Patent Grant
11000719
This is a National Stage application of PCT international application PCT/FR2017/051752, filed on Jun. 29, 2017, which claims the priority of French Patent Application No. 16 56083, filed Jun. 29, 2016, both of which are incorporated herein by reference in their entireties.
The invention relates to the field of immobilization of wastes comprising mercury, also referred to as mercury wastes.
More specifically, the invention relates to a method for immobilizing a waste comprising mercury, which comprises the stabilization of this mercury by precipitation in the form of mercury(II) sulfide (or mercuric sulfide), having the formula HgS and which is referred to more simply as “mercury sulfide” in the following sections, then followed by the encapsulation by means of cementation, that is to say by means of embedding in a cementitious matrix, the waste comprising the mercury sulfide thus obtained.
The invention in particular finds application in the immobilization of mercury wastes originating from nuclear facilities and, therefore, contaminated or potentially contaminated with radioelements.
However, it goes without saying that it has the ability to be effectively used for immobilizing any mercury waste regardless of the origin thereof.
Mercury is a toxic metal that is in liquid form under normal conditions of temperature and pressure. It is a very volatile element that vaporises easily at ambient temperature by forming vapours which are all the more pernicious being that they are colourless and odourless.
Mercury is present in many devices such as batteries, accumulators, fluorescent tubes and low-energy bulbs (or compact fluorescent bulbs) which are used in particular in nuclear facilities, in which case it is associated with nuclear waste. It is also used in the chemical industry as a liquid cathode in electrolysis cells. Finally, it is used in the manufacture of metal amalgams and, in particular, dental amalgams.
According to the French National Plan for the Management of Materials and Radioactive Wastes (PNGMDR) established pursuant to the provisions of Law No. 2006-739 dated 28 Jun. 2006, of the French Republic, relating to the sustainable management of radioactive materials and wastes, mercury and mercury wastes, along with asbestos wastes, organic fluids and oils, are part of wastes for which there does not at the present time exist a waste management chain, that is to say for which there does not yet exist a waste disposal chain.
Taking into account the aforementioned toxicity and volatility of mercury, direct storage or incineration of mercury and mercurial wastes is not an option that can be envisaged.
This is why processes and methods aimed at reducing the mobility of mercury in the environment have been proposed.
These immobilization methods are essentially aimed at preventing the mercury from being released into the atmosphere, by volatilisation, and into the ground or soil, by leaching.
The methods for immobilization are amalgamation, stabilization and encapsulation.
Amalgamation is the physical immobilization of mercury by dissolution in another metal in order to form an amalgam or semi-solid alloy. Thus, for example, the U.S. Pat. No. 6,312,499 (hereinafter referenced as [1]) proposes an amalgamation with copper, with a minimum of 50% by weight of mercury in the amalgam.
The problem with this technique is that it does not reduce the risks of volatilisation and leaching of the mercury. The amalgamation must therefore be followed by an encapsulation, for example in a cementitious matrix as described in the patent application US 2008/0234529 (hereinafter referenced as [2]), in which case the mercury, even if amalgamated, can easily be volatilise under the effect of any increase in temperature such as the one which induced by the hydration of the cement used for the encapsulation.
Stabilization is the chemical immobilization of mercury by combination thereof with suitable chemical species. The stabilization of mercury most commonly proposed in the literature is the process consisting of inducing the reaction of mercury with sulfur in order to form mercury sulfide.
It is thus that stabilization methods by dry processes and stabilization methods by wet processes have been proposed.
The stabilization methods by dry processes are, for example, those described in the patent applications EP 1 751 775, EP 2 072 467 and EP 2 476 649 (hereinafter referenced as [3], [4] and [5] respectively). These methods have in common processes whereby the mercury is induced to react with sulfur in the solid state, in a reactor having a specific structure (reference [3]), a mixer (reference [4]), or a planetary ball mill (reference [5]), and to result in a product that comprises mercury sulfide crystallised in β form, which is black in colour and commonly referred to as “metacinnabar”, in an admixture with sulfur (references [3] and [5]) or with mercury sulfide crystallised in α form, which is red in colour and commonly referred to as “cinnabar” (reference [4]).
The stabilization methods by wet processes consist in dissolving the mercury in a concentrated strong acid, such as nitric acid or hydrochloric acid, and adding to the resulting solution a sulfur source, such as sodium sulfide, potassium sulfide, or ammonium sulfide, in order to lead to the precipitation of mercury in the metacinnabar form. A method of this type has been described by S. Chiriki (Schriften Forschungszentrums Jülich-Reihe Energie and Umwelt/Energy and Environment 2010, 67, 151 pages, hereinafter referenced as [6]).
In the light of the results presented in this reference document, the wet stabilization technique appears to present the advantages of being simple to implement, in particular with the possibility of working in batches and thus limiting the amount of mercury to be precipitated—which is advantageous in terms of safety —, and of resulting in a mercury/sulfur reaction which is both rapid and complete.
On the other hand, this technique generates large quantities of effluents that are aqueous, acidic and contaminated with mercury. In addition, gaseous hydrogen sulfide, which is a gas being, on the one hand, dangerous and, on the other hand, capable of leading, during its formation and its passage into the atmosphere, to other elements that one may also want to stabilize, is likely to be released over the course of this type of stabilization.
Encapsulation is the physical immobilization of mercury by entrapment within an impermeable matrix.
For the encapsulation of mercury, several types of matrices have been studied including, in particular, cementitious matrices based on Portland cements or phosphomagnesium cements, and sulfur based polymer matrices.
These studies show that the cementation process is a route of interest for the physical immobilization of mercury because it makes it possible to obtain leaching levels that are situated below the regulatory thresholds permissible, provided that the mercury has already been stabilized beforehand, in particular into mercury sulfide (C. R. Cheeseman et al., Waste Management 1993, 13 (8), 545-552, hereinafter referenced as [7], W. P. Hamilton and A. R. Bowers, Waste Management 1997, 17 (1), 25-32, hereinafter referenced as [8]) or by means of adsorption on a trap such as activated charcoal (J. Zhang and P. Bishop, Journal of Hazardous Materials 2002, 92(2), 199-212, hereinafter referenced as [9], or a zeolite having thiol functional groups (X. Y. Zhang et al., Journal of Hazardous Materials 2009, 168 (2-3), 1575-1580, hereinafter referenced as [10]).
Recently, results from tests designed to stabilize mercury in the form of mercury sulfide by reaction with sodium thiosulfate have been reported by M. B. Ullah (Thesis for Master of Applied Sciences 2012, University of British Columbia, 73 pages, hereinafter referenced as [11]). These results show that mercury reacts only very partially with sodium thiosulfate, with this being for pH values ranging from 6 to 12. Thus, only 10 to 15% of the mercury is attacked by the sodium thiosulfate after a period of 9 days of reaction therewith at a pH ranging from 6 to 10. At pH 12, the results are better, but the degree of mercury content that reacts with sodium thiosulphate is however only 50% after a period of 8 days of reaction. According to the author of these reported tests, the partial attack of mercury by sodium thiosulfate would lead to the precipitation of metacinnabar on the surface of the residual mercury, which would have the effect of then preventing this attack from being total. In any case, he concludes therefrom that a complete stabilization of mercury by sodium thiosulphate is impossible (see pages 35 and 52 of reference [11]).
However, in the context of their work on the development of a method for immobilizing mercury wastes, the inventors have found that, contrary to what reference [11] teaches, it is possible to precipitate mercury in the form of mercury sulfide, with a quantitative yield and within a time period that is compatible with an implementation on an industrial scale, by inducing the reaction of mercury with a thiosulfate in a basic aqueous medium, in particular at a pH of the order of 11-12, if this reaction is conducted in the presence of an alkali metal sulfide.
It is thus possible to completely stabilize the mercury present in a mercury waste by means of a wet process with mercury sulfide, with no production of hydrogen sulfide.
The inventors have also found that the embedding of the mercury sulfide thus obtained in cementitious pastes has little impact on the hydration of these cementitious pastes and on the mechanical properties of the materials resulting from the hardening thereof, which allows for a high degree of encapsulation of this mercury sulfide within the cementitious matrices and, consequently, for obtaining a reduced number of packaging parcels, for a given volume of mercury waste.
And it is therefore on these findings that the invention is based.
The invention relates to a method for immobilizing a waste comprising mercury, which method comprises:
and is characterized in that the precipitation of the mercury as mercury(II) sulfide is obtained by reacting the mercury with a thiosulfate in a basic aqueous medium, under agitation and in the presence of an alkali metal sulfide, the molar ratio of the thiosulfate to the mercury in the aqueous medium being at least equal to 1.
Thus, according to the invention, the waste comprising mercury is immobilized by a method which includes two successive steps, namely:
According to the invention, the stabilization of the mercury preferably comprises:
Although the molar ratio of the thiosulfate to the mercury present in the waste has a little effect on the duration and the yield of the precipitation so long as it is at least equal to 1, it is nevertheless preferred that the molar ratio of the mercury to the thiosulfate be equal to or greater than 2, typically comprised between 2 and 3 and, for example, of 2.5.
With regard to the molar ratio of the sulfide of an alkali metal to the mercury present in the waste, it is preferably at most equal to 1, and still better, less than 0.5, typically comprised between 0.1 and 0.3, and for example, of 0.2.
The thiosulfate used for the precipitation is advantageously a thiosulfate of an alkali metal and, more preferably, sodium thiosulfate (Na2S2O3) or potassium thiosulfate (K2S2O3) which are to be used preferentially in hydrated form.
However, it goes without saying that other thiosulphates also have the ability to be used as long as they are soluble in water (which is the case, for example, of magnesium thiosulfates Mg2S2O3 and ammonium thiosulfates (NH4)2S2O3) and that their cation (whether metallic or otherwise) does not interfere with the other ions in solution thereby leading to the precipitation of undesired compounds.
As for the alkali metal sulfide which is used for the precipitation, it is advantageously sodium sulfide (Na2S) or potassium sulfide (K2S) which are also to be used preferably in hydrated form.
In a preferred embodiment of the method of the invention, the stabilization of the mercury comprises:
As previously indicated, the binder used for the cementation may be selected, first of all, from the hydraulic cements.
The term “hydraulic cement” is understood to refer to a cement whose hardening is the result of the hydration by water of a finely milled material, constituted in whole or in part of a clinker, that is to say a product resulting from the firing of a mixture of limestone and clay. Thus, the term “hydraulic cement” does not include the so-called “geopolymer” cements whose hardening is the result of a polycondensation of a finely milled alumino-silicate material that is free of clinker, in an alkaline solution, or cements whose hardening is the result of a chemical reaction between the constituent material or materials of these cements and an acidic or basic solution (magnesium cements, alkali-activated slags, etc).
When the binder is selected from among hydraulic cements, it may then in particular be selected from:
These cements are in particular available from LAFARGE, HOLCIM, HEIDELBERGCEMENT, CEMEX, ITALCEMENTI and its subsidiary CALCIA.
The binder may also be selected from base-activated cements and, in particular, from vitrified blast-furnace slags, in which case it may be any slag deriving from the production of cast iron in the blast furnace and obtained either by vitrification under water (granulated slag) or by air vitrification or “pelletising” (pelletised slag). This type of slag is typically composed of from 38% to 48% by mass of calcium oxide (CaO), from 29% to 41% by mass of silica (SiO2), from 9% to 18% by mass of alumina (Al2O3), from 1% to 9% by mass of magnesia (MgO), and at most 3% by mass of secondary constituents. By way of example of such a slag, mention may be made of the ground granulated blast furnace slag produced by the company ECOCEM.
The binder may also be selected from acid-activated cements and, in particular, from phosphomagnesium cements, that is to say cements that are composed of an oxidized magnesium source, that is to say in the oxidation state +II, this source being typically a magnesium oxide (MgO) calcined at high temperature (of “hard burnt” or “dead burnt” type), either pure or presenting impurities of the type SiO2, CaO, Fe2O3, AlO3, etc., and a phosphate source soluble in water, this source being typically a phosphoric acid salt.
The phosphomagnesium cement that may be used in the invention may be any phosphomagnesium cement known to the person skilled in the art. However, it is preferred that this cement be composed of:
Finally, the binder may also be composed of a mixture of one or more hydraulic cements and/or one or more base-activated cements.
According to the invention, the binder is advantageously selected from CEM I, CEM II, CEM III, CEM V cements, vitrified blast furnace slags, mixtures thereof, and phosphomagnesium cements and, still better, from CEM I cements and phosphomagnesium cements.
Depending on the nature of the binder (hydraulic cement, base-activated cement or acid-activated cement), the aqueous mixing solution may be of neutral pH, basic (in which case this solution preferably comprises a strong base of the sodium hydroxide or potassium hydroxide type, preferentially at a concentration of at least 1 mol/L) or acidic (in which case this solution preferably comprises a phosphoric acid salt such as those mentioned previously above).
In addition to including the binder powder and the aqueous mixing solution, the composition may comprise at least one adjuvant selected from plasticisers (water-reducing or not), superplasticisers, setting retarders and compounds that combine several effects such as superplasticisers/setting retarders, depending on the properties of workability, setting and/or hardening that it is desired to confer to the cementitious paste.
In particular, the composition may comprise a superplasticiser and/or a setting retarder.
Superplasticisers that are likely to be suitable are, in particular, high water-reducing superplasticisers of the polynaphthalene sulphonate type, such as the one available from the company BASF under the product reference Pozzolith™ 400N, whereas setting retarders that are likely to be suitable, in particular are hydrofluoric acid (HF) and especially salts thereof (sodium fluoride for example), phosphoric acid (H3PO4) and salts thereof (sodium phosphate for example), boric acid (H3BO3) and salts thereof (sodium borate of borax type for example), citric acid and salts thereof (sodium citrate for example), malic acid and salts thereof (sodium malate for example), tartaric acid and salts thereof (sodium tartrate for example), sodium carbonate (Na2CO3), and sodium gluconate.
When the composition comprises a superplasticiser, the latter preferably does not represent more than 4.5% by mass of the total mass of this composition whereas, when the composition comprises a setting retarder, in particular, citric acid or a salt thereof, the latter preferably does not represent more than 3.5% by mass of the total mass of said composition.
The composition may in addition comprise sand, for example of the type marketed by the company SIBELCO under the product reference CV32, in which case the sand/binder mass ratio could reach 6.
The composition typically has a W/B ratio (that is that is to say a mass ratio between the water and the binder present in the composition) ranging from 0.1 to 1, preferably from 0.2 to 0.6 and, still better, from 0.35 to 0.55.
According to the invention, the stabilization of the mercury and the encapsulation of the waste may be carried out in the same container or “conditioning container”, for example a barrel type container, in which case the encapsulation of the waste comprises:
If adjuvants and/or sand are provided for, they may be introduced into the container at the same time as the binder or, if the adjuvants are soluble in water, in a form dissolved in the aqueous mixing solution.
As an alternative, the stabilization of the mercury may be carried out in a first container and the encapsulation of the waste is carried out in a second container or “conditioning container”.
A number of ways of carrying out the encapsulation are thus then possible.
Thus, for example, the encapsulation of the waste may, in the first place, comprise:
In which case, if adjuvants and/or sand are provided for, they are then preferably introduced into the second container at the same time as the binder and the aqueous mixing solution.
The encapsulation of the waste may, in the second place, comprise:
In which case, if adjuvants and/or sand are provided for, they may then be introduced into the container at the same time as the binder or, if the adjuvants are soluble in water, in a form dissolved in the aqueous mixing solution.
In the two cases, the waste may be introduced into the second container in two forms:
According to the invention, the mass of the waste which is embedded in the cementitious paste may represent from 5 to 70% of the mass of the ensemble formed by the waste and this paste.
The hardening of the cementitious paste may, for example, be carried out by storage of the conditioning container at ambient temperature and under controlled hygrometry conditions.
This container is hermetically sealed, either between the embedding and the hardening, or after the hardening.
The waste may be any waste comprising mercury and may in particular be earth, rubble (for example, originating from the demolition of mercury-containing facilities), sludge (for example, originating from halogen chemistry), a technological mercury waste, that is to say, consisting of used equipment such as waste comprising batteries containing mercury (button cells, stick batteries, etc), accumulators, fluorescent tubes, low energy light bulbs, mercury thermometers, mercury barometers, mercury sphygmomanometers, tubes, absorbents, electronic cards, etc., or even a mixture of different types of mercurial waste.
The mercury present in the waste may be in a wide variety of forms prior to its stabilization: thus, it may entail mercury in the metallic state (that is, in the oxidation state 0), also referred to as “elemental mercury”; mercury in the form of mercurous or mercuric inorganic compounds such as Hg2Cl2 or calomel, Hg2O, HgCl2, Hg(OH)2, HgO, HgSO4, HgNO3, Hg(SH)2, HgOHSH, HgOHCI, HgClSH, etc; or mercury in the form of organomercury compounds such as mono methyl mercury compounds CH3Hg+X− (where X− represents any anion, for example Cl− or NO3−), often referred to by the generic term “methylmercury”, or monoethyl mercury compounds C2H5Hg+X− (where X− represents any anion, for example Cl− or NO3−), often referred to by the generic term “ethylmercury”.
Preferably, the waste is derived from one or more nuclear facilities.
More preferably, the waste comprises mercury in the metal state.
Depending on the nature and the size of the waste to be treated, the method in addition includes a preliminary treatment for reducing the dimensions of the waste, for example a mechanical treatment such as crushing, fragmentation or the like.
In addition to the previously mentioned advantages (quantitative stabilization of mercury as mercury sulfide, absence of H2S production, high encapsulation rate), the method of the invention presents other advantages, in particular:
Other characteristic features and advantages of the method of the invention will emerge from the additional description which follows, which relates to examples of implementation of the two steps—stabilization and encapsulation by cementation—that it comprises as well as to the presentation of the properties of the mercury sulfide thus obtained and of the materials resulting from the encapsulation of this mercury sulfide in cementitious matrices.
It goes without saying that this additional description is provided by way of illustration of the subject matter of the invention and is in no way intended to be interpreted as a limitation of this subject matter.
At ambient temperature (21±2° C.), an aqueous solution of sodium thiosulphate is prepared by dissolution of 6 g of sodium pentahydrate thiosulphate Na2S2O3.5H2O in 50 ml of deionised water and then adding to this solution 2.04 g of mercury metal Hg(0), under agitation. The mercury is dispersed in the solution in the form of small droplets.
After agitation for a period of 2-3 hours, the solution becomes greyish and its pH, which was 7-8 prior to the addition of mercury, increases until reaching the value of 11-12. These modifications are due to the formation in the reaction medium of mercury thiosulfates of the type Hg(S2O3) and/or Hg(S2O3)22−.
After respectively 24 hours and 48 hours of agitation, 0.20 g of sodium sulfide Na2S.H2O is added to the solution, i.e. amounting to a total of 0.40 g.
After 120 hours of agitation, the solution, which is red in colour, is filtered in order to recover all of the solid phase dispersed in this solution.
This solid phase is subjected to X-ray diffraction analysis (XRD). The diffractogram obtained, which is illustrated in
Moreover, the optical microscopic observation of these particles shows that they measure from 5 to 10 μm.
The mercury sulfide obtained in Example 1 here above is encapsulated in cementitious matrices which are obtained by hardening two types of mortar, respectively M1 and M2, whose composition is presented in Table I here below.
In order to do this, the mercury sulfide is added to the mixture of the solid constituents of the mortars, at a level of 10% or 20% by mass relative to the total mass of the mortars, and then, after homogenisation, the mixing water is added. The mixing of the mortars is carried out according to the rules defined in the standards in force for the preparation of typical standard mortars for the measurements of mechanical resistance.
The setting time, as determined by means of a Vicat setting time tester according to the standard EN 196-3+A1 (Methods of testing cement. Part 3: Determination of setting times and soundness), as well as the maximum temperature reached during hydration, as determined under Langavant semi-adiabatic conditions according to the standard EN 196-9 (Methods of testing cement. Part 9: Heat of hydration—semi-adiabatic method), of the mortars thus added of mercury sulfide are shown in Table 2 here below.
By way of comparison, also indicated in this table are the Vicat setting time and the maximum hydration temperature obtained for mortars M1 and M2 free of mercury sulfide α-HgS.
Moreover,
Table 2 and
The materials resulting from the hardening of the mortars M1, M1+10% of α-HgS, M1+20% of α-HgS, M2, M2+10% of α-HgS, and M2+20% of α-HgS are subjected to compressive and flexural strength tests according to the standard NF EN 196-1 (Methods of testing cement. Part 1: Determination of mechanical strength).
The results of the compressive strength tests are illustrated in
These figures show that, for a given type of mortar (M1 or M2), the adding of mercury sulfide α-HgS in the mortar does not substantially modify the mechanical properties of the material resulting from the hardening of this mortar.
The materials resulting from the hardening of the mortars M1, M1+10% of α-HgS, M1+20% of α-HgS, M2, M2+10% of α-HgS, and M2+20% of α-HgS are also subjected to leaching tests according to the standards XP CEN/TS 15862 (Leaching on monoliths) and NF EN 12457-2 (Leaching on fragments).
The main operating conditions for these tests are presented in Table 3 here below.
At the end of the 24 hours of leaching, the leachates are filtered on a 0.45 μm membrane filter using a vacuum filtration device and then the eluates are analysed by plasma torch atomic emission spectrometry (ICP-AES).
These analyses show that all the eluates have a mercury concentration of less than 0.01 part per million (ppm), which corresponds to maximum leaching values of 0.005 mg/kg for monolithic tests and 0.1 mg/kg for fragment tests, that is to say leaching values well below the regulatory thresholds as set by ANDRA.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1656083 | Jun 2016 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/FR2017/051752 | 6/29/2017 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2018/002540 | 1/4/2018 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 5173286 | Audeh | Dec 1992 | A |
| 6312499 | Rehmat et al. | Nov 2001 | B1 |
| 20080019900 | Riviere-Huc et al. | Jan 2008 | A1 |
| 20080234529 | Chan et al. | Sep 2008 | A1 |
| Number | Date | Country |
|---|---|---|
| 103736387 | Apr 2014 | CN |
| 4123907 | Jan 1993 | DE |
| 2072467 | Jun 2009 | EP |
| 2476649 | Jul 2012 | EP |
| 1751775 | Oct 2012 | EP |
| 2005014472 | Feb 2005 | WO |
| Entry |
|---|
| International Search Report for PCT/FR2017/051752 dated Sep. 29, 2017. |
| Written Opinion for PCT/FR2017/051752 dated Sep. 29, 2017. |
| Preliminary French Search Report for FR 1656083 dated Feb. 23, 2017. |
| Chiriki, S., “Disposal strategy of proton irradiated mercury from high power spallation sources” INL Energy and Environment, 2010, vol. 67, 151 pages. |
| Cheeseman, C.R. et al., “Heavy Metal Leaching From Hydroxide, Sulphide and Silicate Stabilished/Solidified Wastes”, In: Waste Management, 1993, vol. 13(8), pp. 545-552. |
| Hamilton, W.P. et al., “Determination of Acute Hg Emissions From Solidified/Stabilized Cement Waste Forms”, in: Waste Management, 1997, vol. 17, No. 1, pp. 25-32. |
| Zhang, J. et al., “Stabilization/Solidification (S/S) of Mercury-Containing Wastes Using Reactivated Carbon and Portland Cement”, In: Journal of Hazardous Materials, 2002, vol. B92(2), pp. 199-212. |
| Zhang, XY. “Stabilization/Solidification (S/S) of Mercury-Contaminated Hazardous Wastes Using Thiol-Functionalized Zeolite and Portland Cement”, In: Journal of Hazardous Materials, 2009, vol. 168(2-3), pp. 1575-1580. |
| Ullah, M.B., “Mercury Stabilization Using Thiosulfate and Thioselenate”, A Thesis submitted in partial fulfillment of the requirements for the degree of master of applied science, The University of British Columbia, Apr. 2012, 73 pages. |
| Number | Date | Country | |
|---|---|---|---|
| 20190336806 A1 | Nov 2019 | US |
