OA21050A

OA21050A - Method for treating solid hazardous heavy metal-containing compositions.

Info

Publication number: OA21050A
Application number: OA1202200435
Authority: OA
Inventors: Patrycja KITA; Tanja Vojnovic; Tom Rames JØRGENSEN; Katrine Lie BØYESEN
Original assignee: Yara International Asa
Priority date: 2020-06-16
Filing date: 2021-06-16
Publication date: 2023-10-09

Abstract

The present disclosure discloses a method for converting a solid hazardous heavy metalcontaining composition into a solid non-hazardous heavy metal-containing composition and an aqueous composition essentially free of heavy metal. The method comprises the steps of a) mixing and dissolving the solid hazardous heavy metal-containing composition with an acid solution, thereby obtaining an hazardous heavy metal acid composition; b) precipitating the heavy metal from the hazardous heavy metal acid composition by: measuring the pH of the acid composition after a 13-fold dilution by volume using water, and adjusting the pH of the solid hazardous heavy metal-containing composition to at least 0.9 if the measured pH is below 0.9; and by reacting the hazardous heavy metal acid composition with a heavy metal-precipitation agent; and c) precipitating the heavy metal from the hazardous heavy metal acid composition by adjusting the pH value of the composition to a value of at least 0.9 if the pH measured in step b) is below 0.9 and by reacting with a heavy metalprecipitation agent; and d) separating out the heavy metal precipitate from the aqueous supernatant, whereby the solid inert heavy metalcontaining composition comprises the heavy metal precipitate and the aqueous composition essentially free of heavy metal comprises the aqueous supernatant. The heavy metalprecipitation agent comprises a diorganodithiophosphinic acid or the alkali metal or ammonia salts thereof represented by Formula 1
wherein R is a linear or branched hydrocarbon group selected from alkyl, aryl, alkylaryl, or aralkyl, and wherein the hydrocarbon group contains 3 to 20 carbon atoms, and M is H, alkali metal or ammonia. The present disclosure further relates to the use of the heavy metal-precipitation agent for converting the solid hazardous heavy metal-containing composition into the solid nonhazardous heavy metal-containing composition and the aqueous composition essentially free of heavy metal.

Description

METHOD FOR TREATING SOLID HAZARDOUS HEAVY METAL-CONTAINING COMPOSITIONS

FIELD OF THE INVENTION

The présent disclosure relates to the field of treating solid hazardous heavy metalcontaîning compositions.

BACKGROUND

Heavy metals such as cadmium, copper, nickel, lead, zinc and mercury are considered unacceptable above a certain level, depending on the application, because of their toxîcity and they thus hâve to be either completely removed or their levels hâve to be reduced significantly. Many processes hâve been developed over the years for their removal.

For example, cadmium is a naturally occurring element in the earth’s crust. in particular, the phosphate rock extracted from phosphate mines typically contains cadmium at levels between 0.15 to 507 mg/kg of phosphate rock having an average phosphorous (P₂O₅) content of about 30 weight% (Swe Swe Mar & Masanori Okazaki, Microchemical Journal 104 (17-21), September2012). Unless cadmium is removed from the phosphate rock prior to its processing in or during the nitro-phosphate process, the fertîlizers resulting from the process wili contain cadmium. Some forms of cadmium can be taken up by plants and, thereby, end up in the food chain. Cadmium can cause damage to lungs, kidneys, and bones. Therefore, it is essentîal to limit the level of cadmium in fertîlizers. The European Union is now considering a limit of 60 mg cadmium per kilogram of phosphorous (expressed as P₂O5). However, Finland is applying an even lower limit such as 21.5 mg of cadmium per kilogram of P₂Os.

The précipitation of heavy metals, such as cadmium in the nitro-phosphate process has previously been reported. US 4,986,970 discloses a method for removal of heavy metals, especially cadmium, primarily from a mother liquor made by the Odda process, using métal salts of dithiocarbonic acid-O-esters, referred to as xanthates.

US 2004/0179984 discloses a process and compositions to remove heavy métal ions, such as cadmium, copper, lead, nickel, arsenic, manganèse, zinc, and mercury ions from the wet phosphoric acid process. The process involves treating phosphoric acid prior to or after gypsum filtration with diorgano-dithiophosphinic acid (or alkaii métal or ammonia salts thereof), a first diorgano-dithiophosphoric acid (or alkaii métal or ammonia salts thereof) and optionally a second diorgano-dithiophosphoric acid (or alkaii métal or ammonia salts thereof), precipitating metals such as cadmium, copper, lead, nickel, arsenic, manganèse, zinc and mercury at a température from about 10 to about 85°C and preferably in the range of about 50 to about 80°C, and separating the fîltrate by either filtration or flotation.

EP 0091043 discloses the use of similar heavy métal removal agents as disclosed in US 2004/0179984 for the removal of cadmium by précipitation from the Odda process.

A problem associated to the précipitation of heavy metals is that they inevitably resuit in the formation of a heavy metal-containing composition as a solid composition that will in turn need to be disposed of. Such heavy metal-containing solid compositions, such as cadmium containing solid compositions, may leach out cadmium and other heavy metals thereby be harmful to the environment. In this respect, the EU Standard NS-EN 12457-2 enables one to classify solid compositions according to a leaching test procedure. Inert and non-hazardous heavy metal-containing compositions are defined in the EU Standard NSEN 12457-2 as compositions respectively leaching less than 0.04 and from 0.04 to 2.00 ppm of cadmium, or less than 0.5 ppm and from 0.5 to 5 ppm of arsenic, or less than 2 and from 2 to 50 ppm of copper, or less than 0.01 ppm and from 0.01 to 0.5 ppm of mercury, or less than 0.4 and from 0.4 to 10 ppm of nickel, or less than 0.5 ppm and from 0.5 to 10 ppm of lead, or less than 4 and from 4 to 50 ppm of zinc, into an aqueous solution, upon treatment ofthe composition according to the standard and which can safely be disposed without additional précautions. On the other hand, compositions leaching more than 2 ppm of cadmium, or more than 5 ppm of arsenic, or more than 50 ppm of copper, or more than 0.5 ppm of mercury, or more than 10 ppm of nickel, or more than 10 ppm of lead, or more than 50 ppm ofzinc, into an aqueous solution upon treatment ofthe composition according to the EU Standard NS-EN 12457-2, are to be classified as hazardous and shall require spécial disposai requirements. Clearly, the viability of a heavy métal extraction process, such as a cadmium extraction process, is inextricably linked to the classification (inert, nonhazardous or hazardous) of the heavy métal composition resulting from the précipitation thereof.

US 4,762,693 discloses a method of treating a cadmium containing waste in which the waste is worked up and transformed into ecologically reliable solid matter and a heavy métal concentrate. The method of the disclosure involves adjusting the pH to values such as 8.5 or 9 in order to separate out cadmium hydroxides. However, in US 4,986,970 it is taught that précipitation at pH 4-6 was not found to be practical because large amounts of précipitâtes of different phosphates then would occur. Similarly, in EP 0091043, it is taught that the treatment of mother acid in a higher pH range is impeded by the simultaneous occurrence of complex précipitâtes of phosphates, silica gel, calcium, magnésium, and aluminium compounds. Hence, it can be concluded that précipitation at pH values as high as 8.5 and 9.0 resuit in the problem of génération of high amounts of waste, including phosphates which could otherwise be used.

There exist, generally, other hazardous heavy métal compositions than compositions generated from the précipitation of cadmium from fertilizers melts and containing phosphorous. Therefore, the problem of leaching of heavy métal from heavy metalcontaining compositions is to be solved for ail types of hazardous cadmium-containing compositions.

Therefore, there remains the need for a solution to treat hazardous heavy metal-containing compositions, such as cadmium containing compositions, into non-hazardous heavy metalcontaining compositions. Said otherwise, there remains a need to fix heavy metals in compositions arising from the précipitation of those heavy metals: not only are the heavy metals to be precipitated to allow for the production of compositions with a level sufficiently low in heavy metals, also the resulting heavy métal precipitated composition is to be nonhazardous, meaning that the heavy metals must not leach from the heavy métal composition more than stated by the régulation standards, such that it can be safely disposed of.

SUMMARY OF THE INVENTION

According to one aspect is disclosed a method for converting a solid hazardous heavy metal-containing composition, comprisîng one or more heavy metals, into a solid nonhazardous heavy metal-containing composition and an aqueous composition essentially free ofthe one or more heavy metals. The method comprises the steps of: a) mixing and dissolving the solid hazardous heavy metal-containing composition with an acid solution, thereby obtaining an hazardous heavy métal acid composition; b) precipitating the heavy metals from the hazardous heavy métal acid composition by reacting the hazardous heavy métal acid composition with a heavy metal-precipitation agent at a pH of at least 0.9, measured after a 13-fold dilution by volume using water; in particular by: measuring the pH of the acid composition after a 13-fold dilution by volume in water and adjusting the pH of the solid hazardous heavy metal-containing composition to at least 0.9 if the measured pH is below 0.9; and reacting the hazardous heavy métal acid composition with a heavy metalprecipitation agent; and c) separating out the heavy métal precipitate from the aqueous supernatant, whereby the heavy métal precipitate is the solid non-hazardous heavy metalcontaining composition and the aqueous supernatant is the aqueous composition essentially free of heavy metals; wherein the heavy metal-precipitation agent comprises a diorgano-dithiophosphinie acid or the alkali métal or ammonia salts thereof, represented by Formula 1

S ^R^l .P--SM

Formula 1 and wherein R is a linear or branched hydrocarbon group selected from alkyl, aryl, alkylaryl, or aralkyl, and wherein the hydrocarbon group contains 3 to 20 carbon atoms, and M is H, alkali métal or ammonia.

For the purpose of this disclosure, a hazardous heavy metal-containing composition is defined as a composition leaching more than 2 ppm of cadmium, or more than 5 ppm pf arsenic, or more than 50 ppm of copper, or more than 0.5 ppm of mercury, or more than 10 ppm of nickel, or more than 10 ppm of lead, or more than 50 ppm of zinc, into an aqueous solution upon treatment of the composition according to a simplification of the European Standard NS-EN 12457-2, using 10 I of water per kg of the composition (the Modified EU Standard” for materials with particle size below 4 mm - as further specified below). For the purpose of this disclosure, it is sufffeient to measure, using the Modified EU Standard and from a solid composition, a level of leaching of more than 2 ppm of cadmium, or more than 5 ppm pf arsenic, or more than 50 ppm of copper, or more than 0.5 ppm of mercury, or more than 10 ppm of nickel, or more than 10 ppm of lead, or more than 50 ppm of zinc, in order to characterize the solid composition as hazardous. For ail practical purposes, anything that would be characterized as hazardous under the actual EU standard is likely to also be characterized as hazardous under the Modified EU Standard.

For the purpose of this disclosure, a non-hazardous heavy metal-containing composition is defined as a composition leaching 2 ppm or less of cadmium, or 5 ppm of less of arsenic, or 50 ppm or less of copper, or 0.5 ppm or less of mercury, or 10 ppm or less of nickel, or 10 ppm or less of lead, or 50 ppm or less of zinc, into an aqueous solution upon treatment of the composition according to the Modified EU Standard. For the purpose of this disclosure, it is sufficient to measure, using the Modified EU Standard and from a solid composition, a level of leaching of 2 ppm or less of cadmium, or 5 ppm of less of arsenic, or 50 ppm or less of copper, or 0.5 ppm or less of mercury, or 10 ppm or less of nickel, or 10 ppm or less of lead, or 50 ppm or less of zinc, in order to characterize the solid composition as non-hazardous. Such a composition may actually be non-hazardous or inert according to the EU Standard but for ail practical purposes, ail that is relevant is that the material is non-hazardous and the Modified EU Standard is sufficientfor most materials. For the purpose of this disclosure, an aqueous composition that is essentially free of heavy metals is an aqueous composition comprising less than 12 ppm, in particular less than 8 ppm, more in particular less than 4 ppm, most in particular less than 1 ppm by weight cadmium, or 5 ppm or less than arsenic, or 50 ppm or less of copper, or 0.5 ppm or less than mercury, or 10 ppm or less than nickel, or 10 ppm or less than lead, or 50 ppm or less than zinc.

Surprisingly, the inventors hâve found that the method ofthe disclosure provides a solution for converting a solid hazardous heavy metal-containing composition into a solid nonhazardous heavy metal-containing composition that can be safely disposed of: the heavy metals are more strongly fixed in the converted heavy metal-containing composition and the converted composition can, therefore, be stored without concerns of, for example under rainy conditions, the heavy metals leaching from the composition, the composition being, thereby, the source of a potentiai environmental hazard. In addition, the heavy métal concentration in the non-hazardous heavy metal-containing composition is higher than the heavy métal concentration in the original hazardous heavy metal-containing composition leading to the total mass and volume of the non-hazardous heavy metal-containing composition being, therefore, lower than the corresponding mass and volume of the hazardous solid heavy metal-containing composition. In other words, the method of the disclosure allows for a réduction of the amount of solid hazardous heavy metal-containing composition.

In one embodiment according to the method ofthe disclosure, the solid hazardous heavymetal containing composition is characterized in that it contains heavy metals and leaches more than 2 ppm of cadmium, or more than 5 ppm of arsenic, or more than 50 ppm of copper, or more than 0.5 ppm of mercury, or more than 10 ppm of nickel, or more than 10 ppm of lead, or more than 50 ppm of zinc, according to the Modified EU Standard.

In one embodiment according to the method ofthe disclosure, the solid hazardous heavy metal-containing composition is a cadmium-containing composition, in particular a cadmium-containing composition that leaches more than 2 ppm cadmium into an aqueous solution, according to the Modified EU Standard, and the solid non-hazardous heavy metalcontaining composition is a cadmium-containing composition, in particular a cadmiumcontaining composition that leaches 2 ppm or less cadmium into an aqueous solution, according to the Modified EU Standard, and the aqueous composition is essentially free of cadmium.

For the purposeof this disclosure, a hazardous cadmium-containing composition is defined as a composition leaching more than 2 ppm of cadmium into an aqueous solution, upon treatment of the composition according to a simplification of the European Standard NSEN 12457-2, using 10 I of water per kg ofthe composition (the “Modified EU Standard” for materials with particle size below 4 mm - as further specified below). For the purpose of this disclosure, it is sufficient to measure, using the Modified EU Standard and from a solid composition, a level of leaching of more than 2 ppm of cadmium, in order to characterize the solid composition as hazardous. For ail practical purposes, anything that would be characterized as hazardous under the actuai EU standard is likely to also be characterized as hazardous under the Modified EU Standard.

For the purpose of this disclosure, a non-hazardous cadmium-containing composition is defined as a composition leaching 2 ppm or less of cadmium into an aqueous solution, upon treatment of the composition according to the Modified EU Standard. For the purpose of this disclosure, it is sufficient to measure, using the Modified EU Standard and from a solid composition, a level of leaching of 2 ppm or less of cadmium, in order to characterize the solid composition as non-hazardous. Such a composition may actually be nonhazardous or inert according to the EU Standard but for ail practical purposes, ail that is relevant is that the material is non-hazardous and the Modified EU Standard is sufficient for most materials.

For the purpose of this disclosure, an aqueous composition that is essentially free of cadmium is an aqueous composition comprising less than 12 ppm, in particular less than 8 ppm, more in particular less than 4 ppm, most in particular less than 1 ppm by weight cadmium.

In one embodiment according to the method of the disclosure, the acid solution has a pK_aof less than 2.3.

In one embodiment according to the method ofthe disclosure, the solid hazardous heavy metal-containing composition further comprises from 1 to 10 weight% phosphorous and from 1 to 18 weight% calcium.

In one embodiment according to the method of the disclosure, the solid hazardous heavymetal containing composition is the end product of a précipitation process of heavy metals, such as the Odda process.

In one embodiment according to the method ofthe disclosure, the solid hazardous heavy metal-containing composition further comprises from 1 to 10 weight% phosphorous and from 1 to 18 weight% calcium, or is the end product of a précipitation process of heavy metals, such as the Odda process, and the pH in step b) is adjusted is adjusted if necessary to values ranging from 0.9 to 1.6, measured after a 13-fold dilution by volume using water. In one embodiment according to the method ofthe disclosure, R in Formula 1 is selected from the group consisting of cyclohexyl, isopropyl, isobutyl, n-propyl, octyl, hexyl, phenylethyl and 2,4,4 trimethylpentyL

In one embodiment according to the method ofthe disclosure, the heavy metat-precipitation agent is sodium diisobutyldithiophosphinate.

In one embodiment according to the method ofthe disclosure, there is solid sludge in the hazardous heavy métal acid composition acid and wherein, before the precipitating step b), the step of;

d) removing at least part of the solid sludge in the hazardous heavy métal acid composition;

is performed.

In one embodiment according to the method ofthe disclosure, the step e) comprises the step of:

e) adding a flocculating agent, thereby forming fiocculants, wherein the flocculating agent is added after the mixing and dissolving step a).

In one embodiment according to the method of the disclosure, the flocculating agent is added before the precipitating step b), and/or during the precipitating step b) and/or after the precipitating step b).

In one embodiment according to the method of the disclosure, the flocculating agent is added after the precipitating step.

In one embodiment according to the method of the disclosure, the flocculating agent is a cationic polymer.

According to another aspect is disclosed the use of a diorgano-dithiophosphfnic acid or the alkali métal or ammonia salts thereof, for converting a solid hazardous heavy metalcontaining composition into a solid non-hazardous heavy metal-containing composition and an aqueous composition essentially free of heavy metals. The diorgano-dithiophosphinic acid or the alkali métal or ammonia salts is represented by Formula 1

S

R\ll .P--SM

Formula 1 wherein R is a linear or branched hydrocarbon group selected from alkyl, aryl, alkylaryl, or aralkyl, and wherein the hydrocarbon group contains 3 to 20 carbon atoms, and M is H, an alkaii métal or ammonia.

In one embodiment according to the use of the disclosure, the solid hazardous heavy metal-containing composition is a cadmium-containing composition, the solid nonhazardous heavy metal-containing composition is a cadmium-containing composition and the aqueous composition is essentially free of cadmium.

In one embodiment according to the use of the disclosure, R in Formula 1 is selected from the group consisting of cyclohexyl, isopropyl, isobutyl, n-propyl, octyl, hexyl, phenylethyl and 2,4,4-trimethylpentyl.

In one embodiment according to the use of the disclosure, the heavy metal-precipitation agent is sodium diisobutyldithiophosphinate.

LEGEND OF THE FIGURES

FIGURE 1 shows a shaking device with a bottle containing the sample in an horizontal position (top) and a bottle containing the sample solution before shaking (bottom).

DETAiLED DESCRIPTION

Throughout the description and claims of this spécification, the words “comprise” and variations thereof mean “including but not limited to”, and they are not intended to (and do not) exclude other moieties, additives, components, integers or steps. Throughout the description and claims of this disclosure, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the disclosure is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.

Features, integers, characteristics, compounds, Chemical moieties, or groups described in conjunction with a particular aspect, embodiment or example of the disclosure are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith. AH ofthe features disclosed in this disclosure (including the description, claims, abstract and drawings), and/or ail ofthe steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. The disclosure is not restricted to the details of any foregoing embodiments. The disclosure extends to any novel one, or any novel combination, of the features disclosed in this disclosure (including the description, claims, abstract and drawings), or to any novel one, or any novel combination, ofthe steps of any method or process so disclosed.

The enumeration of numeric values by means of ranges of figures comprises ail values and fractions in these ranges, as well as the cited end points. The term “ranges from ... to ’’ as used when referring to a range for a measurabie value, such as a parameter, an amount, a time period, and the like, is intended to include the limits associated to the range that is disclosed.

The term “about as used when referring to a measurabie value, such as a parameter, an amount, a time period, and the like, is intended to represent the measurement error associated with the technique to measure such parameter, amount, time period, and the like, and is considered to be 5 % or less, depending on the measurement technique used. It should be understood that the value to which the term “about” refers per se has also been disclosed.

In the present application, unless otherwise stated, the pH values are measured after a 13fold dilution by volume with water. Stated dîfferently, the pH value is measured after mixing one volume of a non-diluted sample with 13 volumes of water.

According to one aspect of the disclosure, a method is disclosed for converting a solid hazardous heavy metal-containing composition into a solid inert heavy metal-containing composition and an aqueous composition essentially free of heavy metals. In particular, a method is disclosed for converting a solid hazardous cadmium-containing composition into a solid inert cadmium-containing composition and an aqueous composition essentially free of cadmium.

The method of the disclosure may be applied on any solid composition containing heavy metals and leaching more than 2 ppm of cadmium, or more than 5 ppm of arsenic, or more than 50 ppm of copper, or more than 0.5 ppm of mercury, or more than 10 ppm of nickel, or more than 10 ppm of lead, or more than 50 ppm of zinc, according to the Modified EU Standard. Examples of materials that may be solid hazardous heavy metal-containing compositions include the compositions generated from the extraction of heavy metals from fertiîizer liquors as described in EP 0091043, US 2004/0179984 or US 4762693. Therefore, in particular, the starting material is a solid hazardous heavy metal-containing composition that may further comprise phosphorous and calcium. In particular, the starting material may contain from 1 to 10 weight % phosphorous and from 1 to 18 weight % calcium. The method may be particularly suitable for being applied on solid heavy metal-containing compositions generated from the extraction of heavy metals from fertiîizer liquors comprisîng phosphates and calcium, such liquors being, in turn, generated by the acid digestion of phosphate rocks.

In a first step, step a), the mixing and dissolving step, the solid hazardous heavy metalcontaining composition is mixed and dissolved with an acid solution. In this mixing and dissolving step, heavy metals are leached from the solid hazardous heavy metal-containing composition into the acid solution, thereby obtaining a hazardous heavy métal acid composition. A pulverization step before the mixing and dissolving step is not necessary. However, the person skilled in the art may perform such pulverization step with a view of reducing the size of the particles of the hazardous heavy metal-containing composition and, thereby, facilitating the dissolving ofthe particles into the acid solution. In particular embodiments, the solid hazardous heavy métal containing composition is a solid hazardous cadmium containing composition.

As defined herein, an acid solution is any solution with a pK_a of 7 or less. The acid solution and the molarity of the acid solution can be selected such as to reduce the volume of the acid solution needed and to maximize the amount of heavy metals leached into the acidic composition. A decrease in the pKa, as well as an increased molarity ofthe selected acid solution may resuit in improved leaching of heavy metals from the solid hazardous heavy metal-containing composition into the aqueous acid composition. In particular, the acid solution may hâve a pKa of less than 2.3, more in particular less than 1.2, most in particular less than 0. In this manner, optimal décomposition ofthe solid hazardous heavy metalcontaining composition in the mixing and leaching step is achieved. This results in the maximization of the amount of precipitated heavy metals in the précipitation step and, thereby, in the minimization of the amount of heavy metals in the aqueous composition essentially free of heavy metals.

The acid solution may be selected from a chlorous, a hypophosphorous, an iodic, a nitric, a perchloric, a periodic, a sulfamic, a tertafluoroboric, a thiocyanic, a chromic, a phosphorous, a selenic, a sulfuric, an arsenic or a pyrophosphoric acid solution, in particular, the molarity of the acid solution is in the range of 3 to 8 M, more in particular 3 to 6 M, most in particular 3.5 to 4.5 M. In particular, solutions of 2 to 8 M nitric acid or hydrochioric acid, more in particular 3 to 6 M nitric acid or hydrochloric acid, most in particular 3.5 to 4.5 Ml nitric acid or hydrochloric acid hâve been found suitable for performing the mixing and dissolving step of the method of the disclosure. By using those solutions, it has been possible to leach from 70 to 80 weight % ofthetotal amount of heavy metals, such as cadmium, that are présent in the solid hazardous heavy metal-containing composition into the acid solution, when the mixing and dissolving step was performed at températures from 20 to 50 ’C, more in particular 25 to 50 °C, most in particular 35 to 45 °C, for periods of time ranging from 30 minutes to 24 hours, more in particular 30 minutes to 1.5 hour, most in particular 45 minutes to one hour, and mixing 30 to 150 g, more in particular 45 to 75 g, most in particular 65 to 75 g of the hazardous heavy metal-containing composition with 100 g of the acid solution. Increasing the température, increasing the réaction time and decreasing the ratio of the weight of the hazardous heavy metalcontaining composition over the weight of the acid solution were ail found to resuit in increasing leaching of heavy metals into the acid solution. It is, therefore, possible to adjust the température, the reaction time and the weight of the acid solution used in the mixing and dissolving step, in order to achieve at least 70 % of leaching of heavy metals, such as cadmium, from the hazardous heavy metal-containing composition into the acid solution. The person skilled in the art will, furthermore, be able to readiîy adjust the reaction conditions in the mixing and dissolving step accordîng to the spécifie type of hazardous heavy metal-containing composition as the starting material. Generaily speaking the stronger the heavy métal bonds in the hazardous heavy metal-containing composition, the lower the pK_a and/or the higher the molarîty of the acid solution and/or the higher the température and/or the higher the ratio of the weight of the hazardous heavy metalcontaining composition over the weight of the acid solution and/or the longer the reaction time should be.

It has been found that not necessarily ail of the heavy metals present in the initial hazardous material is leached into the acid solution. As stated above, in particular, 70 to 80 weight % of the total amount of heavy metals, such as cadmium, and copper, that is present in the solid hazardous heavy metal-containing composition may leach into the aqueous acidic composition. Any heavy metals that are not leached will remaîn in solids, typically in small particles, and will, therefore, be separated in later steps, together with the heavy métal precipitate. This remaining solid material will be hereafter referred to as the remaining sludge. Hence, the amount of heavy metals that is not leached in the mixing and dissolving step may be part of the final solid non-hazardous heavy metal-containing composition. However, to the extent that the heavy metals did not leach during initial contact with acid in the mixing and dissolving step, remaining sludge has been found to be non-hazardous and does not affect the nature of the final non-hazardous heavy métal containing composition.

In a different embodiment accordîng to the method of the disclosure, at least part of the remaining sludge can be removed in a pre-treatment step prior to the addition of the précipitation agent. The effect of this pre-treatment step may be to improve the efficiency of the reaction ofthe heavy métal precipitating agent. The séparation of the sludge may be accomplished by any standard technology for séparation such as, but not limited to, filtration, centrifugation, flotation or décantation. In particular, the séparation may be performed by centrifugation for most effectively separating solids from the sludge.

In a second step b) according to the method of the disclosure, the precipitating step, the heavy metals from the hazardous heavy métal acid composition is precipitated by reacting the hazardous heavy métal acid composition with a heavy metal-precipitation agent at a pH of at least 0.9 (measured after a 13-fold dilution by volume using water). More in particular, the pH the pH ofthe hazardous heavy métal acid composition is first measured. The purpose of this step is to verify whether or not the pH value is sufficiently high for précipitation of the heavy métal precipitate to occur in the precipitating step. It has been found that in order to recover at least 80 % of the heavy metals in the hazardous heavy metaî-containîng composition in the non-hazardous heavy metal-containing composition separated in the separating step, a pH of at least 0.9 (measured after a 13-fold dilution by volume using water) should be reached in the précipitation step. Therefore, in the pH measuring step, it measured whether or not the pH is lower than 0.9. This will dépend on the pK_a and on the molarity ofthe acid solution used in the mixing and dissolving step a).

If the pH measured in the pH measuring step is lower than 0.9 (measured after a 13-fold dilution by volume using water), the pH may be adjusted in the precipitating step. The pH may be adjusted either before or after the reaction with the heavy métal precipitating agent. Any agent suitable for increasing the pH or, in other words, any conventional Chemical base such as, but non-limited to, sodium hydroxide, potassium hydroxide or ammonium hydroxide may be used for increasing the pH. However, according to an embodiment, the increase ofthe pH is performed using gaseous ammonia. By using gaseous ammonia, it is possible to minimize the amount of liquid, in particular water, introduced into the system. In addition, as ammonia is commonly used in various production processes, in particular the production of fertilizers, sufficient ammonia can easily be diverted for this purpose and will not cause any problems or concerns if recycled back into the fertilizer production process. Furthermore, as mentioned above, the method of the disclosure may be particularly suitable for being applied on solid heavy metal-containing compositions generated from the extraction of heavy metals from fertilizer liquors. Therefore, it is advantageous to generate an aqueous composition essentially free of heavy metals in the separating step but that may contain ammonia that can subsequently be recycled to the fertilizer production process from which the hazardous heavy metal-containing composition was generated.

When the hazardous starting material is obtained from, for example, fertiliser applications where a desired end product contains phosphorous, a potential objective would be to precipitate the heavy metals but to retaîn phosphorous in the aqueous supernatant. The phosphorous in the supernatant could then be recycled for further use. In the précipitation step where the pH is adjusted if necessary, a pH above 0.9 and measured after a 13-fold dilution by volume using water, allows for the efficient précipitation of the heavy métal precipitate, as discussed above. in comparison, précipitation of phosphorous has been seen to become more significant at pH values above 1.6. For example, in some embodiments, the hazardous heavy métal acid composition obtained in the mixing and dissolving step may comprise from 1 to 10 weight % phosphorous. In such embodiments, the pH in step the précipitation step may be adjusted, if necessary, to values ranging from 0.9 to 1.6 (measured after a 13-fold dilution by volume using water), from 1.2 to 1.6 (measured after a 13-fold dilution by volume using water) or from 1.4 to 1.6 (measured after a 13-fold dilution by volume using water). Using this range, a relatively high ratio of heavy metal-precipitation over phosphate précipitation can be achieved. This means that it is possible to maximize the heavy metal-precipitation such as to achieve an aqueous composition that is essentially free of heavy metals and, at the same time, minimize the amount of precipitated phosphorous. With reduced amount of phosphorous precipitating, the size of the solid non-hazardous heavy metal-containing composition that then needs to be disposed of is also reduced. Furthermore, as discussed above phosphorous recovery from the heavy metal-free aqueous composition can be particularly important for alfowing the recycling of valuable phosphorous to a fertilizer process. Accordingly, in certain embodiments of the method of the present disclosure, the method further comprises the step of recovering phosphorous from the heavy metal-free aqueous composition.

The reaction with the heavy meta! precipitating agent is performed in the precipitating step. According to one embodiment ofthe method ofthe disclosure, R in Formula 1 is selected from the group consisting of cyclohexyl, isopropyl, isobutyl, n-propyl, octyl, hexyl, phenylethyl and 2,4,4-trimethylpentyl. In particular, R is selected from cyclohexyl, octyl, hexyl and phenylethyl. The two R groups in Formula 1 can be the same or different.

According to one embodiment of the method, the heavy métal precipitating agent is selected from dicyclohexyl, dicyclopentyl, di(o-tolyl)phosphine, diphenyl, tertbutylphenyldithiophosphinate and the sodium and ammonium salts thereof.

According to one embodiment ofthe method, the heavy metal-precipitation agent is sodium diisobutyldithiophosphinate.

Generally, the heavy métal precipitating agent can be prepared according to the procedure described in US 4308214 and the corresponding examples by heating 67.2 parts of sulfur 114.8 to 284.8 parts of water to a température of about 70 °C. To the mixture are then steadily metered in 29.5 to 64.5 of the commercially available di-phosphine. After the diphosphine has been metered, an additional 67.5 to 193,5 additional parts of diethyl phosphine are metered in at a rate such that within the time necessary to meter in ail of the diethylphosphine, 80.0 parts of a 50% solution of sodium hydroxide are also metered in at a constant rate to neutralize the corresponding dithiophosphinic acid that forms.

The dosage of the heavy métal-précipitation agent and the efficiency of heavy metalprecipitation will dépend on the amount of heavy metals présent in the aqueous acidic composition obtained from the mixing and the dissolving step. Generally, the higher the concentration of heavy metals, the greater will be the overall dosage of the heavy metafprecipitation agent. The person skiited in the art will be abie to readily détermine and establish the optimum dosage of the heavy metal-precipitation agent using no more than routine expérimentation. In particular, the heavy metal-precipitation agent in the precipitating step is reacted in an amount ranging from 0.01 to 50 kg, from 0.1 kg to 10 kg or from 0.15 kg to 1.5 kg per ton of acid composition obtained in the mixing and dissolving step.

The reaction with the heavy métal precipitating agent may be performed for 3 minutes to 1.5 hour, for 5 minutes to one hour, or for 10 to 30 minutes, and at température ranging from 5 to 80 °C, from 10 to 50 °C or from 20 to 40 °C. As the heavy métal precipitate may be less stable, at températures above 40 °C, it may be désirable to react for less than 10 minutes at higher températures. The person skilled in the art will be able to readily adjust the reaction conditions for reacting the heavy métal precipitating agent in order to achieve sufficient précipitation of heavy metals such as to produce an aqueous composition essentially free in heavy metals in the separating step.

The separating step, step c), may be accomplished by any standard technology for séparation such as, but not limited to, filtration, centrifugation, flotation or décantation. For example, a flocculation step may be performed before the precipitating step. A flocculation step may likewise be performed before the above mentioned séparation of at least part of the sludge from part of the hazardous acid heavy métal composition. This allows solids to be more effectively separated out.

In some embodiments, flocculation can also be done at the same time as, or subsequently to, adding the precipitating agent in the precipitating step. Such formation of flocculants may assist with separating the solid inert heavy metal-containing composition from the aqueous composition essentially free of heavy metals.

Flocculation may occur either before, during or after the precipitating step or in combinations thereof or, in some embodiments, there is no flocculation step. In one embodiment, a flocculation step is performed after the precipitating step.

If there is flocculation being performed at more than one step, the flocculating agent may be the same or different. A flocculation agent that can be used is, for example, a cationic polymer with a charge ranging from 20 to 60 %, or from 25 to 50 % or from 35 to 45 %: as defined herein, a cationic polymeric flocculant is a polymer wherein from 20% to 60%, more particularly from 25 % to 50 %, even more particularly from 20% to 50% of the moieties making up the cationic polymeric flocculant are cationic charged moieties, an anionic polymeric flocculant wherein from 1% to 10% of the moieties making up the anionic polymeric flocculant are anionic charged moieties, or a mixture thereof. Examples of cationic polymers include, but are not limited to, 40% linear cationic powder polyacrylamide (that is a polyacrylamide having 40% of its moieties positively charged) with a molecular weight ranging from 7,1 to 9,5 *10⁶ Dalton. In particular, a polymer of acrylamide and a chloro-methylated monomer may be used.

Surprisingly, the inventors hâve found that the method provides a solution for converting a solid hazardous heavy metal-containing composition, such as a solid hazardous cadmium containing composition, into a solid non-hazardous heavy metal-containing composition that can be safely disposed of. In addition, the heavy métal concentration in the inert solid heavy metal-containing composition is higher than the heavy métal concentration in the solid hazardous heavy metal-containing composition and the mass and volume ofthe inert solid heavy metai-containing composition are, therefore, lower than the corresponding mass and volume of the hazardous solid heavy metal-containing composition. In other words, the method ofthe disclosure allowsfora réduction ofthe amount of solid hazardous heavy metal-containing composition.

It has further been found that précipitation can be obtained without the addition of a précipitation agent in the precipitating step, by merely încreasing the pH and at a pH of about 2, 40% of the heavy métal in the acid solution can be expected to precipitate. However, the resulting precipitated composition has been found to continue to be hazardous.

According to another aspect of the disclosure, the use for converting a solid hazardous heavy metal-containing composition into a solid non-hazardous heavy metal-containing composition and an aqueous composition essentially free of heavy metals, of the heavy métal precipitating agents ofthe type of Formula I described above, is disclosed.

According to one aspect of the disclosure, the application thus provides a method for converting a solid hazardous heavy metal-containing composition into a solid inert heavy metal-containing composition and an aqueous composition essentially free of heavy metals. For the purpose of this disclosure, a hazardous cadmium-containing composition is defined as a composition leaching more than 2 ppm of cadmium into an aqueous solution, upon treatment of the composition according to a simplification of the European Standard NS-EN 12457-2, using 10 I of water per kg of the composition (the “Modified EU Standard” for materials with particte size below 4 mm - as further specified below). Therefore, in another aspect of the disclosure, a method is provided to evaluate the leaching capacity of a test composition according to the Modified EU Standard as disclosed herein. This method comprises the following steps:

providing a dry solid test composition; preferably in the range of 2 to 40 g;

preparing a liquid test composition by the addition of a solvent, preferably water, to the dry solid test composition, thereby establishing a liquid-to-solid ratio of 10 ± 0,2 l/kg;

agitating the liquid test composition for a time period between 23.5h and 24.5h on a shaking device; preferably wherein the agitating is performed at about 90 rpm;

after agitation, allowing seulement of the suspended solids, preferably for 15 to 20 min;

performing a first filtration step of the liquid test composition with the suspended solids; preferably said first filtration step using a filter device with a pore size between 1518 pm;

performing a second filtration step of the fîltered eluate obtained after the first filtration step, thereby using a filtration device with a pore size of about 0.8 pm;

optionally, performing a third filtration step of the fîltered eluate obtained after the second filtration step, thereby using a filtration device with a pore size of about 0.45 pm; and measuring the conductivity (ps/cm), the température T (°C), pH, the total dissolved solids (TDS in (g/l)) and/or the amount of one or more solids selected from As, Ba, Cd, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Se, Zn, Chloride, Fluoride, Sulphate, dissolved organic carbon (DOC) in the fîltered eluate obtained after the second or third filtration step;

wherein ail steps are performed at a température range between 15° and 25°C.

EXAMPLE

AH the heavy métal values provided in this Example Section were measured by ICP-OES (Thermo Scientific, iCAP 7400 Duo, wavelength: Cd: 226.502 nm; Cu: 204.379 nm; Zn: 206.200 nm, ail axial mode).

Hazardous Heavy Métal Containing Composition

A heavy metal-containing composition was analysed. It comprised 7.2 weight % of phosphorous as analysed by XRF, 6.03 weight % phosphate as analysed by gravimetry, 310 ppm by weight of cadmium and leached 17 ppm of cadmium, and 75 ppm of copper when submitted to the Modified EU Standard procedure and was, therefore, classified as hazardous. This heavy métal (cadmium) containing composition is referred to as the hazardous heavy métal (cadmium) containing composition in the remaîning ofthe Example section.

Example 1

1. Leaching of the hazardous heavy metal-containing composition a. Leaching the hazardous heavy métal composition with nitric acid The freshly produced hazardous heavy metal-containing composition was dîrectly leached by acid to demobilize the heavy metal-containing composition. The heavy metal-containing composition was treated with 4.5 M nitric acid, at 133% pulp density, meaning 133 g solid composition per 100 g acid, and stirred for 5 hours with a magnetic bar at ambient température.

After leaching, a centrifugation step was performed in order to separate part of the sludge from the acid composition. The composition separated from part of the sludge contained 88 % of the cadmium, 88 % of copper, 88 % of zinc from the hazardous cadmiumcontaining composition.

b. Leaching the hazardous heavy-metal composition with hydrochloric acid The freshly produced hazardous heavy metal-containing composition was treated with 2 M hydrochloric acid, at 75 % pulp density, meaning 75 g solid composition per 100 g acid, and stirred for 1 hourwith a magnetic bar at 35^C‘C . After leaching filtering was performed în order to separate the solids and liquids. The composition separated from the solids contained 69 % of Cd, 2.5 % of Cu, 71 % of Zn, 68 % of Ni, 65 % of Pb and 22 % of Mn from the hazardous cadmium-containing composition.

2a Précipitation of a non-hazardous heavy metal-containing composition at pH 1.3 (measured after a 13-fold dilution by volume using water)

The pH value of the composition separated from part the sludge was measured and determined to be 1.3 using gaseous ammonia. The pH was the value measured from a sample prepared by consecutively sampting a composition for which a pH value is to be determined, weighing the amount of sampled composition, adding to the sampled composition 13 grams of water per gram of sampled composition, and mixing the added water and the sampled composition so as to make a homogenous sample. 3.6 weight % of sodium diisobutyldithiophosphinate solution in water was added to the composition with a pH value of 1.3 (measured after a 13-fold dilution by volume using water), ata ratio of 0.081 g ofthe sodium diisobutyldithiophosphinate solution per g ofthe composition. The resulting solution was then stirred for 3 minutes at 30 °C. A precipitate was formed. A flocculation step was subsequently performed in order to facilitate the séparation of the precipitate. A 0.1% solution of the 40% linear cationic powder poiyacrylamide (that is a polyacrylamide having 40% of its moieties positively charged) with a molecular weight ranging from 7,1 to 9,5 *10⁶ Dalton as the flocculant was introduced in the reaction tank at 600 rpm at a ratio of 0.003 ml polymer/g of liquor. The agitation was then reduced to 150 rpm in order to produce flocculants. The resulting flocculants were separated by vacuum filtration using Whatman fiiter 520A (pore size: 15-18pm, typical thickness 300 pm, basis weight 90g/m²).

Comparative Examples

The hazardous heavy metal-containing composition was leached according to 1a and the resulting composition was subsequently treated according to the method described in US4762693: the précipitation step was performed at pH 8.5 without sodium diisobutyldithiophosphinate.

For comparison purposes, the précipitation step 2 above was also performed adjusting the pH to 2.0 and no reaction with sodium diisobutyldithiophosphinate was performed.

Comparative Example 1

2b. Précipitation at pH 2.0 without reaction with sodium diisobutyi dithiophosphinate

The pH value ofthe composition separated from part ofthe sludge was increased ίο 2.0. The pH was the value measured from a sample prepared by consecutively sampling a composition for which a pH value is to be determined, weighing the amount of sampled composition, adding to the sampled composition 13 grams of water per gram of sampled composition, and mixing the added water and the sampled composition so as to make a homogenous sample. The pH was adjusted using a 50 % sodium hydroxide solution in water. As the pH increased, précipitation occurred along with moderate heat evolvement (40.5 °C). A precipitate was formed. The precipitate was separated by vacuum filtration using Whatman filter 520A (pore size: 15-18pm, typical thickness 300 pm, basis weight 90g/m²). The resulting precipitate was dried at room température before further characterisation.

Only 10 % of the cadmium, 14 % of the nickel and 6 % of the zinc initially present in the composition was precipitated.

Comparative Example 2

2c. Précipitation at pH 8.5 without reaction with sodium diisobutyl dithioph osphinate

The pH value of the composition separated from part of the sludge was increased to 8.5. The pH was the value measured from a sample prepared by consecutively sampling a composition for which a pH value is to be determined, weighing the amount of sampled composition, adding to the sampled composition 13 grams of water per gram of sampled composition, and mixing the added water and the sampled composition so as to make a homogenous sample. The pH was adjusted using a 50 % sodium hydroxide solution în water. As the pH increased, précipitation occurred along with moderate heat evolvement (67 °C). A precipitate formed. The precipitate was separated by vacuum filtration using Whatman filter 520A (pore size: 15-18pm, typical thickness 300 pm, basis weight 90g/m²). The resulting precipitate was dried at room température before further characterisation.

Analysis

This procedure describes the stability test performed on the dry heavy metal-containing solid composition, before and after the treatment according to the method ofthe disclosure. The procedure is based on the Norwegian and European Standard procure “Leaching: Compliance test for leaching of granular solid composition materials and sludges Part 2:

One stage batch test at a liquid to solid ratio of 10l/kg for materials with particle size below 4 mm (without or with size réduction). [Norsk Standard NS-EN 12457-2, 2003].

Table 1 Cadmium leaching results - example 1 and comparative examples

Example	Leached heavy métal conc from hazardous composition/ppm	Leached heavy métal conc from composition step 2/ppm	% recovered heavy metals after step 2 with respect to hazardous waste	Concentration factor of heavy metals with respect to hazardous waste	% phosphate composition obtained after step 2.
	Cd	Cu	Zn	Cd	Cu	Zn	Cd	Cu	Zn	Cd	Cu	Zn
1	17	75	22	0.03	0.6	12	76	75	47	96	100	63.5	0.6
Comparative example 1	2.97	1.1	37.2	10	14	6	0.5	0.2	1.11
Comparative example 2	0.01	0.65	1	74	55	67	1.2	1.2	1.2	14.6

From table 1, it can be concluded that only the method of the disclosure, using a phosphinate and précipitation at pH 1.3 (measured after a 13-fold dilution by voiume using water), provides ail the benefits of high cadmium recovery, réduction of the amount of composition, as reflected by the concentration of cadmium în the composition treated according to the method of the disclosure, high recovery of phosphate as reflected in the low amount of phosphate in the composition treated according to the method of the disclosure, and a non-hazardous classification for the composition.

Modified EU Standard based on the EU standard procedure NS-EN 12457-2

In the Modified EU Standard, the amount of composition analysed ranges from 2 to 40 g.

In addition, the end-over-end tumbler with 5-10 rpm recommended in NS-EN 12457-2 is substituted for a shaking apparatus shown in Figure 1.

1. Equipment I Apparatus • Crushing equipment (mortar) • Sieving equipment with sieves of4mm nominal screen size • Glass or high-density polyethylene bottle with caps made of inert material (for example PTFE) • Shaking device according to Figure 1;

• Filtering apparatus or vacuum filtration device or high-pressure filtration apparatus • 0.45 pm membrane filters for filtration

If filtration device is not available, use syringe and syringe filters; use 0.8 pm and after first filtration use 0.45 pm (hydrophobie filter made of PTTE) • A device for measuring electrical conductivity of eluate • A device for measuring TDS of eluate • A pH meters for measuring pH of eluate • Thermometer for measuring T of eluate • A balance

2. Reagents • The dry hazardous heavy métal solid composition before and after treatment according to the method of the disclosure: originally 10 l/kg, if the amount of dry Cd solid composition is smaller use the same ratio for example 0.11/1 Ûg (100ml/10g) • Distilled water, dernineralised water, de-ionised water of équivalent purîty (5 < pH< 7,5) with a conductivity < 0,5 mS/m. Before performing stability test, it îs recommended to wash ail laboratory glass, beakers to avoid contamination. Especiaîly for conductivity measurement, since this analysis is overly sensitive

3. Testing conditions • Test should be done at room T (20 +/-5) °C • Analyse water content of the dry Cd water • Place the test portion of dry solid composition for test in a bottle, add an amount of leachant (water) establishing a liquid to solid ratio L/S = 10l/kg +/- 2% or équivalent-for example 100ml/10g • Place the capped bottle in the agitation device, place the bottle in horizontal position, use 90 rpm speed • Agitate on shaking device in for 24 h +/- 0.5h and after 24h, allow the suspended solids to settle for 15-20 min.

• It is recommended to run a blank sample for the vérification of the leaching procedure and analysis

4, Liquid-solid separating step • At first filter the solution with suspended solids through ceramic funnel using Whatman filter 520A (pore size: 15-18pm, typical thickness 300 pm, basis weight 90g/m²) • Filter the eluate again using syringe filter 0.8 pm. If it is possible the eluate could be one more time filtered using 0.45 pm (hydrophobie filter made of PTTE) • Measure the volume of filtered eluate and measure amount of solids • Measure immediateîy conductivity in (ps/cm), T (OC), pH and TDS (g/l) of eluate

5. Analysis

Divide the eluate to an appropriate number of samples for different chemical analysis, which should be performed to establish leaching limit values according to the “Toxicity of recycled Concrète Aggregates: review on leaching tests.’’, The Open Construction and Building Technology Journal 2018, 12, 187-196, and Table 2:

• As, Ba, Cd, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Se, Zn (analysis by ICP-OES) • chloride, fluorîde, sulphate (analysis by Ion Chromatography) • Dissolved Organic Carbon (analysis by LECO) • Total Dissolved Solids (Conductivity analysis using the Mettler Toledo Inlab 742 ISM electrode)

6. Leaching limit values for solid composition acceptable in landfills qualification

These spécifications indicate that the release of dangerous substances should be evaluated in a leaching test according to European standard EN 12457 - 4 “Characterization of solid composition-leaching-compliance test for leaching of granular solid composition materials and sludges - part 4: One stage batch test at a liquid to solid ratio of 10l/kg with particle size below 10mm, 2002.”

Table 2 Leaching limit values (mg/kg of dry mass) for solid composition acceptable in landfills for inert, non-hazardous, and hazardous solid composition (council decision 2003/33/EC)[2],

Chemical parameters	Maximum Limit Values (mg/kg of dry mass) According to Classification
Inert solid composition	Non-hazardous solid composition	Hazardous solid composition
	L/S=2l/kg	L/kg=10 l/kg	L/S=2l/kg	L/kg=10 l/kg	L/S=2l/kg	L/kg=10 l/kg
As	0.1	0.5	0.4	5	6	25
Ba	7	20	30	100	100	300
Cd	0.03	0.04	0.6	2	3	5
Cr	0.2	0.5	4	20	25	70
Cu	0.9	2	25	50	50	100
Hg	0.003	0.01	0.05	0.5	0.5	2
Mo	0.3	0.5	5	10	20	30
Ni	0.2	0.4	5	10	20	40
Pb	0.2	0.5	5	10	25	50
Sb	0.02	0.06	0.2	0.7	2	5
Se	0.06	0.1	0.3	0.5	4	7
Zn	2	4	25	50	90	200
Chloride	550	800	10000	50000	17000	25000
Fluoride	4	10	60	250	200	500
Sulphate	560	1000	10000	20000	25000	50000
DOC	240	500	380	1000	480	1000
TDS	2500	4000	40000	60000	70000	100000

7. Landfills for non -hazardous solid composition in Norway

Council Decision 2003/33/EC does not set any general criteria for acceptance of solid 5 composition at landfills for non-hazardous solid composition. However, it does define and set WAC (solid composition acceptance criteria) for one spécifie sub-category of nonhazardous solid composition landfills, namely non-hazardous solid composition landfills or landfill cells receiving stable, non-reactive hazardous solid composition. It also spécifiés that gypsum-based materials can only be placed in non-hazardous solid composition 10 landfills in cells where no biodégradable solid composition is accepted.

Norway has defined two sub-categories of non-hazardous solid composition landfills:

General landfills for non-hazardous solid composition • Non-hazardous solid composition landfills receiving stable, non-reactive 5 hazardous solid composition.

Norway is enforcing the EU WAC for hazardous solid composition to be accepted at nonhazardous solid composition landfills receiving stable, non-reactive hazardous solid composition. From July 1,2009, a limit of 10 % TOC or 20 % loss on ignition will be imposed on non-hazardous solid composition to be accepted at landfills for non-hazardous solid composition. For al! three classes of landfills, the solid composition must be tested both at L/S = 0.1 l/kg and at L/S = 10 l/kg when testing is relevant.

8. Landfills for hazardous solid composition in Norway

Norway has implemented the EU WAC for granular hazardous solid composition to be landfiiled at hazardous solid composition iandfills.

Claims

1. A method for converting a solid hazardous heavy metal-containing composition into a solid non-hazardous heavy metal-containing composition and an aqueous composition essentially free of heavy metais, comprising the steps of

a) mixing and dissolving the solid hazardous heavy metal-containing composition with an acid solution, thereby obtaining an hazardous heavy métal acid composition;

b) precipitating the heavy metals from the hazardous heavy métal acid composition by reacting the hazardous heavy métal acid composition with a heavy metal-precipitation agent at a pH ranging from 0.9 to 1.6, measured after a 13-fold dilution by volume using water; particularly by: measurîng the pH ofthe acid composition after a 13-fold dilution by volume in water, and adjusting the pH of the solid hazardous heavy metal-containing composition to values ranging from 0.9 to 1.6 if the measured pH is below 0.9; and reacting the hazardous heavy métal acid composition with a heavy metal-precipitation agent; and c) separating out the heavy métal precipitate from the aqueous supernatant, whereby the heavy métal precipitate is the solid non-hazardous heavy metal-containing composition and the aqueous supernatant is the aqueous composition essentially free of heavy métal; wherein the heavy metal-precipitation agent comprises a diorgano-dithiophosphinic acid or the alkali métal or ammonia salts thereof, represented by Formula 1

S

R II ^P-SM

Formula 1 and wherein R is a linear or branched hydrocarbon group selected from alkyl, aryl, alkylaryI, or aralkyl, and wherein the hydrocarbon group contains 3 to 20 carbon atoms, and M is H, alkali métal or ammonia.

2. The method according to claim 1, wherein the solid hazardous heavy-metal containing composition is characterized in that it contains heavy metals and leaches more than 2 ppm of cadmium, or more than 5 ppm of arsenic, or more than 50 ppm of copper, or more than 0.5 ppm of mercury, or more than 10 ppm of nickel, or more than 10 ppm of lead, or more than 50 ppm of zinc, according to a Modified EU Standard NS-EN 12457-2 using 10 I of water per kg of the composition.

3. The method accordîng to any one of claims 1 to 2, wherein the solid hazardous heavy metai-containing composition is a solid cadmium-containing composition, and wherein the solid non-hazardous heavy metal-containing composition is a solid cadmiumcontaining composition, and wherein the aqueous composition is essentîally free of cadmium.

4. The method accordîng to claims 1 to 3, wherein the acid solution used in step a) has a pK_a of less than 2.3.

5. The method accordîng to any one of claims 1 to 4, wherein the solid hazardous heavy metal-containing composition further comprises from 1 to 10 weight% phosphorous and from 1 to 18 weight% calcium.

6. The method accordîng to claim 1 to 5 wherein the solid hazardous heavy-metal containing composition is the end product of a précipitation process of heavy metals, such as the Odda process.

7. The method accordîng to any one of claims 1 to 7, wherein the pH value of the composition in step c) is adjusted using gaseous ammonia.

8. The method accordîng to any of claims 1 to 1, wherein R in Formula 1 is selected from the group consisting of cyclohexyl, isopropyl, isobutyl, n-propyl, octyl, hexyl, phenylethyl and 2,4,4-trimethylpentyl.

9. The method accordîng to any one of claims 1 to 8, wherein the heavy metalprecipitation agent is sodium diisobutyldithiophosphinate.

10. The method accordîng to any one of claims 1 to 9, wherein the hazardous heavy métal acid composition comprises a solid sludge and wherein, and wherein the method comprises, before the precipitating step b), the step of:

d) removing at least part of the solid sludge in the hazardous heavy métal acid composition.

11. The method according to any one of claims 1 to 10, wherein the method further comprises the step of:

e) adding a flocculating agent, thereby forming flocculants, wherein the flocculating agent is added after the mixing and dissolving step a).

12. The method according to claim 11, wherein the flocculating agent is added before the precipitating step b), and/or during the precipitating step b) and/or after the precipitating step b).

13. The method according to claim 12 wherein the flocculating agent is added after the precipitating step b).

14. The method according to any of claims 11 to 13, wherein the flocculating agent is a cationic polymer.

15. Use of a diorgano-dithiophosphinic acid or the alkaii métal or ammonia salts thereof for converting a solid hazardous heavy metal-containing composition having a pH ranging from 0.9 to 1.6 measured after a 13-fold dilution by volume using water, into a solid nonhazardous heavy metal-containing composition and an aqueous composition essentially free of heavy métal, wherein the diorgano-dithiophosphinic acid or the alkaii métal or ammonia salts thereof is represented by Formula 1

S ^R || —_SM

Formula 1 wherein R is a linear or branched hydrocarbon group selected from alkyl, aryl, alkyîaryl, or aralkyl, and wherein the hydrocarbon group contains 3 to 20 carbon atoms, and M is H, an alkaii métal or ammonia.

16. The use according to claim 15, wherein the solid hazardous heavy metal-containing composition is a cadmium-containing composition, and wherein the solid non-hazardous heavy metal-containing composition is a cadmium-containing composition, and wherein the aqueous composition is essentially free of cadmium.

17. The use according to claims 15 or 16, wherein R in Formula 1 is selected from the group consisting of cyclohexyl, isopropyl, isobutyl, n-propyl, octyl, hexyl, phenylethyî and 2,4,4-trimethylpentyî.

18. The use according to any one of claims 15 to 17, wherein the diorganodithiophosphinic acid or the alkali métal or ammonia salts thereof is sodium diisobutyldithiophosphinate.