADIATION IN FLUID CIRCULATION WITH A BUFFER TANK
In an optional embodiment, the process may further comprise circulation of at least a portion of the irradiated effluent to flow from the UV/peroxygen step to a buffer tank and flow from the buffer tank back to the UV/peroxygen step. One of the advantage of the use of the buffer tank in this process’ embodiment is to permit to hold a large volume of water in that tank for the UV peroxidation, thereby increasing the residence time of the water subjected to this UV peroxidation step. Since the reaction with the peroxygen typically requires more time for completion than the photo-dissociation of metal-cyanide complexes as well as of free cyanides, passing at least a portion of the irradiated effluent back and forth through the buffer tank allows for extra time for the peroxidation to take place in the buffer tank and further permits repetitive exposure of the water stream to ultraviolet light.
The residence time in the buffer tank may be at least 15 minutes, or at least 30 minutes, or at least 45 minutes, or at least 60 minutes and/or at most
180 minutes, or at most 150 minutes, or at most 120 minutes.
The buffer tank may comprise at least one mixed tank in which a stirrer containing one or more impellers stirs its content or at least one tank where its content is recirculated for example by an internal or external pump.
In such embodiment, because at least a portion of the irradiated effluent circulates via the buffer tank and gets repetitive exposure to UV, this provides an advantage in the process of requiring less numbers of UV units in the
UV/peroxygen step. The use of the buffer tank circulating at least a portion of the irradiated effluent from and to the UV/peroxygen step thus allows for a lower capital expenditure for the process.
For example, when the process is operated without a buffer tank, the UV/peroxygen step may require 8 to 10 UV units, while in contrast when the process is operated with a buffer tank, the UV/peroxygen step may require 3 to 5 UV units.
CONTACTING STEP WITH A SOLID APATITIC ADSORBENT
The second step in the present invention relates to the use of the solid adsorbent comprising apatite, preferably a synthetic hydroxyapatite, for removing at least a portion of one or more contaminants, for example in the form of metals, non-metals, their ions, and/or organics from at least a portion of the water stream, either before UV peroxidation and preferably after UV
peroxidation.
Contacting at least a portion of the irradiated effluent with a solid adsorbent comprising apatite is preferably effective in removing simultaneously a large variety of contaminants such as organics (e.g., PAHs, phenolic compounds, naphtol and derivatives), color, and/or inorganics such as metals and non-metals from a contaminated water stream. The organic contaminants may be dissolved and/or suspended, and the metal and non-metal contaminants may be in cationic and anionic forms. For simplicity sake, this contacting step for metal and optionally organics removal may be termed as“adsorption step”.
Contacting the water stream with the solid adsorbent comprising apatite is preferably effective in removing at least part of metallic ions containing a metal such as: Al, Ag, Ba, Be, Ce, Co, Cd, Cu, Cr, Fe, Hg, La, Li, Mn, Mg, Mo, Ni,
Pb, Pd, Rb, Sb, Sn, Sr, Th, Ti, U, V, Y, Zn and/or non-metallic elements such as As, B, F, Se, preferably selected from the group consisting of barium, cadmium, cobalt, copper, iron, magnesium, manganese, nickel, selenium, zinc, and combinations thereof, more preferably selected from the group consisting of cobalt, copper, iron, nickel, and combinations thereof
The contacting step with the solid adsorbent comprising apatite may be carried out at a pH of at least 6.5, or at least 7, or at least 7.5, and/or at most 10, or at most 9.5, or at most 9, or at most 8.8, or at most 8.5.
The contacting step with the solid adsorbent comprising apatite is preferably carried out at a pH from 7 to 9, preferably a pH from 7 to 8.8, more preferably a pH from 7.5 to 8.8, yet more preferably a pH from 7.5 to 8.5.
The contacting step is carried out for at least 5 minutes, or at least 10 minutes, and/or less than 120 min, or less than 60 min, or less than 30 min.
The conditions for the adsorption step include a temperature from 0°C to about 60°C, preferably from 0°C to about 40°C, more preferably from l5°C to about 25°C. The conditions for the adsorption step more preferably include ambient temperature and atmospheric pressure of the location where the process is operated.
The contacting step with the solid adsorbent and the UV irradiation step with peroxygen may be carried out in different units, alternatively these two steps may be carried out in a same unit, such as a mixed tank or a tank where the water stream is recirculated for example by an internal or external pump.
The contacting with the solid adsorbent may be carried out in a mixed tank or a tank where its content is recirculated for example by an internal or external pump, and in such case, the solid adsorbent is in the forms of particles which are suspended in water in the tank.
The contacting with the solid adsorbent and the separation step may be carried out in a same unit, preferably wherein the unit is a settler and wherein the solid adsorbent is added to the settler in a zone to allow contact with the irradiated effluent to remove some organics and metallic contaminants and for the solid adsorbent to settle after contact. In the purification or removal process according to the invention, the contaminated water stream may be an irradiated water effluent containing metallic contaminants, such as: Al, Ag, Ba, Be, Ce, Co, Cd, Cu, Cr, Fe, Hg, La, Li, Mn, Mg, Mo, Ni, Pb, Pd, Rb, Sb, Sn, Sr, Th, Ti, U, V, Y, Zn and/or non- metallic elements such as As, B, F, Se, whether these elements may be in the form of cations and/or anions, such as oxyanions, and optionally colored and/or organic contaminants (e.g., PAHs, phenolic compounds, naphtol and
derivatives), according to which the solid adsorbent comprising hydroxyapatite (preferably in suspension form) is mixed into the water stream (preferably wherein a portion of which has been irradiated) for a sufficient time so that the hydroxyapatite adsorbs at least a portion of the contaminants. The so-formed mixture is preferably subjected to a separation (such as settling and/or clarification) in order to produce a treated water which is partially purified of organic, colored, metallic and/or non-metallic contaminants and a spent solid adsorbent loaded with organic, colored, metallic and/or non-metallic
contaminants that is then removed from the treated effluent.
In the contacting step, the solid adsorbent may be used with the water stream, wherein a portion of which has been irradiated, in a contact reactor, such as a sludge blanket reactor or a fluidized bed. The contact time between the solid adsorbent and the irradiated water effluent is in general at least one minute, advantageously at least 15 minutes, more advantageously at least 30 minutes, even more advantageously at least one hour.
The solid adsorbent which is suitable to be used for the adsorption step is described in more detail below.
In one particularly advantageous embodiment of the invention, the water stream, wherein a portion of which has been irradiated, may be introduced into a sludge blanket contact reactor in which the solid adsorbent is present at a weight concentration from at least 0.5% by weight to in general at most 10% by weight, preferably from 1 to 10 wt%, more preferably from 2 to 5 wt%; a liquid is recovered as overflow from the sludge blanket reactor; a flocculant is added to the recovered liquid in order to form a mixture comprising particles of the solid adsorbent entrained out of the contact reactor and flocculated; said mixture is then introduced into a settling tank where the mixture is separated into:
- the treated water partially purified of organic, metallic elements and/or of non- metallic elements, and said treated water is recovered as overflow from the settling tank, - and into an underflow from the settling tank comprising flocculated and settled particles of solid adsorbent recovered as underflow from the settling tank; and at least one portion of the underflow from the settling tank containing flocculated and settled particles of adsorbent is recycled to the sludge blanket contact reactor. The effectiveness of the treatment of organics, metallic elements and/or non-metallic elements may be monitored by comparing the concentrations of the elements upstream (in the water stream) and downstream of the treatment (in the partially purified liquid), for example by an automatic analyser or by sampling and analysis. The solid adsorbent charge of the contact reactor is in general regularly renewed in portions. For example, by partial purging of the spent solid adsorbent loaded with organics, metallic and/or non-metallic elements at the underflow from the settling tank, and by adding fresh solid adsorbent to the contact reactor. Such a process thus ensures a "chemical polishing" of the water effluent. The process is particularly advantageous in the case where the treated water partially purified of organics, colored species, metallic and/or non-metallic elements is then treated in a biological treatment plant producing sewage sludges. This makes it possible to reduce the
concentrations of such elements of said sewage sludges and to reutilize them, for example in agriculture or in land development.
OPTIONAL ADSORPTION PRE-TREATMENT PRIOR TO UV
PEROXIDATION STEP
According to some optional embodiment, the process may further comprise an adsorption pre-treatment of the water stream prior to being directed to the UV/peroxygen step.
The various embodiments described in the context of the contacting step with the solid adsorbent comprising apatite are equally applicable to this embodiment for the optional adsorption pre-treatment.
Preferably in this embodiment of the process, the solid adsorbent used in the adsorption pre-treatment is suitable for removing color. Color in the water stream may originate for example from iron species, and may be a yellowish to light brownish color. It is believed that the presence of color in the water stream to be treated may indeed hinder the performance of the UV light in the
UV/peroxygen step. Hence removing some of the color from the water stream prior to the UV/peroxygen step may be beneficial to maximize the use of the UV light for the photo-disassociation of the metal-cyanide complexes and it would minimize the possible interaction / reaction with UV of the colored species present in the water stream.
To estimate color removal, a spectrophotometric analysis can generate an absorbance spectrum of the water stream sample to be pre-treated to find out a peak or peaks at particular wavelength(s) which is/are representative of the colored species to be removed. The absorbance at the selected wavelength(s) can be measured on unfiltered samples of water streams with a spectrophotometer using a 1 cm path length quartz cell. For example a wavelength may be selected in the range of 565-590 nm to monitor the removal of yellow-colored species, or a wavelength may be selected in the range of 590-625 nm to monitor the removal of orange-colored species. In all instances, the data collected represents apparent color. The percent color reduction of the pre-treated samples (after being subjected to the adsorption) are compared to the time-zero samples (before adsorption).
Preferably in this embodiment of the process, in addition to removing color from the water stream, the solid adsorbent used in the adsorption pre-treatment is further suitable for removing at least a portion of organics and/or free metallic species such as metallic ions, in particular free species of arsenic, selenium, heavy metals, e.g., iron, copper, cobalt, and/or nickel. Indeed, the water stream generally contains free metallic species such as metallic ions that are not complexed with cyanide and/or organics.
In preferred embodiment, the adsorption pre-treatment prior to
UV/peroxygen step and the adsorption step with the solid adsorption carried out on at least a portion of the irradiated effluent after the UV/peroxygen step are performed in a same adsorption unit in which one or more solid adsorbents comprising apatite can be used.
Therefore a unit for adsorption can be used prior to and after UV peroxidation step and to this unit is added a solid adsorbent comprising apatite as described herein in the description.
A particular preferred solid adsorbent used in this particular adsorption pre-treatment comprises a synthetic hydroxyapatite and/or a synthetic
hydroxyapatite composite with activated carbon. The synthetic hydroxyapatite composite with activated carbon is particularly preferred for removal of free (not-complexed) heavy metals, at least a portion of organics and/or colored species. The solid adsorbent, particularly the solid adsorbent comprising a hydroxyapatite composite, which is suitable to be used for adsorption pre- treatment is described in more detail below.
SOLID ADSORBENT COMPRISING APATITE
The second step in the present invention relates to the use of a solid adsorbent comprising apatite, preferably an hydroxyapatite, for removing at least a portion of one or more contaminants, for example in the form of organics, metallic and/or non-metallic ions from the irradiated water effluent.
The term "apatite" denotes a family of mineral compounds, the chemical formula of which can be written in the following general form:
Meio(X04)6Y2
In this formula, Me generally represents a divalent cation (Me2+), X04 a trivalent anionic group (X04 3 ) and Y a monovalent anion (Y ).
Calcium phosphate hydroxyapatite Caio (P04)6(0H)2 crystallizes in the space group of the hexagonal system. This structure consists of a close-packed quasi-hexagonal stack of X04 groups, forming two types of parallel tunnels.
The existence of these tunnels gives apatites chemical properties akin to those of zeolites. Vacancies may also be created either by the departure of anions and cations, or by the presence of cations or anions of different valency. Apatites therefore appear to be particularly stable structures which may tolerate large gaps in their composition.
Hydroxyapatite should not be confused with tricalcium phosphate (TCP), which has a similar weight composition : Ca3(P04)2. The Ca/P molar ratio of TCP is 1.5 whereas the Ca/P molar ratio is 1.67 for hydroxyapatite. Industrial apatites sold as food additives or mineral fillers are, as a general rule, variable mixtures of TCP and hydroxyapatite.
Other salts of calcium and phosphate, including TCP, do not have the same properties as hydroxyapatite. Although TCP can also react with heavy metals, hydroxyapatite is more advantageous as it can enclose metals in the form of an insoluble, and therefore relatively inert, matrix.
The solid adsorbent may have a particularly high BET specific surface area (at least 110 m2/g) and/or a particularly high pore volume (at least 0.3 cm3/g) measured after heat treatment of the solid adsorbent at l05°C.
Such solid adsorbent particles are composed on their surface of plate-like crystallites, of thickness of a few nano-meters (nm). Particles of solid adsorbent may be covered with plate-like crystallites, having a thickness of at most 25 nm, preferably of at most 20 nm, more preferably of at most 10 nm. The thickness of plate-like crystallites may be at least 1 nm, preferably at least 2 nm, more preferably at least 4 nm.
The solid adsorbent used in the present invention may further have a remarkably low solubility of the phosphates contained in the solid adsorbent particles.
The adsorbent preferably comprises solid particles with a mean
diameter D50 of which is greater than 10 pm, in general greater than 20 pm, or even greater than 25 pm, or even at least 30 pm, or even at least 35 pm, and/or preferably less than 200 pm, or even less than 150 pm, or even less than 100 pm. In some preferred embodiments, the adsorbent comprises solid particles with a mean diameter D50 from 20 microns to 60 microns, or from 25 microns to 60 microns, or from 30 microns to 60 microns. The mean diameter in question is the D50, that is to say the diameter such that 50 % by weight of the particles have a diameter less than said value.
The mean particles size D50 is the diameter such that 50 % by weight of the particles have a diameter less than said value. The particle size
measurement may be measured using laser diffraction, such as using a
Beckman Coulter LS 230 laser diffraction particle size analyser (laser of wavelength 750 nm) on particles suspended in water and using a size distribution calculation based on Fraunhofer diffraction theory (particles greater than 10 pm) and on Mie scattering theory (particles less than 10 pm), the particles being considered to be spherical.
In preferred embodiments, the solid adsorbent is inorganic.
In other embodiments, the solid adsorbent contains less than 1 wt% organics.
Solid adsorbent comprising a hydroxyapatite
The solid adsorbent comprising apatite preferably comprises an
hydroxyapatite, preferably a hydroxyapatite which is synthetically made.
Suitable hydroxyapatite includes a calcium-deficient hydroxyapatite with a Ca/P ratio more than 1.5 and less than 1.67, preferably with a Ca/P molar ratio more than 1.54 and less than 1.65. The calcium-deficient hydroxyapatite is generally in crystalline form or in vitreous form.
The solid adsorbent comprises at least 60 wt % of a calcium-deficient hydroxyapatite. The solid adsorbent may comprise at least 65 wt%, preferably at least 70 wt%, more preferably at least 75 wt%, yet more preferably at least 80 wt%, yet most preferably at least 85 wt%, of the calcium-deficient hydroxyapatite, and/or
- at most 99 wt%, preferably at most 98 wt%, more preferably at most 97 wt%, yet more preferably at most 95 wt%, even more preferably at most 93 wt%, most preferably at most 91 wt% of the calcium-deficient hydroxyapatite.
In preferred embodiments, the solid adsorbent may further include one or more additional components different from the calcium-deficient hydroxyapatite.
Calcium may be and is preferably present in another form (other than the calcium-deficient hydroxyapatite) in the solid adsorbent. Calcium carbonate is generally present in the solid adsorbent. The weight ratio of the calcium-deficient hydroxyapatite to calcium carbonate is generally equal to or greater than 3, preferably equal to or greater than 4, more preferably equal to or greater than 5, yet more preferably greater than 7, most preferably equal to or greater than 9.
Generally, because of that other form of Ca in the solid adsorbent, the solid adsorbent generally has a higher Ca/P molar ratio than the calcium-deficient hydroxyapatite present in the solid adsorbent. For that reason, even though the calcium-deficient hydroxyapatite in the solid adsorbent may have a Ca/P molar ratio less than 1.67, the entire solid adsorbent may have a Ca/P molar ratio equal to or more than 1.67. In preferred embodiments, the calcium-deficient hydroxyapatite in the solid adsorbent may have a Ca/P molar ratio of about 1.55-1.59, while the solid adsorbent may have a Ca/P molar ratio of about 1.60-1.67.
In preferred embodiments, the solid adsorbent may further comprise calcium carbonate in an amount of less than 20 wt% and more than 0 wt%, preferably from 1 wt% to 19 wt%, more preferably from 2 wt% to 18 wt%, even more preferably from 5 wt% to 15 wt%, yet even more preferably from 7 wt% to 13 wt%, most preferably from 8 wt% to 12 wt%.
The solid adsorbent may further comprise less than 1 wt% of calcium dihydroxide Ca(OH)2, preferably less than 0.5 wt% calcium dihydroxide
Ca(OH)2, more preferably less than 0.3 wt% calcium dihydroxide Ca(OH)2, even more preferably less than 0.2 wt% calcium dihydroxide Ca(OH)2, most preferably being substantially free of calcium dihydroxide Ca(OH)2. The solid adsorbent may further comprise water in an amount of less than 20 wt% and more than 0 wt%, preferably from 1 wt% to 18 wt%, more preferably from 2 wt% to 15 wt%, even more preferably from 4 wt% to 12 wt%, yet even more preferably from 5 wt% to 11 wt% most preferably from 6 wt% to 11 wt%.
In preferred embodiments, the solid adsorbent comprises at least 60 wt% of a calcium-deficient hydroxyapatite with a Ca/P ratio more than 1.5 and less than 1.67; calcium carbonate in an amount between 0.5 to 20 wt% and/or contains less than 1 wt% Ca(OH)2.
In some preferred embodiments, the solid adsorbent is substantially free of carbon, i.e., less than 0.5 wt% of carbon.
In some other embodiments, the solid adsorbent may comprise carbon for example in an amount of at least 0.5 wt% carbon but in an amount of less than 7 wt% carbon, preferably less than 6 wt% carbon, more preferably less than 5 wt% carbon or less than 4 wt% carbon.
Solid adsorbent comprising a hydroxyapatite composite
A hydroxyapatite composite can be effective in trapping simultaneously a large variety of contaminants such as organics (e.g., PAHs, phenolic compounds, naphtol and derivatives) and/or inorganics such as metals and non- metals from a contaminated water stream. The organic contaminants may be dissolved and/or suspended, and the metal and non-metal contaminants may be in cationic and anionic forms.
To enhance the sorption of the hydroxyapatite towards a larger spectrum of contaminants, it has been found that the hydroxyapatite structure can be supplemented or modified by incorporating at least one additive during the synthesis of the hydroxyapatite to yield a hydroxyapatite composite with an improved adsorption affinity and/or efficiency with respect to at least one contaminant, such adsorption affinity and/or efficiency being greater than that of ae hydroxyapatite structure not containing the activated carbon.
Depending on the physical (size) and chemical forms (treated or not) of the additive which is present during the synthesis of the hydroxyapatite structure (e.g., added prior to the hydroxyapatite synthesis or to a vessel where the hydroxyapatite synthesis takes place), the additive in the hydroxyapatite composite may be embedded or incorporated into or coated onto the
hydroxyapatite structure, or otherwise associated with the hydroxyapatite structure via cohesive forces. Regardless on how the additive is included in the resulting composite, its presence during the hydroxyapatite synthesis results in forming the hydroxyapatite composite.
The hydroxyapatite composite is different than a mere physical mixture of a hydroxyapatite and the additive, which in this case would be made after each material (hydroxyapatite and the additive) would be formed separately and then mixed or blended.
One advantage of embedding or incorporating the additive into the hydroxyapatite during its synthesis is to provide a much more stable material (compared to a mere physical mixture of a hydroxyapatite and the additive) which does not release the additive when in use, particularly in an aqueous solution when the hydroxyapatite composite is intended to perform as adsorbent for removal of contaminants from water.
In preferred embodiments, the additive in the hydroxyapatite composite is a co-sorbent.
The additive is preferably selected based on its own particular affinity and/or efficacy to adsorb or trap at least one contaminant that the hydroxyapatite structure (without additive) does not adsorb or weakly adsorbs. The contaminant may be in the form of organics (e.g., PAHs, phenolic compounds, naphtol and derivatives) and/or inorganics such as a metal or a non-metal in the form of a cation or an oxyanion. For example, the additive may be selected based on its own particular affinity and/or efficacy to adsorb organics (e.g., PAHs, phenolic compounds, naphtol and derivatives) or mercury such as in the form of mercury cation, selenium such as in the form of its oxyanions (selenate and/or selenite), arsenic such as in the form of its oxyanions (H2As04 /HAs04 2 ) and uncharged H3ASO3 form of As(III), and/or boron such in the form of borate.
The additive may be further selected based on its ability to increase the porosity of the hydroxyapatite structure. For example, it is preferred that the pore volume and/or the BET surface area of the resulting hydroxyapatite composite synthesized with the additive is higher than that of the hydroxyapatite structure synthesized without the additive.
One advantage of the present invention is improving the sorption affinity of the hydroxyapatite composite for at least one contaminant that would otherwise not be adsorbed or poorly adsorbed from a contaminated effluent by a hydroxyapatite synthesized without the additive. The at least one contaminant may be an organic compound, or a metal or non-metal in the form of a cation or an oxyanion. Another advantage of a hydroxyapatite composite is improving the sorption capacity of the hydroxyapatite composite, for example by increasing its pore volume and/or BET surface area.
When the additive can be used as a co-sorbent in powder form for water treatment, the inclusion of the additive powder as co-sorbent in the
hydroxyapatite composite provides yet another advantage. While the use of a co-sorbent in a loose powder offers large surface area and high adsorption capacity, a loose powder needs specific and costly equipment to be removed from treated water streams, and solid/liquid separation problems limit reactor configurations that require incorporating large sedimentation basins or filtration. There is therefore a benefit for a powdered co-sorbent to be incorporated into the hydroxyapatite structure to form the composite, so it can be used in practical adsorption processes. The hydroxyapatite synthesis which comprises the presence of the additive powder generates solid particles of larger size than the powder, and these larger particles are easier to separate from a treated water stream, using a solid/liquid separation technique such as by settling.
One embodiment according to the present invention relates to the use of a hydroxyapatite composite in the solid adsorbent during the contacting step. Such hydroxyapatite composite comprises:
a hydroxyapatite; and
at least one additive which is present during the hydroxyapatite synthesis.
The at least one additive or a precursor thereof may be added to a vessel where hydroxyapatite synthesis takes place, prior to or during the synthesis of the hydroxyapatite. That is to say, when the synthesis of the hydroxyapatite takes place in a vessel, the additive or a precursor thereof may be added to the vessel before the synthesis is initiated or while the hydroxyapatite structure is synthetized in this vessel.
A particular embodiment according to the present invention relates to a hydroxyapatite composite which comprises:
a hydroxyapatite; and
at least one additive which increases the porosity of the hydroxyapatite. The at least one additive is present while the hydroxyapatite structure is synthetized. The at least one additive may be added to the vessel before the synthesis is initiated or while the hydroxyapatite structure is synthetized in this vessel. The hydroxyapatite composite may have a higher total pore volume and/or a higher BET surface area than a hydroxyapatite material made without the additive.
The hydroxyapatite composite according to the present invention is an effective reactant for immobilizing contaminants from water, in particular when employed in dispersed mode in water treatment units.
The hydroxyapatite composite may comprise at least 50wt%
hydroxyapatite, advantageously at least 60wt%, and more advantageously still at least 70wt% hydroxyapatite or at least 75wt% hydroxyapatite, based on the total weight of dry matter.
In some embodiments, the hydroxyapatite composite may comprise a calcium-deficient hydroxyapatite, preferably with a Ca/P molar ratio more than 1.5 and less than 1.67.
In some embodiments, the hydroxyapatite composite may comprise a calcium-deficient hydroxyapatite and has an overall Ca/P molar ratio higher than the calcium-deficient hydroxyapatite.
The hydroxyapatite composite may further comprise, on the basis of total weight of dry matter,
- water, of the order of from 1 wt% to 30 wt%, advantageously from 2 wt% to 25 wt%, or from 2 wt% to 20 wt%, or from 3 wt% to l5wt% , and/or
- calcium carbonate in an amount of less than 20 wt%, preferably from 1 wt% to 19 wt%, more preferably from 2 wt% to 18 wt%, even preferably from 3 wt% to 15 wt%, yet even more preferably from 4 wt% to 13 wt%, most preferably from 5 wt% to 10 wt%.
The hydroxyapatite composite may further comprise, based on the total weight of dry matter, less than 1 wt% of calcium dihydroxide Ca(OH)2, preferably less than 0.5 wt% calcium dihydroxide, more preferably less than 0.3 wt% calcium dihydroxide, even more preferably less than 0.2 wt% calcium dihydroxide, or even less than 0.1 wt% Ca(OH)2).
The hydroxyapatite composite preferably comprises a weight ratio of hydroxyapatite to additive (HAP:A) of from 1 :0.0l to 1 :0.5. That is to say, when lOOg of hydroxyapatite in the composite, a minimum of 1 g of additive is present and/or a maximum of 50 g is present in the composite. The weight ratio of is preferably at least 1 :0.02 or at least 1 :0.03. The weight ratio of is preferably at most 1 :0.3, more preferably at most 1 :0.25. The hydroxyapatite composite may comprise a weight ratio of hydroxyapatite to additive (HAP: A) of from 1 :0.0l to 1 :0.5, preferably from 1 :0.02 to 1 :0.4 or from 1 :0.03 to 1 :0.4, more preferably from 1 :0.04 to 1 :0.3, yet more preferably from 1 :0.05 to 1 :0.25, yet even more preferably from 1 :0.05 to 1 :0.20.
A range of 5 to 20 g additive per 100 g of hydroxyapatite is particularly suitable.
The hydroxyapatite composite may comprise at least 2 wt%, or at least 3 wt%, or at least 4 wt% of the additive based on the total weight of dry matter.
The hydroxyapatite composite may comprise at most 50 wt%, or at most 30 wt%, or at most 20 wt% of the additive based on the total weight of dry matter.
The hydroxyapatite composite may further comprise: water, of the order of from 0 to 20 wt%, advantageously from 1 % to 20 wt%, more advantageously from 2 % to 10 wt%, based on the total weight of dry matter.
In some embodiments, the hydroxyapatite composite may comprise water, of the order of from 5 wt% to 20 wt%, advantageously from 6 wt% to 20 wt%, based on the total weight of dry matter.
In some embodiments, the hydroxyapatite composite may comprise, based on the total weight of dry matter, less than 5 wt% water, preferably less than 5 wt% and down to 0.1 wt% or even lower
In some embodiments, the hydroxyapatite composite may further comprise, based on the total weight of dry matter, calcium carbonate in an amount of less than 20 wt% and more than 0 wt%, preferably from 1 wt% to 19 wt%, more preferably from 2 wt% to 18 wt%, even more preferably from 5 wt% to 15 wt%, yet even more preferably from 7 wt% to 13 wt%, most preferably from 8 wt% to 12 wt%.
The hydroxyapatite composite may further comprise, based on the total weight of dry matter, calcium dihydroxide Ca(OH)2 from 0 to 20 %,
advantageously from 0 to 4 %, or more advantageously from 0 to 1 wt%, or alternatively more than 0 wt% but at most 4 wt%, or from 1% to 4wt%.
In some embodiments, the hydroxyapatite composite may comprise less than 1 wt% of calcium dihydroxide Ca(OH)2, preferably less than 0.5 wt% calcium dihydroxide, more preferably less than 0.3 wt% calcium dihydroxide, even more preferably less than 0.2 wt% calcium dihydroxide. In some embodiments, the hydroxyapatite composite is substantially free of calcium dihydroxide (i.e., less than 0.1 wt% Ca(OH)2). In some embodiments, the hydroxyapatite composite may comprise at least 2 wt%, preferably at least 2.5 wt% or at least 3 wt%, more preferably at least 5 wt%, and yet more preferably at least 6 wt% of hydroxide ions.
In some embodiments, the hydroxyapatite composite may comprise, on the basis of the total weight of dry matter,
- water, of the order of from 1 wt% to 20 wt%, advantageously from 2 wt% to 20 wt%, or from 2 wt% to 10 wt%, or from 3 wt% to 8 wt% , and/or
- calcium carbonate in an amount of less than 20 wt% and more than
0 wt%, preferably from 1 wt% to 19 wt%, more preferably from 2 wt% to 18 wt%, even preferably from 3 wt% to 15 wt%, yet even more preferably from 4 wt% to 13 wt%, most preferably from 5 wt% to 10 wt%.
In some embodiments, the hydroxyapatite composite may be in the form of particles having a specific surface area of at least 110 m2/g, preferably of at least 120 m2/g, more preferably of at least 130 m2/g, yet more preferably of at least 140 m2/g.
In additional embodiments, the hydroxyapatite composite may be in the form of particles having a total pore volume of at least 0.3 cm3/g, or at least 0.32 cm3/g, or at least 0.35 cm3/g, or at least 0.4 cm3/g.
In preferred embodiments, the additive is inorganic.
The hydroxyapatite composite may comprise more than one additive.
In such embodiments, a first additive may serve as support for a second additive.
In some embodiments, the additive may comprise at least one activated carbon, iron (which may be in the form of metal of oxidation state 0, salt, oxide, oxyhydroxide, or hydroxide, preferably oxyhydroxide or hydroxide), or combinations of two or more thereof.
In some embodiments, the hydroxyapatite composite may comprise an activated carbon as a first additive and iron (for example in the form of zero- valent metal, salt, oxide, oxyhydroxide, or hydroxide) as a second additive.
In some embodiments, the additive may comprise or consist of at least one activated carbon.
Activated carbon may originate from various sources. It can be produced from carbonaceous source materials such as bamboo, coconut husk/shell, willow peat, wood, coir, lignite, coal, petroleum coke, and/or petroleum pitch. In preferred embodiments, the activated carbon used as additive is in a powder form. Its average particle size is generally in size of less than 1 mm. The preferred average particle size for activated carbon may be at most 500 microns, preferably at most 400 microns, or at most 300 microns, or at most 200 microns, or at most 100 microns, or at most 80 microns, or at most 60 microns. Generally, the average particle size for activated carbon may be at least 5 microns, or at least 10 microns.
In particular embodiments, the average particle size for activated carbon is preferably within +/- 50% of the average particle size of the hydroxyapatite which is to be synthesized in the presence of this activated carbon.
In particular preferred embodiments, the average particle size for activated carbon is preferably less than the average particle size of the hydroxyapatite which is to be synthesized in the presence of this activated carbon.
The activated carbon may be selected based at least on the following criteria: the activated carbon yields a pH of at least 5 when dispersed in a suspension at 0.3 wt% in deionized water for 5 hours.
When the additive comprises an activated carbon or blend of two or more activated carbons, the activated carbon or blend of two or more activated carbons is selected so that a 0.3 wt% dispersion of the activated carbon(s) in deionized water provides a pH of 5 or more.
If the selected activated carbon yields a pH of less than 5 when dispersed in a suspension at 0.3 wt% in deionized water for 5 hours, then a blend with another more-alkaline activated carbon may be used in the additive to provide a pH of 5 or more.
The activated carbon may comprise a pore volume of at least 0.25 cm3/g, preferably of at least 0.35 cm3/g, more preferably of at least 0.4 cm3/g.
The activated carbon may have a BET surface are of at least 500 m2/g, preferably of at least 750 m2/g.
The activated carbon may have a unique distribution of pore sizes that contributes to the ability of the composite to remove specific contaminants from aqueous systems. In one embodiment, the activated carbon has a porosity of at least about 0.25 cm3/g. The pores diameter of the activated carbon may be at least about 10 and at most about 500 A (Hg intrusion porosimetry, such as using a Micromeritics model AutoPore-II 9220 porosimeter). In another embodiment, the activated carbon has a porosity of at least about 0.4 cm3/g in pores diameter of at least about 10 and at most about 500 A. In some embodiments, the activated carbon has been subjected to a treatment prior to being used into the hydroxyapatite composite synthesis. Such treatment may enhance the sorption capability of the activated carbon and/or modify the porosity of the activated carbon.
For example the activated carbon may be impregnated by sulfur to enhance the sorption of mercury cations. An example of such sulfur- impregnated activated carbon is MerSorb® from NUCON International.
In another treatment example, the activated carbon may be subjected to an acid treatment such as with nitric acid.
Yet in another treatment example, the activated carbon may be subjected to steam, generally to impact its porosity.
In some embodiments, the activated carbon is not treated with acid prior to being used into the hydroxyapatite composite synthesis.
In some embodiments concerning the formulation of the hydroxyapatite composite, the additive may exclude activated carbon.
The additive may comprise or consist of an iron-containing additive, preferably in the form of metal of oxidation state 0, salt, oxide, oxyhydroxide, or hydroxide, preferably in the form of metal of oxidation state 0, oxide, oxyhydroxide, or hydroxide. The iron in the additive may be of oxidation state 0, 2 or 3. The iron-containing additive is preferably inorganic. If the additive comprises an iron salt, the iron salt is preferably inorganic.
The additive may comprise or consist of an iron oxide. The iron oxide may be iron(III) oxide or ferric oxide of formula Fe203, iron(II) oxide (FeO), or iron(II,III) oxide (Fe304). The additive may comprise or consist of Fe304. Fe304 can occur naturally as the mineral magnetite or may be synthesized, for example in the form of nanoparticles. Examples of synthesis of Fe304 nanoparticles can be found in Gonzales et al., 2012, Journal of Hazard Materials, vol. 211-212, pg. 138-145 using non microwave-assisted or microwave-assisted synthetic techniques or using chemical co-precipitation method similar to previously described in Onar & Yakinci, Journal of Physics: Conference Series 667 (2016) 012005, the International Conference on Magnetic and Superconducting
Materials (MSM15), IOP Publishing doi: 10.1088/1742-6596/667/1/012005, and Meng et al, Applied Surface Science, Vol.280, pg. 679-685.
When the additive comprises iron, the additive more preferably comprises iron(III) hydroxide, and/or iron(III) oxyhydroxide; more preferably comprises iron(III) oxyhydroxide. Iron(III) hydroxide has the chemical formula Fe(OH)3.
Iron(III) oxyhydroxide has the chemical formula FeOOH. It can be obtained for example by reacting ferric chloride with sodium hydroxide.
Alternatively, iron(II) may be oxidized to iron(III) by hydrogen peroxide in the presence of an acid. Furthermore, ferric hydroxide can be prepared as described in W02003/053560 or can be prepared as described in [0045] of
W02017/109014 using solution of Fe(N03)3 and acetic acid and solution of ammonia. Alternatively, commercially available iron(III) oxide-hydroxide may be used. Iron(III) oxide-hydroxide occurs in anhydrous and hydrated forms. Ferrihydrite (FeOOH 0.4H2O) is a hydrous ferric oxyhydroxide mineral which is also suitable for use as additive. Furthermore, iron(III) oxyhydroxide occurs in four different polymorphic forms, known as alpha-, beta-, gamma- and delta- FeOOH. All these forms may be used in the present invention. Goethite is a widespread mineral of formula -FeO(OH) and lepidocrocite is a less common mineral of formula y-FeO(OH) with the same chemical composition as goethite but with a different crystal structure.
The iron(III) oxyhydroxide particles may have a median particle size in the range of from about 1 to about 3,000 nm, preferably about 5 to about 2,000 nm, more preferably from about 10 to about 700 nm, even more preferably from about 50 to about 500 nm, such as in the range of from about 100 to about 400 nm. The iron(III) oxyhydroxide may be formed in situ during the synthesis of the hydroxyapatite by adding the Fe precursor and adding a base to form the FeOOH, or FeOOH may be added as an aqueous slurry or solution comprising from at least 1 wt% to at most 20 wt% FeOOH, or from at least 2 wt% to at most 15 wt% FeOOH, or from at least 2 wt% to at most 10 wt% FeOOH.
The iron may be added during the synthesis of the hydroxyapatite in the form of an iron precursor such as a salt. A suitable precursor of iron may be iron chloride, iron nitrate, iron sulfate, or any combination thereof. A base (source of OH ) is generally added to this iron precursor to generate iron(III) hydroxide or oxyhydroxide.
In some embodiments concerning the formulation of the hydroxyapatite composite, the additive may exclude iron.
Consequently the adsorbent material used for removal of contaminants from the water stream, may comprise one of the following materials:
- one synthetic hydroxyapatite (made without additive); - one hydroxyapatite composite with at least one additive selected from the group consisting of one or more activated carbons, iron (such as in the form of metal, salt, hydroxide, oxyhydroxide, or oxide); and
combinations thereof;
- two or more hydroxyapatite composites, wherein the additives in the hydroxyapatite composites are different; preferably wherein at least one of the additives in a first hydroxyapatite composite comprises an activated carbon or blend of two or more activated carbons, and wherein at least one of the additives in a second hydroxyapatite composite comprises iron (such as in the form of metal, salt, hydroxide,
oxyhydroxide, or oxide); or
- a blend of a synthetic hydroxyapatite without additive and at least one hydroxyapatite composite with at least one additive selected from the group consisting of one or more activated carbons, iron (such as in the form of metal, salt, hydroxide, oxyhydroxide, or oxide); and
combinations thereof.
In particular embodiments of the process according to the present invention, an adsorption pre-treatment step can be carried out to remove at least a portion of one or more contaminants from the water stream prior to
UV/peroxygen step, for example organic contaminants (e.g., PAHs, phenolic compounds, naphtol and derivatives), colored species, and/or inorganic contaminants in the form of metals, non-metals, their cations and/or oxyanions, particularly Hg or its cation, As, B, and/or Se, or their respective oxyanions. The adsorption pre-treatment step preferably comprises contacting the water stream to be treated with a synthetic hydroxyapatite and/or a hydroxyapatite composite.
In particular embodiments of the process according to the present invention, the contacting step can remove at least a portion of one or more contaminants from the water stream, for example organic contaminants
(e.g., PAHs, phenolic compounds, naphtol and derivatives), colored species, and/or inorganic contaminants in the form of metals, non-metals, their cations and/or oxyanions, particularly Hg or its cation, As, B, and/or Se, or their respective oxyanions. The contacting step preferably comprises contacting the water stream, at least a portion of which being irradiated in the UV/peroxygen step, with a hydroxyapatite composite or the adsorbent material comprising at least one hydroxyapatite composite. For removing at least a portion of organic contaminants (e.g., PAHs, phenolic compounds, naphtol and derivatives) and/or colored species from the water stream prior to and/or after the UV/peroxygen step, it is particularly advantageous in the contacting/adsorption step to use a hydroxyapatite composite comprising at least one activated carbon.
For removing at least a portion of Hg, particularly Hg cations from the water stream prior to and/or after the UV/peroxygen step, it is particularly advantageous in the contacting/adsorption step to use a hydroxyapatite composite comprising at least one activated carbon, at least one iron (such as in the form of iron(III) hydroxide and/or iron(III) oxyhydroxide), or combination thereof
For removing at least a portion of As, particularly As oxyanions from the water stream prior to and/or after the UV/peroxygen step, it is particularly advantageous in the contacting/adsorption step to use:
a hydroxyapatite composite comprising activated carbon, iron in the form of iron(III) hydroxide and/or iron(III) oxyhydroxide, or combination thereof or
- two hydroxyapatite composites, one comprising activated carbon, while the other comprises iron in the form of iron(III) hydroxide and/or iron(III) oxyhydroxide, or combination thereof
For removing at least a portion of Se, particularly Se oxyanions from the water stream prior to and/or after the UV/peroxygen step, it is particularly advantageous in the contacting/adsorption step to use:
a hydroxyapatite composite comprising activated carbon, iron in the form of iron(III) hydroxide and/or iron(III) oxyhydroxide, or combination thereof or
- two hydroxyapatite composites, one comprising activated carbon, while the other comprises iron in the form of iron(III) hydroxide and/or iron(III) oxyhydroxide, or combination thereof
For removing at least a portion of metallic cations from the water stream prior to and/or after the UV/peroxygen step, such as cations of Al, Ag, Ba, Be, Ce, Co, Cd, Cu, Cr, Fe, La, Li, Mn, Mg, Mo, Ni, Pb, Pd, Rb, Sb, Sn, Sr, Th, Ti, U, V, Y, and/or Zn, and particularly Fe, Ni, Co, and/or Cu, it is particularly advantageous in the contacting/adsorption step to use a synthetic hydroxyapatite and/or a hydroxyapatite composite comprising at least one activated carbon, at least one iron (such as in the form of iron(III) hydroxide and/or iron(III) oxyhydroxide), or combination thereof
METHODS FOR MAKING THE SOLID ADSORBENT
For the solid adsorbent comprising a synthetic hydroxyapatite:
The solid adsorbent may be made by a process comprising:
- in a first step, a source of calcium and a source of phosphate ions are mixed in water in a molar ratio that is adjusted to obtain a Ca/P molar ratio of between 0.5 and 1.6, preferably between 0.7 and 1.3, and reacting the source of calcium with the phosphate ions at a pH of between 2 and 8, in order to obtain a suspension (A) of calcium phosphate,
- in a second step, adding to the suspension (A) an alkaline compound comprising hydroxide ions in order to set a pH of at least 7.5, preferably at least 8, or at least 8.5, or at least 9, or of at least 10; further adding an additional source of calcium in order to obtain a suspension (B) of composite having a Ca/P molar ratio of greater than 1.6, preferably greater than 1.65 to form a hydroxyapatite structure.
A particular process for producing the hydroxyapatite adsorbent can be found in WO 2015/173437 by Solvay SA, the details of such production process being herein incorporated by reference.
The source of calcium advantageously comprises calcium carbonate, or calcium oxide, or calcium hydroxide, or calcium chloride, or calcium nitrate, or calcium acetate. The source of calcium is more advantageously a limestone, or a mixture of limestone and calcium oxide or hydroxide. More advantageously, the source of calcium is in the form of powder or aqueous suspension of powder and the powder is selected from: calcium carbonate, calcium oxide, calcium hydroxide, or a mixture thereof, and the powder has a mean particle size of less than 300 pm.
It is advantageous for the source of calcium selected from calcium carbonate, calcium oxide, calcium hydroxide or mixtures thereof to be in the form of a powder or aqueous suspension of powder, and to have a small particle size. In one recommended variant, the mean diameter of the particles of the powder is less than 300 pm, advantageously less than 200 pm and preferably less than 100 pm. The mean diameter in question is the D50, that is to say the diameter such that 50% by weight of the particles have a diameter less than said value. In the present invention, various sources of phosphate ions may be used, in particular:
- phosphoric acid,
- or a dihydrogen phosphate salt such as a sodium, potassium or ammonium dihydrogen phosphate salt, preferably a sodium dihydrogen phosphate salt,
- or a monohydrogen phosphate salt such as a sodium, potassium or ammonium monohydrogen phosphate salt, preferably a sodium monohydrogen phosphate salt.
In the present invention, phosphoric acid is preferred due to its greater availability and lower cost compared to dihydrogen and monohydrogen phosphate salts.
The suspended solids density of the suspension (A) in the first step is in general at most 20% by weight.
The suspended solids density of the suspension (B) in the second step is in general at most 25% by weight. A preferred range of suspended solids density of the suspension (B) in the second step is from 16 wt% to 24 wt%. It has been indeed observed that a too low density of suspension decreases the efficacy of the produced reactant particles in heavy metal adsorption. Moreover a too low density of suspension induces longer time of water separation when decantation or filtration is used in the process.
In the process for making the adsorbent, the stirring of the suspension during the first and second steps corresponds generally to a stirring dissipated energy in the reactors volume of at least 0.2 and at most 1.5 kW/ m3, preferably at least 0.5 and at most 1.0 kW/ m3.
In the process for making the adsorbent, the first step is preferably carried out at a temperature of less than 50°C, preferably at a temperature of at most 45°C, or at a temperature of at most 40°C, more preferably at a temperature of at most 35°C. This makes it possible to obtain an adsorbent at the end of the second step in the form of particles of large to medium particle size and having a high specific surface area.
An embodiment of the present invention further relates to the use of particles of hydroxyapatite adsorbent,
- having a mean size of at least 20 pm, or of at least 25 pm, or of at least 30 pm; - having a specific surface area of at least 110 m2/g, or of at least 120 m2/g, or of at least 130 m2/g, or of at least 140 m2/g; and/or
- having a total pore volume of at least 0.3 cm3/g, or of at least 0.32 cm3/g, or at least 0.4 cm3/g.
In the process of the present invention, it is advantageous for the second step to be carried out at a temperature of at least 45°C, preferably of at least 50°C, more preferably of at least 55°C, or of at least 60°C, or of at least 80°C. Specifically, this makes it possible to rapidly convert the calcium phosphate compound of low Ca/P ratio (such as brushite) from the first step into the adsorbent comprising a hydroxyapatite of higher Ca/P ratio, with a good fixation of the hydroxide ions at the core and at the surface of the adsorbent, and to more rapidly consume the phosphates from the solution of the suspension (B).
Advantageously, the second step is carried out for a duration of at least 0.5 hour.
In a particular preferred embodiment, the method takes place in two steps, a first step called "acid attack" and a second step, called "lime maturation". The first step includes the decarbonation of calcium carbonate (as source of calcium) by the addition of phosphoric acid (as source of phosphate ions). Carbonic acid formed by this acid attack decomposes into water and carbon dioxide, as soon as the maximum solubility of C02 in the aqueous phase is reached. Calcium hydrogenphosphate (CaHP04.2H20, also known as brushite) formed in the first step has a Ca/P molar ratio of 1. However, the Ca/P molar ratio of a
stoichiometric hydroxyapatite is 1.67. So there is a calcium deficit that has to be filled by the second step. In the second step "lime maturation", the addition of lime (Ca(OH)2) as an additional source of calcium to the brushite contributes the calcium necessary to approach a stoichiometric hydroxyapatite. But this addition of lime also allows the addition of hydroxide anions necessary for the structure of the hydroxyapatite and the neutralization of H + hydrogenphosphate. This method has the advantage that it allows the synthesis of hydroxyapatite from relatively inexpensive reagents, compared to other methods, and uses relatively mild conditions of synthesis (temperature and pH).
In some embodiment, the synthetized hydroxyapatite in the adsorbent approaches the molar Ca/P hydroxyapatite stoichiometry of 1.67 but generally comprises a Ca/P more than 1.5 and less than 1.67, that is to say, the synthetized hydroxyapatite in the adsorbent is deficient in calcium compared to the stoichiometry. Some of the calcium source (e.g., calcium carbonate when it is used in the first step) which is not utilized in the hydroxyapatite would remain inside the hydroxyapatite adsorbent composition.
In this particular preferred method, the first step is to attack limestone with phosphoric acid at a temperature of from 20 to 25°C to make a brushite type structure. At the end of the addition of acid, the second step is initiated by heating the mixture up to at least 50°C. A suspension of Ca(OH)2 (such as 25 wt%) is then added to maintain the pH of the suspension at a maximum 8.9. The second step preferably uses an overall Ca/P molar ratio of about 1.67. The goal of this second step is to convert the brushite type structure created in the first step to a hydroxyapatite structure in the second step.
The suspension (B) may be left to cool for 1 to 24 hours, preferably at least 10 hours, down to ambient temperature (generally 20-25°C). This makes it possible to mature the adsorbent and to reduce the residues of MCP/DCP or brushite, or of octacalcium (precipitated during the first step), into
hydroxyapatite and into calcium phosphate and calcium hydroxide complexes, within the suspension (B).
Optionally, in the process of making the adsorbent, at the end of the second step, the suspension (B) comprises an aqueous solution (C) and composite particles, and
- in a third step, a portion of the aqueous solution (C) is separated from the suspension (B) in order to obtain an aqueous suspension (D) comprising at least 18% and at most 50% of adsorbent particles, or in order to obtain a wet solid (D') comprising at least 50% and at most 80% of composite particles, or a pulverulent solid (D") comprising at least 80% and at most 95% of adsorbent particles and at least 5% and at most 20% of water.
In a third step, the separation may comprise a dewatering step which increases the solids content. The separation may comprise for example a filter, such as a filter press. This type of separation may provide an aqueous suspension (D) or a wet solid (D') of higher solids content than the
suspension (B) taken out of the reactor.
In some embodiments, the method for making the hydroxyapatite adsorbent particles may further comprise drying the suspension (B) or aqueous suspension (D) or wet solid (D') at a temperature between 50 to l80°C, preferably from 80 to 130 °C, or more preferably from 90 to 120 °C, most preferably from 95 to 115 °C. Drying may comprise any suitable technique suitable for decreasing the water content of the suspension (B) or aqueous suspension (D) or wet solid (D'), such as, but not limited to, spray drying, flash drying, and/or drying in a fluidized bed.
In some embodiments, the method for making the hydroxyapatite adsorbent particles may comprise spray drying the suspension (B) or aqueous suspension (D) to provide a pulverulent solid (D").
Consequently, the present invention also relates to the use of an aqueous suspension (D) comprising at least 25%, preferably at least 40% and at most 50% of adsorbent particles, or to a wet solid (D') comprising at least 50% and at most 80% of adsorbent particles, or a pulverulent solid (D") comprising at least 70%, preferably at least 80%, and at most 95% of adsorbent particles and at least 5% and at most 20% of water.
The adsorbent obtained according to such method is effective for treating the irradiated water stream contaminated by metallic ions.
For the solid adsorbent comprising a synthetic hydroxyapatite composite:
The process for producing a hydroxyapatite composite, may comprise the following step:
- in a first step, a source of calcium and a source of phosphate ions are mixed in water in a molar ratio that is adjusted to obtain a Ca/P molar ratio of between 0.5 and 1.6, preferably between 0.7 and 1.3, and reacting the source of calcium with the phosphate ions at a pH of between 2 and 8, in order to obtain a suspension (A) of calcium phosphate,
- in a second step, adding to the suspension (A) an alkaline compound comprising hydroxide ions in order to set a pH of at least 7.5, preferably at least 8, or at least 8.5, or at least 9, or of at least 10; further adding an additional source of calcium in order to obtain a suspension (B) of composite having a Ca/P molar ratio of greater than 1.6, preferably greater than 1.65 to form a hydroxyapatite structure; and
- further adding at least one additive or a precursor thereof in the first step, in the second step, or in both in the first and second steps.
When the additive or precursor thereof is added in the first step, it may be added at the beginning of the first step before the reaction takes place, during the reaction, or after the reaction is completed in the first step (this being preferred). It is envisioned that the additive or precursor thereof may be added not all at once, for example in at least two portions, for example a first portion in the first step and another portion in the second step.
It is also envisioned that two or more additives or precursors thereof may be added. In an example, a first additive or precursor thereof is added in the first step and a second additive or precursor thereof is added in the second step.
Alternatively, the first and second additives or precursors thereof may be added in the first step or in the second step.
Examples of additives or precursors thereof that may be added in the first step include activated carbon and/or chloride salts of iron.
A particular embodiment of the present invention relates to a process for producing the hydroxyapatite composite, comprising:
- in a first step, a source of calcium and a source of phosphate ions are mixed in water in a molar ratio that is adjusted to obtain a Ca/P molar ratio of between 0.5 and 1.6, preferably between 0.7 and 1.3, and reacting the source of calcium with the phosphate ions at a pH of between 2 and 8, in order to obtain a suspension (A) of calcium phosphate, and
- in a second step, adding to the suspension (A) an alkaline compound comprising hydroxide ions in order to set a pH of at least 7.5, preferably at least 8, or at least 8.5, or at least 9, or of at least 10; further adding an additional source of calcium in order to obtain a suspension (B) of composite having a Ca/P molar ratio of greater than 1.6, preferably greater than 1.65, and further adding at least one additive or a precursor thereof, to form a composite material comprising a hydroxyapatite structure.
An alternate embodiment of the present invention relates to a process for producing the hydroxyapatite composite, comprising:
- in a first step, a source of calcium and a source of phosphate ions are mixed in water in a molar ratio that is adjusted to obtain a Ca/P molar ratio of between 0.5 and 1.6, preferably between 0.7 and 1.3, and reacting the source of calcium with the phosphate ions at a pH of between 2 and 8, in order to obtain a suspension (A) of calcium phosphate,
- further adding at least one additive or a precursor thereof during the first step, such as at the beginning of the first step before the reaction takes place, during the reaction, or after the reaction is completed in the first step (this being preferred); - in a second step, adding to the suspension (A) an alkaline compound comprising hydroxide ions in order to set a pH of at least 7.5, preferably at least 8, or at least 8.5, or at least 9, or of at least 10; further adding an additional source of calcium in order to obtain a suspension (B) of composite having a Ca/P molar ratio of greater than 1.6, preferably greater than 1.65, to form a composite material comprising a
hydroxyapatite structure.
Examples of additives or precursors thereof that may be added in the first step include activated carbon and/or chloride salts of iron.
The additive may be added as a precursor of the additive, and this precursor is converted to the form of the additive during the synthesis of the composite in order for the additive to be present in the final composition of the composite. For example, a precursor of the additive may be a salt of iron, and during the synthesis of the composite, the salt of iron is converted to iron hydroxide or oxyhydroxide to generate the additive in the final composition of the hydroxyapatite composite.
In some embodiments, the additive or precursor thereof may be in the form of a solution or a slurry before it is added to at least one of the first and second steps of the method of making the composite.
The additive is preferably incorporated or embedded into or coated onto the hydroxyapatite structure, or otherwise associated with the hydroxyapatite structure via cohesive forces.
In some embodiments, the additive or precursor thereof may be in the form of a solid before it is added to at least one of the first and second steps.
In some embodiments, when the additive or precursor thereof may be in the form of a powder (either sold‘as is’ or ground before use), the method of making the composite may further include sieving the powder of the additive or precursor thereof to remove large particles, such as those exceeding a size of 100 microns, or exceeding a size of 90 microns. For example, the powder of the additive or precursor thereof which passes through a sieve No. 170 (under ASTM El l) equivalent to a size of less than 90 microns, or through a sieve No. 200 (under ASTM El 1) equivalent to a size of less than 75 microns, or through a sieve No. 230 (under ASTM El l) equivalent to a size of less than 63 microns can be added to at least one of the first and second steps of the method of making the composite. During the synthesis of apatite structure and more precisely during the second step corresponding to the addition of the hydroxide ions, the pH reaches 8-8.5 to a maximum of 8.9, and this addition becomes more difficult, if not impossible without raising the pH too much. This moment is called "plateau".
The plateau is where the additive is preferably added out at one time, although the addition of additive may be carried out in several increments.
However, it is to be understood that the addition of the additive in the second step may be carried out during the same period of time when the hydroxide ions are added (that is to say, before the pH plateau is reached), such as a one-time addition, in several increments, or in a continuous manner.
The additive needs to be present during the hydroxyapatite synthesis but its addition does not have to necessarily take place at the time of the hydroxyapatite synthesis. The additive or a precursor thereof may be added prior to the plateau in the second step, or even before the conversion of the low Ca/P calcium- phosphate compound (such as brushite of Ca/P = 1) formed in the first step to the hydroxyapatite structure formed in the second step. For example, the additive or a precursor thereof may be added before the addition of the hydroxide ions is initiated in the second step. The additive or a precursor thereof may be added even during the first step, parti cul arly if the additive or precursor thereof is compatible with the pH condition of the first step, which is generally less than 7, or less than 6.5, or even less than 6.“Compatible” here means that the additive or precursor thereof added in the first step is not degraded/reacted or otherwise rendered ineffective as an additive for making a hydroxyapatite composite in the second step.
FIG. 1 to 5 represent various embodiments of simplified process flow diagrams for carrying out the process according to the present invention. In the description of these figures, there is a mention of a UV/H2O2 unit 10, and it should be understood that any suitable UV/peroxygen unit is suitable in these embodiments.
FIG. 1 represents a schematic process flow diagram of an embodiment of the process according to the invention for treating a water stream, for example originating from an ore mining process, containing cyanide, metallic ions (such as barium, cadmium, cobalt, copper, iron, manganese, nickel, lead, zinc) and metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion (such as hexacyanoferrate(II), hexacyanoferrate(III), hexacyanocobaltate(III), tetracyanonickelate(II), tetracyanocuprate(II), or combinations thereof). The water stream may also comprise organic species and/or colored species.
This process includes a UV/H2O2 unit 10, an adsorption unit 20 (for metals/organics removal), and a separation unit 30 (for solids removal). A H2O2 source 50 is fed to the UV/H2O2 unit 10 which comprises a UV lamp (UV light source), preferably emiting UV-C, preferably with a wavelength from 200 to 290 nm. A water feedstream 40 to be treated enters the UV/H2O2 unit 10 under suitable peroxidation conditions as described herein to form an irradiated effluent 60. The irradiated effluent 60, in part or in totality, is directed to the adsorption unit 20 while fresh solid adsorbent 70 comprising apatite (preferably hydroxyapatite, more preferably a synthetic hydroxyapatite) is fed to this adsorption unit 20 in order for contaminants, such as free metallic species, to be removed from the irradiated effluent. The treated effluent 80 which is contacted with the solid adsorbent exiting the adsorption unit 20 is fed to the separation unit 30 where the solids are separated from the liquid phase (water). A treated water 90 exits the separation unit 30 while a stream 100 containing separated solids can be directed at least in part back to the adsorption unit 20 (spent adsorbent recycle), while a portion 110 of the stream 100 containing separated solids is purged out of the process. The entry point of the recycled solids into the adsorption unit 20 may be the same as the fresh adsorbent 70 (not illustrated), or may be different (as illustrated in FIG. 1). An optional pH adjustment step may be done on at least a portion of the irradiated effluent 60 before entering the adsorption unit 20. An optional addition of an acid 115 may be carried out in order to reduce the pH of at least a portion of the irradiated effluent 60 to a value from 7 to 9, preferably from 7.5 to 8.8, yet more preferably from 7.5 to
8.5. FIG. 2 represents another schematic process flow diagram of an embodiment of the process according to the invention for treating a water stream originating from an ore processing process, containing cyanide, metallic ions (such as barium, cadmium, cobalt, copper, iron, nickel, manganese, lead, zinc) and metal- cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion (such as hexacyanoferrate(II),
hexacyanoferrate(III), hexacyanocobaltate(III), tetracyanonickelate(II), tetracyanocuprate(II), or combinations thereof). The water stream may also comprise organic species and/or colored species. This embodiment of the process illustrated in FIG. 2 is similar to what is shown in FIG. 1 except that the adsorption (e.g., for metals/organics removal) and the separation are combined into one single unit 120. The UV/H2O2 treatment proceeds as previously described in FIG. 1 in the UV/H2O2 unit 10 and the irradiated effluent 60 is directed to this adsorption + separation unit 120. Preferably, the unit 120 includes a settler, where fresh solid adsorbent 70 is fed generally in a zone of the settler which allows sufficient time of contact of the apatite with the metallic ions and optionally organic contaminants. It is preferred that the addition of the fresh adsorbent 70 is carried out away from the treated water outlet of the unit 120 in order to avoid bypass of the fresh solids into the treated water 90. The separation in unit 120 is effective in settling the solids originating from the spent adsorbent and also the particles of metal hydroxides that may form from the metal(s) extracted from the metal-cyanide complexes during the UV/H2O2 treatment in the UV/H2O2 unit 10. The stream 100 containing separated solids can be directed at least in part back to the adsorption + separation unit 120 (spent adsorbent recycle), while a portion 110 of the stream 100 containing separated solids is purged out of the process. The entry point of the recycled solids to unit 120 may be the same as the entry point of fresh adsorbent 70 (not illustrated), or may be different (as illustrated in FIG. 2). As previously described, there may be an optional pH adjustment step on the irradiated water 60 before entering the adsorption + separation unit 120 by the optional addition of acid 115 in order to reduce the pH to a value from 7 to 9, preferably from 7.5 to 8.5.
Although not illustrated in FIG. 1 & 2, the UV/H2O2 unit 10 may comprise a plurality of UV units, each comprising a UV lamp, and the H2O2 source 50 may be split to be fed to the plurality of these UV units. The plurality of UV units may be operated in parallel or in series (preferred). For example, FIG. 4
illustrates two (2) UV units lOa, lOb operated in series, and the H2O2 source 50 is split into two streams 50a and 50b, which are fed respectively to the 2 UV units lOa and lOb. Any embodiment described with respect to the plurality of the UV units concerning FIG. 4 is equally applicable for the UV/H2O2 unit 10 of FIG. 1 & 2.
FIG. 3 represents another schematic process flow diagram of an embodiment of the process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, and optionally organics. This process is similar to what is shown in FIG. 1 except that the UV/H2O2 step and the adsorption step (for metals/organics removal) are carried out into one combined unit 210. The UV/H2O2 treatment step and the adsorption step proceed as previously described in FIG. 1 except that these two steps are done in the same unit 210. The pH selected for this UV peroxidation in unit 210 must be compatible with the operational pH of the metals/organics removal step. The separation in unit 30 is effective in settling the solids originating from the adsorbent and also the particles of metal hydroxides that may form from the metal(s) extracted from the metal-cyanide complexes during the UV/H2O2 treatment step in combined unit 210. The stream 100 containing separated solids exiting the separation unit 30 can be directed at least in part back to the combined unit 210 (spent adsorbent recycle), while a portion 110 of the stream 100 containing separated solids is purged out of the process. The entry point of the recycled solids to combined unit 210 may be the same as the fresh adsorbent 70 (not illustrated), or may be different (as illustrated in FIG. 3). There may be an optional pH adjustment on the water feedstream 40 before entering the combined UV/H2O2 + adsorption unit 210 by an optional addition of acid 215 in order for the pH of the water feedstream 40 entering the unit 210 to be a value from 8 to 11, preferably from 8.5 to 10 suitable for both UV peroxidation and adsorption of metals and optionally organics on the solid adsorbent comprising apatite in the combined unit 210.
FIG. 4 represents another schematic process flow diagram of an embodiment of the process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, comprising a UV/H2O2 treatment step in a UV/H2O2 unit 10, a buffer tank 220, an adsorption step (for metals/organics removal) in an adsorption unit 20 and a separation step (for solids removal) in a separation unit 30. This process is similar to what is shown in FIG. 1 except that the UV/H2O2 unit 10 is in fluid circulation with the buffer tank 220.
In this process, the UV/H2O2 unit 10 comprises a plurality of UV units and the peroxygen source is fed to the plurality of UV units. Each of the UV units comprises a UV lamp, preferably a Hg lamp. The plurality of UV units may comprise at least 2, preferably at least 3 UV units, and/or at most 15, preferably at most 12, more preferably at most 10 UV units. The UV units are preferably sized the same so as to accommodate the same incoming flow rate of water stream to be treated. The plurality of UV units preferably comprises the same type of UV lamp, preferably the same type of Hg lamp, but not necessarily.
The plurality of UV units may be operated in series, that is to say, wherein the irradiated water effluent exiting a UV unit is sent to a subsequent UV unit to get another round of UV treatment. In this manner, the water effluent being fed to the UV/H2O2 step is subjected several times to UV irradiation in the presence of peroxygen. FIG. 4 illustrates two (2) UV units lOa, lOb operated in series, and the H2O2 source 50 is split into two streams 50a and 50b, which are fed respectively to UV units lOa and lOb.
Although FIG.4 illustrates two UV units operated in series, it is to be understood that the plurality of UV units may be operated in parallel, that is to say, wherein a water stream feeding the UV/H2O2 step is split into several feedstreams to feed the plurality of the UV units.
At least some or all of the UV lamps in the plurality of UV units (e.g., lOa, lOb) preferably emit UV-C, preferably with a wavelength from 200 to 290 nm.
The water feedstream 40 to be treated by the process is fed to the buffer tank 220.
At least a portion of the tank content represented by water effluent 170 exiting the buffer tank 220 is directed to the UV/H2O2 unit 10 where the water is irradiated under suitable peroxidation conditions as described herein to form an irradiated effluent 60 that exists the UV/H2O2 unit 10. The irradiated effluent 60 is then sent back to the buffer tank 220. The stream 170 exiting the buffer tank 220 and entering the UV/H2O2 unit 10 and the irradiated effluent 60 exiting the UV/H2O2 unit 10 and entering the buffer tank 220 thus create a fluid circulation between the UV/H2O2 unit 10 and the buffer tank 220.
As such the volumetric flow rates of incoming stream 60 and exiting stream 170 in the buffer tank 220 are preferably about the same. Additionally, the volumetric flow rates of the incoming water feedstream 40 and of the exiting effluent 160 in the buffer tank 220 are also preferably about the same. This permits the maintenance of the hydraulic balance in the buffer tank 220 between the incoming streams (40, 60) and exiting streams (160, 170).
The effluent stream 160 (at least a portion of which has been irradiated) which exits the buffer tank 220 and which is directed to the adsorption unit 20 may be withdrawn from the buffer tank 220 by way of an overflow. This would permit to maintain the contents’ level in the buffer tank 220 at a constant value. To allow a longer reaction time for the peroxidation to take place compared to what is needed for the photo-dissociation of the metal-cyanide complexes and also of the free cyanides, the volumetric capacity of the buffer tank 220 may be sized to be at least 2 times greater, preferably at least 5 times greater, more preferably at least 10 times greater, yet more preferably at least 15 times greater, or at least 20 times greater, than the volumetric capacity of the UV unit(s). In an example, when the UV/H2O2 unit 10 contains from 2 to 4 UV units, each having a volumetric capacity of 1 m3, the buffer tank 220 may be sized to be at least 20 m3, preferably at least 30 m3, more preferably at least 40 m3.
The residence time in the buffer tank 220 may be at least 15 minutes, or at least 30 minutes, or at least 45 minutes, or at least 60 minutes and/or at most 180 minutes, or at most 150 minutes, or at most 120 minutes.
The buffer tank 220 may comprise at least one mixed tank in which a stirrer containing one or more impellers stirs its content or at least one tank where its content is circulated for example by an internal or external pump.
At least a portion of the effluent 160 (at least a portion of which has been irradiated) exiting the buffer tank 220 is directed to the adsorption unit 20 in order for free metallic ions to be removed. At least a portion of this effluent is contacted with the solid adsorbent and exits the adsorption unit 20 as treated effluent 80. The treated effluent 80 is fed to the separation unit 30 where the solids are separated from the liquid phase (water). A treated water 90 exits the separation unit 30. A stream 100 containing separated solids and exiting the separation unit 30 can be directed at least in part back to the adsorption unit 20 (solid adsorbent recycle), while a portion 110 of the stream 100 containing separated solids is purged out of the process. The entry point of the recycled solids into the adsorption unit 20 may be the same as the fresh adsorbent 70, or may be different (illustrated with different entry points for fresh and spent recycled adsorbents in FIG. 4).
An optional pH adjustment step may be carried out on at least a portion of the effluent 160 (at least a portion of which has been irradiated) exiting the buffer tank 220 before entering the adsorption unit 20. For example, an optional addition of an acid 115 may be carried out in order to reduce the pH of the effluent 160 to a value from 7 to 9, preferably from 7.5 to 8.8, yet more preferably from 7.5 to 8.5. FIG. 5 represents another schematic process flow diagram of an embodiment of the process according to the invention for treating a water stream originating from an ore mining process, containing cyanide, metallic ions and stable metal-cyanide complexes, comprising an adsorption step (pre-treatment for removal of organics, free metals, and/or colored species), a separation step (for solids removal), a UV/H2O2 treatment step in fluid circulation with a buffer tank, wherein at least a portion of the irradiated effluent is sent to an adsorption step (for removal of free metals liberated from cyanide complexes), wherein the adsorption step prior to irradiation and the adsorption step after irradiation are preferably carried out in a same unit (unit 20).
This process includes a UV/H2O2 unit 10, a buffer tank 220, an adsorption unit 20 (for metals/organics/ color removal), and a separation unit 30 (for solids removal).
This process is similar to what is shown in FIG. 4 in that the UV/H2O2 step is in fluid circulation with the buffer tank 220, but the adsorption unit 20 in this process is used for an adsorption pre-treatment of the water feedstream prior to being directed to the UV/H2O2 unit 10 and also used for an adsorption of at least a portion of the irradiated effluent which exits either the UV/H2O2 unit 10 (not illustrated) or the buffer tank 220 in fluid circulation with the UV/H2O2 unit 10 (as illustrated in FIG. 5).
The water feedstream 40 is fed to the adsorption unit 20 which serves as a pretretament step for the removal of organics, free metallic species and/or color. The solid adsorbent 70 is added to the adsorption unit 20.
Preferably in this process, the solid adsorbent 70 used in the adsorption unit 20 is suitable for removing color. The presence of color in the water feedstream 40 to be treated may indeed hinder the performance of the UV in the UV/H2O2 step. Hence removing some of the color of the water feedstream prior to the UV/H2O2 step may be beneficial to maximize the use of the UV light for the photo-disassociation of the metal-cyanide complexes and not for the treatment of colored species in the water stream.
Preferably in this process, the solid adsorbent 70 used in the adsorption unit 20 is further suitable for removing at least a portion of organics and free metallic species such as ions, in particular free species of heavy metals, arsenic, selenium, .... Indeed the water feedstream 40 generally contains free metallic species such as metallic ions that are not complexed with cyanide and/or organics. Therefore the adsorption unit 20 used in FIG. 5 for adsorption prior to and after irradiation step preferably uses a solid adsorbent 70 comprising apatite as described herein in the description. A particular preferred solid adsorbent used in this particular adsorption unit comprises a synthetic hydroxyapatite and/or a synthetic hydroxyapatite composite with activated carbon. The synthetic hydroxyapatite composite with activated carbon is particularly preferred for removal of free (not-complexed) heavy metals, at least a portion of organics and colored species.
An effluent 80 exiting the adsorption unit 20 is directed to the separation unit 30 in which the solids are separated from the liquid phase (water).
A pre-treated water 180 exits the separation unit 30 while a stream 100 containing separated solids can be directed at least in part back to the adsorption unit 20 (recycle), while a portion 110 of the stream 100 containing separated solids is purged out of the process. The entry point of the recycled solids into the adsorption unit 20 may be the same as the fresh adsorbent 70, or may be different.
The pre-treated water 180 is directed to the buffer tank 220.
A water effluent 170 exiting the buffer tank 220 which is to be treated enters the UV/H2O2 unit 10 under suitable peroxidation conditions as described herein to form an irradiated effluent 60 that exists the UV/H2O2 unit 10. The irradiated effluent 60 is then sent back to the buffer tank 220.
A treated water 190 is withdrawn from the buffer tank 220 and exits the process.
The stream 170 exiting the buffer tank 220 and entering the UV/H2O2 unit 10 and the irradiated effluent 60 exiting the UV/H2O2 unit 10 and entering the buffer tank 220 thus create a fluid circulation between the UV/H2O2 unit 10 and the buffer tank 220. As such the volumetric flow rates of incoming stream 60 and exiting stream 170 are preferably about the same. Additionally, the volumetric flow rates of feedstream 180 and of effluents 190 and 160 are also preferably about the same. This allows to maintain hydraulic balance in the buffer tank 220 between the incoming streams (180, 60) and exiting
streams (160, 170, 190).
At least a portion of the irradiated effluent 160 exiting the buffer tank 220 is directed to the adsorption unit 20 in order for free metallic ions to be removed from the irradiated effluent. At least a portion of this irradiated effluent is contacted with the solid adsorbent and exits the adsorption unit 20 as treated effluent 80. The effluent stream 160 which exits the buffer tank 220 and which is directed to the adsorption unit 20 may be withdrawn from the buffer tank 220 by way of an overflow. This would permit to maintain the contents’ level in the buffer tank 220 at a constant value.
Similarly as in FIG. 4, the UV/H2O2 unit 10 comprises a plurality of UV units comprising UV lamps and the peroxygen source is fed to the plurality of UV units. FIG. 5 illustrates two (2) UV units lOa, lOb operated in series, and the H2O2 source 50 is split into two streams 50a and 50b, which are fed respectively to the 2 UV units lOa and lOb. Any embodiment described with respect to the plurality of the UV units concerning FIG. 4 is equally applicable for FIG. 5.
To allow a longer reaction time for the peroxidation to take place compared to what is needed for the photo-dissociation of the metal-cyanide complexes and also the free cyanides, the volumetric capacity of the buffer tank 220 may be sized to be at least 2 times greater, preferably at least 5 times greater, more preferably at least 10 times greater, yet more preferably at least 15 times greater, or at least 20 times greater, than the volumetric capacity of the UV unit(s). In an example, when the UV/H2O2 unit 10 contains from 2 to 4 UV units, each having a volumetric capacity of 1 m3, the buffer tank 220 may be sized to be at least 20 m3, preferably at least 30 m3, more preferably at least 40 m3.
The residence time in the buffer tank 220 may be at least 15 minutes, or at least 30 minutes, or at least 45 minutes, or at least 60 minutes and/or at most 180 minutes, or at most 150 minutes, or at most 120 minutes.
The buffer tank 220 may comprise at least one mixed tank in which a stirrer containing one or more impellers stirs its content or at least one tank where its content is circulated for example by an internal or external pump.
An optional pH adjustment step may be carried out on at least a portion of the water feedstream 40 entering the adsorption unit 20 for pre-treatment in order to remove at least a portion of organics, free metallic species (e.g., metals in the forms of ions and not complexed), and/or color. For example, an optional addition of an acid 215 may be carried out in order to reduce the pH of the water feedstream 40 to a value from 7 to 9, preferably from 7.5 to 8.8, yet more preferably from 7.5 to 8.5.
An optional pH adjustment step may be carried out on at least a portion of the irradiated effluent 160 exiting the buffer tank 220 before entering the adsorption unit 20 on on at least a portion of the irradiated effluent 60 exiting the UV/H202 unit 10 before entering the buffer tank 220. For example, an optional addition of an acid 115 may be carried out in order to reduce the pH of the effluent 60 or effluent 160 to a value from 7 to 9, preferably from 7.5 to 8.8, yet more preferably from 7.5 to 8.5.
In particular the present invention relates to the following embodiments. ITEM 1. A process for treating a water stream, preferably originating from a ore mining process, containing cyanide, metallic ions and metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, where K is the constant for the equilibrium between the metal-cyanide complex and the free metal ion and cyanide ion, said method comprising:
irradiating at least a portion of the water stream at a pH greater than 7, preferably greater than 8 with ultraviolet light in the presence of a peroxygen at a selected wavelength to form an irradiated effluent, wherein at least one of said metal-cyanide complexes undergoes photo dissociation and liberates free cyanide ligand from the complex in order for the free cyanide to be converted to cyanate (and optionally for the metal from the complex to be converted to an hydroxide form);
contacting at least a portion of the irradiated effluent with a solid adsorbent comprising apatite to remove from the irradiated effluent at least part of said metallic ions to form a treated effluent; and
separating the treated effluent from the solid adsorbent.
ITEM 2. The process of ITEM 1, wherein the pH during irradiation is greater than 7 and up to 11, preferably from 8 to 11, more preferably from 8.5 to 10.5, yet more preferably from 9 to 10.5, even more preferably from 9.5 to 10.5, most preferably from 10 to 10.5.
ITEM 3. The process of any of the preceding ITEMS, wherein the at least one metal-cyanide complex which undergoes photo-dissociation contains a metal in the complex selected from the group consisting of Fe(II), Fe(III), Co(II), Ni(II), Cu(I), Cu(II), and Hg(II), preferably selected from the group consisting of Fe(II), Fe(III), Co(II), Cu(I), Cu(II), and Ni(II).
ITEM 4. The process of any of the preceding ITEMS, wherein said metal- cyanide complex which undergoes photo-dissociation is selected from the group consisting of hexacyanoferrate(II), hexacyanoferrate(III),
hexacyanocobaltate(III), tetracyanonickelate(II), tetracyanocuprate(II), and combinations thereof. ITEM 5. The process of any of the preceding ITEMS, wherein during irradiation, the ultraviolet light has a wavelength in the region from 200 to 375 nm, preferably from 200 to 350 nm, more preferably from 200 to 300 nm, most preferably at 254 nm, or the ultraviolet light is emits by a UV-C lamp, preferably with a wavelength from 200 to 290 nm, preferably in order for the metal-cyanide complexes to undergo photo-disassociation and for the peroxygen to form hydroxyl radicals.
ITEM 6. The process of any of the preceding ITEMS, wherein the irradiation with ultraviolet light is carried out for at least 5 minutes and preferably less than 30 min.
ITEM 7. The process of any of the preceding ITEMS, wherein the irradiation with ultraviolet light is carried out with a Hg lamp with a minimum electric rating of 8 W, preferably a low pressure UV Hg lamp with an electric rating from 8 to 100 W.
ITEM 8. The process of any of the preceding ITEMS, wherein the UV irradiation step with peroxygen further forms particles of metal hydroxides with the metal liberated from said metal-cyanide complex, and wherein the process further includes removing said particles of metal hydroxides from the treated effluent in said separating step or removing said particles of metal hydroxides from the irradiated effluent in a different separation step prior to contacting with the solid adsorbent.
ITEM 9. The process of any of the preceding ITEMS, wherein the peroxygen used during the irradiation step comprises or consists of H202, and wherein H202 is used in a H202:CN molar ratio of at least 2:1, preferably at least 5:1, more preferably at least 10:1, compared to cyanide in the effluent which is free and which can be liberated from one or more of said metal-cyanide complexes during UV irradiation.
ITEM 10. The process of any of the preceding ITEMS, wherein the adsorbent comprises a calcium-deficient hydroxyapatite with a Ca/P ratio more than 1.5 and less than 1.67, preferably wherein the calcium- deficient hydroxyapatite is synthetically made.
ITEM 11. The process of ITEM 10, wherein the adsorbent further comprises calcium carbonate in an amount between 0.5 to 20 wt% and/or contains less than 1 wt% Ca(OH)2.
ITEM 12. The process of any of the preceding ITEMS, wherein the solid adsorbent comprises a synthetic hydroxyapatite composite, said synthetic hydroxyapatite composite comprising a hydroxyapatite and at least one additive which is present during the hydroxyapatite synthesis.
ITEM 13. The process of ITEM 12, wherein the at least one additive in the synthetic hydroxyapatite composite is embedded or incorporated into or coated onto the hydroxyapatite.
ITEM 14. The process of ITEM 12 or 13, wherein the at least one additive comprises at least one activated carbon, iron (such as in the form of metal, salt, oxide, oxyhydroxide, or hydroxide), or combinations thereof.
ITEM 15. The process of any of ITEM 12-14, wherein the solid adsorbent comprises:
- two or more synthetic hydroxyapatite composites, wherein the additives in the synthetic hydroxyapatite composites are different; preferably wherein at least one of the additives in a first synthetic hydroxyapatite composite comprises an activated carbon or blend of two or more activated carbons, and another additive in a second synthetic
hydroxyapatite composite comprises iron (such as in the form of metal, salt, oxide, oxyhydroxide, or hydroxide); or
- a blend of at least one synthetic hydroxyapatite composite and a synthetic hydroxyapatite made without additive, wherein the at least one additive in the synthetic hydroxyapatite composite comprises at least one activated carbon, iron (such as in the form of metal, salt, oxide, oxyhydroxide, or hydroxide), or combinations thereof.
ITEM 16. The process of any of the preceding ITEMS,, wherein the contacting step with the solid adsorbent comprising apatite is carried out at a pH from 6.5 to 10, preferably a pH from 7 to 9.5, more preferably a pH from 7 to 9, yet more preferably a pH from 7.2 to 8.8, still more preferably a pH from 7.5 to 8.8, yet still more preferably a pH from 7.5 to 8.5.
ITEM 17. The process of any of the preceding ITEMS, wherein the contacting step with the solid adsorbent comprising apatite is carried out by mixing the solid adsorbent in the irradiated effluent with a content from 1 to 10 wt% of solid adsorbent, preferably from 2 to 5 wt% of solid adsorbent.
ITEM 18. The process of any of the preceding ITEMS, further comprising reducing the pH of at least a portion of the irradiated effluent with an acid (such as sulfuric acid or hydrochloric acid) before contacting with the solid adsorbent. ITEM 19. The process of any of the preceding ITEMS, wherein the contacting with the adsorbent is carried out in a mixed tank or a tank where its content is recirculated, and wherein the solid adsorbent is in the forms of particles which are suspended in water in the tank.
ITEM 20. The process of any of ITEMS 1-19, wherein the contacting with the solid adsorbent and the irradiation step are carried out in different units.
ITEM 21. The process of any of ITEMS 1-19, wherein the contacting with the adsorbent (adsorption) and the irradiation step are carried out in a same unit. ITEM 22. The process of ITEM 21, wherein the combined UV irradiation step with peroxygen and the contacting step with solid adsorbent (adsorption) are carried out at a pH from 7 to 10 or from 7.5 to 10, or from 8 to 10, preferably a pH from 8to 9.5 or from 8.5 to 9.5, more preferably a pH from 8.5 to 9.
ITEM 23. The process of any of ITEMS 1-19, wherein the contacting step with the adsorbent (adsorption step) and the separation step are carried out in a same unit, preferably wherein the unit is a settler, and wherein the solid adsorbent is added to the settler in a zone to allow contact with the treated effluent to remove the metallic ions and for the solid adsorbent to settle after contact.
ITEM 24. The process of any of the preceding ITEMS, wherein contacting at least a portion of the irradiated effluent (adsorption step) with a solid adsorbent comprising apatite is effective to remove at least part of said metallic ions containing one or more metals selected from the group consisting of Al, Ag, Ba, Be, Ce, Co, Cd, Cu, Cr, Fe, Hg, La, Li, Mn, Mg, Mo, Ni, Pb, Pd, Rb, Sb, Sn, Sr, Th, Ti, U, V, Y, Zn, As, B, F, Se, and combinations thereof.
ITEM 25. The process of any of the preceding ITEMS, wherein the water stream further comprises organic contaminants, particularly those of PAHs, phenolic compound, naphtol and derivatives, and wherein the contacting step (adsorption step) removes at least a portion of said organic contaminants.
ITEM 26. The process of any of the preceding ITEMS, wherein separating the treated effluent includes settling.
ITEM 27. The process of any of the preceding ITEMS, wherein separating the treated effluent includes adding a flocculant to the treated effluent before or during settling.
ITEM 28. The process of any of the preceding ITEMS, wherein the peroxygen used during the irradiation step comprises or consists of H202, and wherein the H202 content in the effluent is from 10 to 1,000 ppm, preferably from 25 to 750 ppm, preferably from 40 to 500 ppm, yet more preferably from 50 to 400 ppm, most preferably from 100 to 400 ppm. ITEM 29. The process of ITEM 28, wherein H202 is injected periodically into a circulation loop hydraulically connected to a photoreactor where the irradiation takes place or to a tank in such a circulation loop in order for H202 content in the effluent to be from 10 to 1,000 ppm, preferably from 25 to 750 ppm, preferably from 40 to 500 ppm, yet more preferably from 50 to 400 ppm, most preferably from 100 to 400 ppm.
ITEM 30. The process of any of the preceding ITEMS, further comprising carrying out the UV irradiation step in the presence of a peroxygen in an UV irradiation unit which is in fluid circulation with a buffer tank, wherein at least a portion of the irradiated effluent flows to the buffer tank and back to the UV irradiation unit.
ITEM 31. The process of ITEM 30, wherein the at least a portion of the water stream which is to be irradiated with ultraviolet light in the presence of a peroxygen is first fed to the buffer tank before being fed to the UV irradiation unit.
ITEM 32. The process of any of the preceding ITEMS, wherein the UV irradiation step is carried out in the presence of peroxygen in a plurality of UV units operated in series, each UV unit comprising a UV lamp.
ITEM 33. The process of any of the preceding ITEMS, further comprising carrying out an adsorption step as a pre-treatment prior to the UV irradiation step in order to remove metals, organics and/or colored species from the at least portion of the water feedstream prior to being directed to the UV irradiation step. ITEM 34. The process of ITEM 33, wherein the adsorption step carried out on the at least portion of the irradiated effluent after the UV irradiation step and the adsorption step carried out as a pre-treatment prior to the UV irradiation step are both performed in a same adsorption unit using the solid adsorbent comprising apatite.
ITEM 35. The process of ITEM 34, wherein the solid adsorbent used in the adsorption unit comprises a synthetic hydroxyapatite composite with activated carbon.
ITEM 36. The process of any of the preceding ITEMS, wherein the UV irradiation step further generates bicarbonate and nitrogen gas from cyanates formed by the UV peroxidation of the metal-cyanide complexes.
ITEM 37. The process of any of the preceding ITEMS, wherein the irradiation with ultraviolet light is carried out with a UV lamp, preferably a Hg lamp, having a power of at least 55W, preferably of at least 95W. ITEM 38. The process of any of the preceding ITEMS, wherein the peroxygen used during the irradiation step comprises or consists of H202, and wherein the H202 content in the water stream to be treated is at least 100 ppm.
EXAMPLES
The examples, the description of which follows, serve to illustrate the invention.
In these examples, the pH measurements were made using a WTW Sentix 41 electrode (pH 0-14, temperature: 0 °C-80 °C), a pH meter WTW pH3l 10.
The calibration of the equipment was made using three buffer solutions: at pH 4.0 (batch Dulco test-0032) Prominent, a WTW pH 7.0 (WTW D-82362) and at pH 10.01 Hach (cat 27702). Note: If multiple sample measurements were to be made with the same electrode, the electrode was rinsed with deionized water between each measurement.
The particle size measurement was carried out on a Beckman Coulter LS 230 laser diffraction particle size analyser (laser of wavelength 750 nm) on particles suspended in water and using a size distribution calculation based on Fraunhofer diffraction theory (particles greater than 10 pm) and on Mie scattering theory (particles less than 10 pm), the particles being considered to be spherical.
The BET specific surface area was determined by gas adsorption on a Micromeritics ASAP2020 machine. Before the analysis, the samples (0.7 to 1 g) are pretreated under vacuum at 250°C until a stable vacuum of 4-5 pbar has been achieved. The measurements were carried out using nitrogen as adsorbent gas at 77°K via the volumetric method, according to the ISO 9277: 2010 standard (Determination of the specific surface area of solids by gas adsorption - BET method). The BET specific surface area was calculated in a relative pressure (R/R0) range varying from around 0.05 to 0.20.
Unless stated otherwise, analysis of metal contents in water samples was carried out after the samples were filtered with a 0.45 pm filter by Inductively Coupled Plasma Mass Spectrometry (ICP-MS).
Example 1
Synthesis of apatite-containing adsorbents
la. Synthesis of hydroxyapatite adsorbent (without additive)
In this example, a hydroxyapatite material was made under similar conditions as those described in example lb of WO2015/173437 patent application by SOLVAY SA. This hydroxyapatite (to be used as adsorbent) is labelled“HAPi”. The process used two steps. In the first step, limestone was dispersed in water at 20-25°C in a 5-liter reactor (with baffles). Then H3PO4 (75%) was added to this suspension and the mixture was stirred at 700 rpm. The first step used an overall Ca/P molar ratio of about 1. The goal of this first step was to attack the limestone to make a brushite type structure. At the end of the addition of acid, the second step was initiated by heating the mixture up to about 50°C. A 25 wt% suspension of Ca(OH)2 was then added to maintain the pH of the suspension at a maximum 8.9. The second step used an overall Ca/P molar ratio of about 1.67. The goal of this second step was to convert the brushite type structure created in the first step to a hydroxyapatite structure in the second step. The reaction time was 120 minutes (2 hrs). After the reaction time, the suspension was continually stirred at half the stirring speed than was used in the first step to allow it to cool down to 20-25°C.
l.b. Synthesis of hydroxyapatite composite with activated carbon
A hydroxyapatite composite with activated carbon (additive) was made using Pulsorb C from Chemviron as the source of activated carbon. The content of activated carbon in the hydroxyapatite composite was about 10% by weight. This hydroxyapatite composite (to be used as adsorbent) is labelled“BHAPi”.
The preparation of the composite with activated carbon (BHAPi) was carried out in a similar manner as in the Example l.a., except that the activated carbon was added during the synthesis of the hydroxyapatite during the lime addition step (2nd step) after the pH had risen to about 8-9 and after the reaction medium was heated to +/- 50 °C. The activated carbon was added in the form of a powder. The reactor used for this synthesis was a baffled 200-L reactor. No significant change during the synthesis of the composite (compared to the synthesis as described in Example l.a.) is noted apart from this addition of activated carbon during the pH plateau in the 2nd step.
The solid portion of the suspension in the second step remained the same, at about 18wt% by weight. The pH used for the making of the composite was similar to that of hydroxyapatite without additive, namely a range between pH 6.5 and 12, and preferred being maintained between 8 and 9. For the BHAPi sample, the temperature for the first step was 20°C and the temperature for the second step was maintained at 50°C. l.c. Porosity and particle size
The porosity characteristics of the HAPi sample (without additive) and BHAPi composite (with activated carbon“A.C.”) are reported in TABLE 2. TABLE 2
Figure imgf000063_0001
Example 2 (not in accordance to the invention)
Adsorption of metal contaminants from ore processing water without prior UV peroxidation treatment
The effectiveness of adsorption of metals on the HAPi adsorbent was tested on two ore processing water streams: WW1 and WW2. The various metal contents of these industrial water samples WW1 and WW2 were measured by ICP-MS and are provided before treatment and after the adsorption with HAPi adsorbent in TABLE 3. These samples were not treated by UV peroxidation before adsorption. The % removal for Cu, Fe, and Ni was calculated from the metal contents measured before and after adsorption with HAPi of WW1 and WW2 and typical % removal values for these 3 metals are also provided for comparison in TABLE 3. TABLE 3
Figure imgf000063_0002
* * % removal data on water sample from metal recuperation and water sample from powder coating of metals from Figures in « EVALUATION OF EFFICIENCY OF Capterall™ FOR THE REMOVAL OF HEA VY METALS ON INDUSTRIAL WASTEWATER », April 2015, by Vito NV, available online at https ://www.solvay. com/en/binaries/Capterall%20 Vito %2 OStudy-33705 O.pdf.
It was observed that in these ore processing effluents WW1 and WW2, the adsorption on hydroxyapatite adsorbent HAPi was much less efficient ( from 0 to 19 % removal) than what would be typically observed % removal (> 90) for Cu, Fe, and Ni.
Based on this assessment, it was believed that these metals may have been complexed with cyanide in the water streams WW1 and WW2, making for instance some moderately strong and strong metal cyanide complexes in anionic form with iron, nickel and copper. It appeared that these ionic complexes were difficult to remove by contacting with a hydroxyapatite adsorbent. An adsorption step carried out alone would not be successful in reducing these metals content in these water streams before discharge without breaking these complexes down to liberate the core metal ions from the complexes.
Example 3 (in accordance to the invention)
UV/H2O2 treatment followed by adsorption for removal of cyanide and metal contaminants from ore mining waters
The removal of cyanides and metal contaminants was tested on the same two ore processing waters WW1 and WW2, wherein the removal of cyanides was carried out in a UV/H2O2 unit, and after a pH adjustment, the irradiated effluent sample was directed to an adsorption either with HAPi adsorbent or with BHAPi adsorbent comprising 10 wt% Pulsorb C activated carbon (see Examples l.a and l.b).
Schematically, the tests were carried out in a method similar to what is illustrated in FIG.l. About 1.5 liters of a water stream (WW1 or WW2) was placed in a UV/H2O2 reactor at a pH of about 9.5. This alkaline pH was selected to avoid the release of HCN gas during this UV/H2O2 treatment. The mixing in this reactor was done by recirculating a portion of the effluent with an external pump in order to homogenize the reactor content. The UV/H2O2 treatment was carried out for 1 hour residence time using a low pressure UV Hg light operated at 95W and at a wavelength of 254 nm. A solution of H2O2 (about 30 wt% with a density of 1.1) was added to the UV/H2O2 reactor in increments, that is to say adding an equal portion (1/3) 3 times during the course of the UV/H2O2 reaction, first at time 0, then at time = 15 min and finally at time=30 minutes. Two H202:CN molar ratios were tested at 5:1 and 10:1. After a residence time of 1 hour, a portion (1 liter) of the irradiated water was extracted from the initial 1.5 L. The pH of this l-L irradiated water was adjusted to 7.6 by addition of hydrochloric acid (1 N).
A first portion (400 ml) of this pH-adjusted effluent was used for carrying out the adsorption test with 2 wt% of the solid adsorbent HAPi, and another portion (400 ml) of this pH-adjusted effluent was used for carrying out the adsorption test with 2 wt% of the solid BHAPi adsorbent (hydroxyapatite composite). The pH at the end of these two adsorption steps was about 8.1-8.2.
Aliquots of these various waters were taken out for analysis of metal contents by ICP-MS. Each of these aliquots was filtered through a 0.45 micron membrane before the metal content was measured.
WW1 had an initial free CN content of 5.8 mg/l and an initial pH of 9.4.
WW2 had an initial free CN content of 8 mg/l and an initial pH of 9.6.
For the treatment of WW1 and WW2, TABLE 4 and TABLE 5
respectively provide the content of several metals (Ba, Cu, Fe, Mn, Ni, Se, Zn) measured by ICP-MS of WW1 and WW2 at different stages of the process:
1. “as is’ before being exposed to UV/ H202,
2. after being treated by the UV/H202,
3. after the irradiated solution being contacted with HAP or
4. after the irradiated solution being contacted with BHAP .
The % removal in TABLES 4 & 5 was calculated based on the difference of the measured value (2) of the metal content after the UV/H202 treatment and the value measured after the adsorption test (3 for HAPi) or (4 with BHAPi) divided by the same measured value (2).
It was observed that there was not much impact of the H202:CN ratio (either 5 or 10) on the % removal for each metal.
For the treatment of WW1:
For Ba removal according to the process of the present invention, the % removal was high in the 95-96 % with the BHAPi (composite) adsorption and with HAPi adsorption.
For Cu removal according to the process of the present invention, the % removal was high in the 97 % with the BHAPi (composite) adsorption but the % removal was poor (15% & 21%) with HAPi adsorption.
For Fe removal according to the process of the present invention, the % removal was high in the 98 % for either of BHAPi (composite) and HAPi adsorptions. For Mn removal according to the process of the present invention, the % removal was high in the 92-98 % for either of BHAPi (composite) and HAPi adsorptions.
For Ni removal according to the process of the present invention, the % removal was high in the 93 % with the BHAPi (composite) adsorption, but there was no removal (0%) with HAPi adsorption.
For Se removal according to the process of the present invention, the % removal was moderately low in the 62-65% with the BHAPi (composite) adsorption but the % removal was lower (42-46 %) with HAPi adsorption.
For Zn removal according to the process of the present invention, the % removal was high in the 92-93 % with the BHAPi (composite) adsorption and with HAPi adsorption.
TABLE 4 : treatment of WW1
Figure imgf000067_0001
For the treatment of WW2:
For Ba removal according to the process of the present invention, the % removal was high in the 89-96 % with the BHAPi (composite) adsorption and with HAPi adsorption.
For Cu removal according to the process of the present invention, the % removal was moderate in the 54-55 % with the BHAPi adsorption but the % removal was very poor (11% & 9%) with HAPi adsorption.
For Fe removal according to the process of the present invention, the % removal was moderate in the 41-42 % with the BHAPi adsorption but the % removal was very poor (26-27%) with HAPi. For Mn removal according to the process of the present invention, the % removal was high in the 87-90 % with the BHAPi (composite) adsorption and with HAPi adsorption.
For Ni removal according to the process of the present invention, the % removal was high in the 85-90 % with the BHAPi adsorption but the % removal was poor (5%) with HAPi adsorption.
For Se removal according to the process of the present invention, the % removal was moderately low in the 33-46% with the BHAPi and HAPi adsorption.
For Zn removal according to the process of the present invention, the % removal was very high in the 99-100 % with the BHAPi (composite) adsorption and with HAPi adsorption.
TABLE 5: treatment of WW2
Figure imgf000068_0001
Figure imgf000068_0002
Example 4
Synthesis of apatite-containing adsorbents
4.a. Synthesis of hydroxyapatite adsorbent (without additive)
Another hydroxyapatite material labelled“HAP2” was made in the similar manner as previously described for Example l.a, except that the synthesis was arried out in a 200-L vessel, the same vessel as described in Example l.b.
4.b. Synthesis of hydroxyapatite composite with activated carbon
Another hydroxyapatite composite labelled“BHAP2” containing activated carbon (additive) was made using 10 wt% Pulsorb C from Chemviron in the same manner as previously described for Example l.b in the same 200-L vessel. 4.c. Porosity and particle size
The porosity characteristics of the HAP2 sample (without additive) and BHAP2 composite (with activated carbon“A.C.”) are reported in TABLE 6. TABLE 6
Figure imgf000069_0001
Example 5 (not in accordance to the invention)
Adsorption of metal contaminants from ore processing waters without UV/H2O2 pretreatment
The effectiveness of adsorption of specific metals (Co, Cu, Fe, and Ni) on the HAP2 and BHAP2 adsorbents (see examples 4.a and 4.b) was tested on two ore processing water streams: WW3 and WW4.
The adsorption step was carried out as follows. In a 200-ml water sample, 7 g HAP2 (or 7.1 g BHAP2) were mixed for 1 hour at 10 rpm at a pH of 8.8 (corresponding to an equivalent loading of 20 g of dry matter/L) following by decantation for 10 minutes, and the supemate water was filtered using a 45-mih syringe filter before measuring the metal contents.
The various metal contents were measured by ICP-MS and the results are provided before any treatment and after the adsorption with HAP2 and BHAP2 adsorbents in TABLE 7 for the water sample WW3 and in TABLE 8 for the water sample WW4. These samples were not treated by UV peroxidation before adsorption. The % removal for Co, Cu, Fe, and Ni was calculated from the metal contents measured before (initial content) and after adsorption (final content) with HAP2 and BHAP2 of the ore processing water streams WW3 and WW4, dividing by their respective initial content.
TABLE 7
Figure imgf000070_0001
As observed previously, the hydroxyapatite HAP2 had very limited activity because it only treats significantly the Fe with removal of 74%. A Cu reduction of 5% was also observed but remained low in comparison with the amount of Cu present in the water sample WW3.
The contact with HAP2 was ineffective on Co and Ni.
The hydroxyapatite composite BHAP2 had better processing capabilities for Ni, Cu and Fe present in the water sample WW3 with respectively 100%, 93% and 74% removal, respectively.
No Co removal with BHAP2 was observed for the water sample WW3 which was not pretreated with UV peroxidation.
It should also be noted that the filtration of WW3 removed 37% of the Fe species which means that Fe was present in soluble form but also in the form of suspended solids. TABLE 8
Figure imgf000071_0001
For the water sample WW4, the use of HAP2 resulted in a removal of 95% for Cu and 73% for Ni. This is in contrast with what was observed for WW3 when HAP2 could not remove these metals.
BHAP2 resulted in a removal of 96% for Cu and 73% for Ni from WW4, and these removals were similarly (albeit slightly lower) for Cu and Ni compared to the WW3, to what was observed with HAP2.
Both HAP2 and BHAP2 were ineffective at removing Fe and Co from the water sample WW4.
The improved efficiency of removal for Ni and Cu from WW4 and the inefficacy for Fe from WW4 may be due to a change in the balance of complexation of these metallic elements.
Example 6 (in accordance to the invention)
UV/H2O2 treatment of an ore processing water followed by adsorption
Tests were carried out in a 3l6-stainless steel 1.7- liter photoreactor in which a UV-C lamp was inserted. The UV lamp used in the photoreactor was a Philips 95W UV-C lamp (with a UV-C power of 27W), respectively. In the center of the reactor, the UV lamp was protected from the water stream by a quartz sheath. The reactor was equipped with a jacket to regulate the temperature of the water stream inside the photoreactor.
During the tests, there was a loop connecting the reactor to a buffer tank permitting a recirculation of the water stream (up to 4 hours depending on the tests) using a recirculation pump between the reactor and the buffer tank. A volume of 2.4 L in the buffer tank allowed a 30 L/h flow rate in the loop.
For the tests including I¾02, a 30 wt% FI202 solution was injected into the buffer tank to achieve a certain concentration of H202 in the effluent entering the photoreactor, and the H202 was mixed for about 1 minute in the tank before the recirculation pump was started.
After a given time for UV peroxidation to take care (generally about 240 m inutes of recircul ation), a 200-ml aliquot was withdrawn from the tank and submitted to adsorption as described in Example 5. In the 200-ml water aliquot, about 7 g HAP2 or BHAP2 were mixed for 1 hour at 10 rpm at a pH of 8.8 (corresponding to an equivalent loading of 20 g of dry matter/L) following by decantation for 10 minutes, and the aqueous supemate was filtered using a
45-Lim syringe filter before measuring the metal contents via ICP-MS.
To determine the UV dose received by the effluent, it was important to correctly reference the flow rate and the volume of solution. It was also important to ensure that during recirculation and injections of H202, the buffer tank was well stirred to avoid dead volume (i.e., zones that did not circulate in the reactor) and in order to disperse the H202 homogeneously.
A final water aliquot after the adsorption step was filtered using a 0.45 pm syringe filter for analysis of metals via ICP-MS.
The % removal in TABLES 9 & 10 was calculated based on the difference of the initial value of the various metal contents measured by ICP-MS in the ore processing water stream WW3 prior to any treatment and the final value obtained after the adsorption (TABLE 9 with HAP2 & TABLE 10 with BHAP2) divided by the same initial value. The UV peroxidation step in this example lasted 240 minutes (4 hours).
TABLE 9
Figure imgf000072_0001
* : frequency of H202 injection = 20 min
** : % removal
It can be seen in TABLE 9 that photolysis (UV only) improved slightly the removal in Co but especially in Cu with respectively 5% and 49% removal at the end of the tests. This phenomenon could be expl ained by the ability of UV to degrade and dissociate complexes containing Cu and Co metals. The UV could also influence the degree of oxidation of the free metal in solution. By modifying the degree of oxidation of these metal s, the UV also can modify the metal properties including its precipitation pH for example. However, in these tests with UV only, there was no efficiency on removal of Ni, nor was there any added benefit for the removal of Fe. The removal on Co was still very small. Even though the results with Cu was better with UV, it still was not achieving the results obtained with the peroxygen was used in conjunction with the UV.
Indeed, when H202 was incorporated into the pretreatment process with UV, the removals in Co, Cu and Ni increased significantly with respectively 50%, 100% and 100%. It is speculated that the activation of H202 by UV generated radicals and thus accelerated the process of dissociation of metal complexes. Once free in solution, these metals could be easily captured by the apatite adsorbent HAP2. But in comparison with the improved removal obtained for Cu, Co and Ni, the benefit of using H202 in the photo-oxidation treatment appeared low for Fe removal.
TABLE 10
Figure imgf000073_0001
* : frequency of H202 injection = 20 min
** : % removal
In the case of the results obtained with the hydroxyapatite composite with activated carbon (BHAP2) shown in TABLE 10, the same phenomenon as explained above with the hydroxyapatite adsorbent (HAP2 without A.C.) was observed with BHAP2, that is to say, there was an increase in the removal % brought in by the addition of H202 especially for Co but also for Fe.
For the Cu and Ni, there already was a very good removal efficacy with the hydroxyapatite composite with activated carbon (BHAP2) without the photolysis or H202 photooxidation, that there was some limited value in performing the UV or UV/H202 treatment prior to the adsorption with the hydroxyapatite composite with activated carbon (BHAP2). For the most stable metal complexes, such as those containing Co, which were not easy to remove by the hydroxyapatite adsorbent or hydroxyapatite composite, it seemed apparent that the addition of H202 with UV exposure was quite useful to accelerate the kinetics of removal these metal pollutants from ore processing contaminated waters.
Example 7 (in accordance to the invention)
Impact of H202 concentration on UV/H202 pretreatment of an ore processing water followed by adsorption
Tests were carried out as similarly described in Example 6. The concentration in H202 was varied from 0 to 400 ppm; the UV lamp was a Philips 95W UV-C lamp; the recirculation flow rate was 30 L/hr and the injection frequency of the H202 into the buffer tank was 20 minutes.
The % removal of targeted metals (Co, Cu, Fe, Ni) in TABLES 11 & 12 was calculated based on the difference of the initial value of the various metal contents measured by ICP-MS in the ore processing water stream prior to any treatment and the final value obtained after the adsorption (TABLE 11 with HAP2 & TABLE 12 with BHAP2) divided by the same initial value. The UV peroxidation step lasted 240 minutes (4 hours), except for the UV peroxidation step with 50 ppm H202 which was carried out for 180 min (3 hours).
TABLE 11
Figure imgf000074_0001
* : UV-C lamp power = 95W; frequency of H202 injection = 20 min;
recirculation flow rate = 30 L/hr
** : % removal
It can be seen from TABLE 11 that the UV/H202 pre-treatment significantly improved the recovery of metals when it was followed by an adsorption using the hydroxyapatite adsorbent (HAP2). This confirmed that the metals were present largely under the complex form in the ore processing water. By performing a UV/H2O2 oxidation before adsorption, one can destabilize the metal complexes, "free" the metals and then remove these‘freed’ metals from the water with the adsorbent. It was also noted that the higher the concentration of H2O2 used in the UV/H2O2 pretreatment, the greater benefit in metal removal is observed, especially for the most stable metal complexes such as those containing Co.
TABLE 12
Figure imgf000075_0001
* : UV lamp power = 95W; frequency of H202 injection = 20 min; recirculation flow rate = 30 L/hr
** : % removal
***: value omitted due to analytical problem
Looking at TABLE 12, similarly to the results obtained with UV/H2O2 followed by adsorption with the hydroxyapatite adsorbent (HAR2), the higher the concentration of H2O2, the higher the removal in metals with the hydroxyapatite composite BHAP2. In the case of BHAP2, the removals (without UV or UV/H2O2 oxidation) were already significant for the following metals: Cu, Fe and Ni, but very poor for Co. Thanks to photo-oxidation by UV/H2O2, the metal removal increased signifi cantly to achieve, in the case of the 400 ppm H2O2 test, 100% removal for Cu, Fe and Ni and 49% removal for Co.
Example 8 (in accordance to the invention)
Impact of UV lamp power on UV/H2O2 treatment of an ore processing water followed by adsorption
Tests were carried out as similarly described in Example 6. The UV lamps used in the UV/H2O2 step were Philips UV-C lamps with either 55W power or 95 W power (equivalent in UV-C power of 17W or 27 W). The recirculation flow rate was 30 L/hr ; the injection frequency of the H2O2 into the buffer tank was 20 minutes; and the concentration in FLO2 was 200 ppm . The UV peroxidation step using the recirculation loop lasted 240 minutes (4 hours). The % removal in TABLES 13 & 14 was calculated based on the difference of the initial value of the various metal contents measured by ICP-MS in the ore processing water stream prior to any treatment and the final value obtained after the adsorption (TABLE 13 with HAP2 & TABLE 14 with BHAP2) divided by the same initial value.
TABLE 13
Figure imgf000076_0001
* : [H202] = 200 ppm; frequency of H202 injection = 20 min; recirculation flow rate = 30 L/hr
** : % removal
As shown in TABLE 13 using the hydroxyapatite adsorbent (HAP2) after the UV/H202 treatment, the impact of the UV-C lamp power was significant for the most stable metal complexes such as those with Co. Indeed, in increasing the power of the lamp from 55 W to 95 W (with equivalent UV-C power of 17W to 27W), the removal of Co increased from 24% to 50%.
However, for the metallic complexes which would be considered easier to destabilize with photo-oxidation such as those containing Cu, Ni and Fe, there was a limited added value to the increase in UV lamp power because the removal yield in the end were very similar if not identical .
TABLE 14
Figure imgf000076_0002
* : [H202] = 200 ppm; frequency of H202 injection = 20 min; recirculation flow rate = 30 L/hr
** : % removal
In the case of the adsorption with the hydroxyapatite composite (BHAP2) after the UV/H202 treatment shown in TABLE 14, the power of the UV lamp only impacted significantly the removal of Co with a yield that increased from 14% to 40% while the power of the lamp increased from 55W to 95W (with equivalent UV-C power of 17W to 27 W). For Cu, Ni and Fe, the removal yields after 240 min of UV/H2O2 treatment were comparable with either UV lamp power.
In conclusion, there was a significant influence of the power of the UV lamp on the performance of metal removal when the metal such as Co was in a form (complexes) which was difficult (stable) to break down, but there was no observed influence on metals forming complexes that were less stable, such as Cu, Fe, and Ni.
Example 9 (in accordance to the invention)
Impact of time on UV/H2O2 treatment of an ore processing water followed by adsorption
All the results presented thus far from Examples 5 to 8 have been compared on the basis of a 240-min time frame for the UV/H2O2 treatment.
Tests were carried out as similarly described in Example 7 with either 150 ppm or 200 ppm H2O2 over a time period for the UV/H2O2 treatment from 60 minutes to 240 minutes, while keeping the adsorption step identical
(see Example 5 for adsorption conditions). The UV lamp was a Philips 95W UV-C lamp (eq. power 27W for UV-C); the recirculation flow rate was 30 L/hr and the injection frequency of the H2O2 into the buffer tank was 20 minutes.
The % removal with HAP2 and UV/H2O2 (using 150 ppm H2O2) in
TABLE 15 and with HAP2 and UV/H2O2 (using 200 ppm H2O2) in TABLE 16 was calculated based on the difference of the initial value of the contents of various metal measured by ICP-MS in the ore processing water stream prior to any treatment and the final value obtained after the adsorption based on the different times by the same initial value, and they are reported in these tables as a function of UV peroxidation time (60-240 min). TABLE 15 : Treatment with 150 ppm H202 over UV/H202 pretreatment time
Figure imgf000078_0001
* : UV lamp power = 95W (eq. 27W UV-C); frequency of H202 injection =
20 min; recirculation flow rate = 30 L/hr
** : % removal
TABLE 16 : Treatment with 200 ppm H202 over UV/H202 pretreatment time
Figure imgf000078_0002
* : UV lamp power = 95W (eq. 27W UV-C); frequency of H202 injection =
20 min; recirculation flow rate = 30 L/hr
** : % removal
As illustrated in TABLES 15 and 16, it was observed that the removal maxima were obtained after 60 minutes of UV/H202 treatment for Cu, Fe and Ni. This indicates that the complexes formed by these three metals are easily dissociable via the UV/H202 treatment to allow the metals recovery by the subsequent adsorption step.
Only Co (as previously observed) required a longer UV/H202 treatment time in order to obtain a significant improvement in removal efficacy. This provides evidence to the hypothesis that the complexes formed by Co were more difficult to dissociate to free the Co metals. It is also possible that Co may quickly form complexes with degradation by-products of other pollutants in the treated water and in such instances, it would be possible to recover the Co, only when the degradation would be well-advanced.
The disclosure of all patent applications, and publications cited herein are hereby incorporated by reference, to the extent that they provide exemplary, procedural or other details supplementary to those set forth herein. Should the disclosure of any of the patents, patent applications, and publications that are incorporated herein by reference conflict with the present specification to the extent that it might render a term unclear, the present specification shall take precedence.
In the present application, where an element or component is said to be included in and/or selected from a list of recited elements or components, it should be understood that in related embodiments explicitly contemplated here, the element or component can also be any one of the individual recited elements or components, or can also be selected from a group consisting of any two or more of the explicitly listed elements or components. Any element or component recited in a list of elements or components may be omitted from such list. Further, it should be understood that elements, embodiments, and/or features of processes or methods described herein can be combined in a variety of ways without departing from the scope and disclosure of the present teaching, whether explicit or implicit herein.
Accordingly, the scope of protection is not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are a further description and are an addition to the preferred embodiments of the present invention.
While preferred embodiments of this invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit or teaching of this invention. The embodiments described herein are exemplary only and are not limiting. Many variations and modifications of systems and methods are possible and are within the scope of the invention.

Claims

1. A process for treating a water stream, preferably originating from a ore mining process, containing cyanide, metallic ions and metal-cyanide complexes having a stability constant K characterized by a logK at 25°C greater than 20, preferably greater than 30, more preferably greater than 35, said method comprising:
- irradiating at least a portion of the water stream at a pH greater than 7.0 with ultraviolet light in the presence of a peroxygen at a selected wavelength to form an irradiated effluent, wherein at least one of said metal-cyanide complexes undergoes photo-dissociation and liberates free cyanide from the complex in order for the free cyanide to be converted to cyanate and for the metal from the complex to be converted to an hydroxide form;
- contacting at least a portion of the irradiated effluent with a solid adsorbent comprising apatite to remove from the irradiated effluent at least part of said metallic ions to form a treated effluent; and
- separating the treated effluent from the solid adsorbent.
2. The process of claim 1, wherein the pH during irradiation is greater than 7 and up to 11, preferably from 8 to 11, more preferably from 8.5 to 10.5, yet more preferably from 9 to 10.5, even more preferably from 9.5 to 10.5, most preferably from 10 to 10.5.
3. The process of claim 1 or 2, wherein the at least one metal-cyanide complex which undergoes photo-dissociation contains a metal in the complex selected from the group consisting of Fe(II), Fe(III), Co(II), Ni(II), Cu(I), Cu(II), and Hg(II), preferably selected from the group consisting of Fe(II), Fe(III), Co(II), Cu(I), and Ni(II).
4. The process of any of the preceding claims, wherein said metal- cyanide complex which undergoes photo-dissociation is selected from the group consisting of hexacyanoferrate(II), hexacyanoferrate(III),
hexacyanocobaltate(III), tetracyanonickelate(II), tetracyanocuprate(II), and combinations thereof.
5. The process of any of the preceding claims, wherein during irradiation, the ultraviolet light has a wavelength in the region from 200 to 375 nm, preferably from 200 to 350 nm, more preferably from 200 to 300 nm, most preferably at 254 nm.
6. The process of any of the preceding claims, wherein the peroxygen used during the irradiation step comprises or consists of H202, and wherein the H202 is used in a H202:CN molar ratio of at least 2:1, preferably at least 5:1, more preferably at least 10:1, wherein CN in the ratio is the total cyanide content in the effluent which is free and which can be liberated from metal-cyanide complexes during UV irradiation.
7. The process of any of the preceding claims, wherein the peroxygen used during the irradiation step comprises or consists of H202, and wherein the H202 content in the effluent is from 10 to 1,000 ppm, preferably from 25 to 750 ppm, preferably from 40 to 500 ppm, yet more preferably from 50 to
400 ppm, most preferably from 100 to 400 ppm.
8. The process of any of the preceding claims, wherein the solid adsorbent comprises a calcium-deficient hydroxyapatite with a Ca/P ratio more than 1.5 and less than 1.67, preferably wherein the calcium-deficient
hydroxyapatite is synthetically made.
9. The process of any of the preceding claims, wherein the solid adsorbent comprises a synthetic hydroxyapatite composite, said synthetic hydroxyapatite composite comprising a hydroxyapatite and at least one additive which is present during the hydroxyapatite synthesis, preferably wherein the at least one additive in the synthetic hydroxyapatite composite is embedded or incorporated into or coated onto the hydroxyapatite.
10. The process of claim 9, wherein the at least one additive comprises at least one activated carbon, iron (such as in the form of metal, salt, oxide, oxyhydroxide, or hydroxide), or combinations thereof.
11. The process of any of the preceding claims, wherein the contacting step with the adsorbent comprising apatite is carried out at a pH from 6.5 to 10, preferably a pH from 7 to 9.5, more preferably a pH from 7 to 9, yet more preferably a pH from 7.2 to 8.8, still more preferably a pH from 7.5 to 8.8, yet still more preferably a pH from 7.5 to 8.5.
12. The process of any of the preceding claims, wherein the contacting step with the adsorbent comprising apatite is carried out by mixing the solid adsorbent in the irradiated effluent with a content from 1 to 10 wt% of solid adsorbent, preferably from 2 to 5 wt% of solid adsorbent.
13. The process of any of the preceding claims, wherein the contacting with the solid adsorbent is carried out in a mixed tank, and wherein the solid adsorbent is in the forms of particles which are suspended in the mixed tank.
14. The process of any of the preceding claims, wherein the contacting with the adsorbent and the irradiation step are carried out in different units.
15. The process of any of the preceding claims, wherein contacting the at least portion of the irradiated effluent with a solid adsorbent comprising apatite is effective to remove at least part of said ions containing one or more elements selected from the group consisting of Al, Ag, Ba, Be, Ce, Co, Cd, Cu, Cr, Fe,
Hg, La, Li, Mn, Mg, Mo, Ni, Pb, Pd, Rb, Sb, Sn, Sr, Th, Ti, U, V, Y, Zn, As, B, F, Se, and combinations thereof.
16. The process of any of the preceding claims, further comprising carrying out the UV irradiation step in the presence of a peroxygen in an UV irradiation unit which is in fluid circulation with a buffer tank, wherein at least a portion of the irradiated effluent flows to the buffer tank and back to the UV irradiation unit.
17. The process of claim 16, wherein the at least a portion of the water stream which is to be irradiated ultraviolet light in the presence of a peroxygen is first fed to the buffer tank before being fed to the UV irradiation unit.
18. The process of any of the preceding claims, wherein the UV irradiation step is carried out in the presence of a peroxygen in a plurality of UV units operated in series, each UV unit comprising a UV lamp.
19. The process of any of the preceding claims, further comprising carrying out an adsorption step as a pre-treatment prior to the UV irradiation step in the presence of a peroxygen in order to remove metals, organics and/or color from the at least portion of the water stream prior to being directed to the UV irradiation step.
20. The process of claim 19, wherein the adsorption step carried out on the at least portion of the irradiated effluent after the UV irradiation step and the adsorption step carried out as a pre-treatment prior to the UV irradiation step are both performed in a same adsorption unit using the solid adsorbent comprising apatite.
21. The process of claim 20, wherein the solid adsorbent used in the adsorption unit comprises a synthetic hydroxyapatite composite with activated carbon.
22. The process of any of the preceding claims, wherein the UV irradiation step further generates bicarbonate and nitrogen gas from cyanates formed by the UV peroxidation of the metal-cyanide complexes.
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CN110921899A (en) * 2019-12-06 2020-03-27 苏州淡林环境科技有限公司 Lithium hexafluorophosphate and low-fluorine lithium phosphate compound wastewater treatment process and device
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RU2811614C1 (en) * 2023-02-01 2024-01-15 Федеральное государственное бюджетное учреждение науки Институт теоретической и экспериментальной биофизики Российской академии наук (ИТЭБ РАН) METHOD FOR SORPTION TREATMENT OF WASTEWATER FROM POTASSIUM HEXACYANOFERRATES K3[Fe(CN)6] OR K4[Fe(CN)6]

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CN109081422A (en) * 2018-08-27 2018-12-25 南京泽辉环保科技有限公司 A method of utilizing low-concentration ammonia-nitrogen in ozone and micro calper calcium peroxide removal water body
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CN110921899B (en) * 2019-12-06 2022-04-19 苏州淡林环境科技有限公司 Lithium hexafluorophosphate and low-fluorine lithium phosphate compound wastewater treatment process and device
CN112047525A (en) * 2020-08-31 2020-12-08 营创三征(营口)精细化工有限公司 Method and system for breaking cyanogen in resin
CN112047525B (en) * 2020-08-31 2021-11-02 营创三征(营口)精细化工有限公司 Method and system for breaking cyanogen in resin
RU2811614C1 (en) * 2023-02-01 2024-01-15 Федеральное государственное бюджетное учреждение науки Институт теоретической и экспериментальной биофизики Российской академии наук (ИТЭБ РАН) METHOD FOR SORPTION TREATMENT OF WASTEWATER FROM POTASSIUM HEXACYANOFERRATES K3[Fe(CN)6] OR K4[Fe(CN)6]

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