WO2011029970A2 - Procedimiento de estabilización de mercurio líquido mediante cemento polimérico de azufre, vía sulfuro de mercurio - Google Patents
Procedimiento de estabilización de mercurio líquido mediante cemento polimérico de azufre, vía sulfuro de mercurio Download PDFInfo
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- WO2011029970A2 WO2011029970A2 PCT/ES2010/070547 ES2010070547W WO2011029970A2 WO 2011029970 A2 WO2011029970 A2 WO 2011029970A2 ES 2010070547 W ES2010070547 W ES 2010070547W WO 2011029970 A2 WO2011029970 A2 WO 2011029970A2
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- WIPO (PCT)
- Prior art keywords
- mercury
- sulfur
- weight
- mixture
- sulfide
- Prior art date
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 98
- 239000011593 sulfur Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 81
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 71
- 239000007788 liquid Substances 0.000 title claims abstract description 37
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 title abstract description 40
- 239000011414 polymer cement Substances 0.000 title abstract description 36
- 230000003019 stabilising effect Effects 0.000 title abstract 3
- 239000000203 mixture Substances 0.000 claims abstract description 59
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
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- 229910052956 cinnabar Inorganic materials 0.000 description 27
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- 150000001875 compounds Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
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- -1 sulfur anions Chemical class 0.000 description 5
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
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- 238000012512 characterization method Methods 0.000 description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 238000007792 addition Methods 0.000 description 2
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
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- 239000006028 limestone Substances 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229940008718 metallic mercury Drugs 0.000 description 2
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- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
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- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- UAGGVDVXSRGPRP-UHFFFAOYSA-N diethylcarbamothioic s-acid Chemical compound CCN(CC)C(S)=O UAGGVDVXSRGPRP-UHFFFAOYSA-N 0.000 description 1
- ZXSBDSGRQIWJPM-UHFFFAOYSA-N dimethylcarbamothioic s-acid Chemical compound CN(C)C(S)=O ZXSBDSGRQIWJPM-UHFFFAOYSA-N 0.000 description 1
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 150000002730 mercury Chemical class 0.000 description 1
- 229940100892 mercury compound Drugs 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G13/00—Compounds of mercury
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/36—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing sulfur, sulfides or selenium
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/24—Organic substances containing heavy metals
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to a process for stabilizing liquid mercury by using sulfur polymer cements, and previously transforming liquid mercury into mercury sulfide (metacinabrium). STATE OF THE TECHNIQUE
- Amalgamation is defined as the combination of mercury with a metallic reagent such as copper, gold, zinc, aluminum, nickel, tin, silver or sulfur, resulting in a solid, non-volatile product.
- a metallic reagent such as copper, gold, zinc, aluminum, nickel, tin, silver or sulfur
- amalgams are semi-solid solutions obtained by dissolving between mercury and a solid metal. This process has been used for the extraction of precious metals from its minerals (after amalgamation, the amalgam is subjected to a heat treatment to volatilize the mercury and recover the precious metal).
- amalgamation is a relatively cheap and rapid process for the treatment of liquid mercury, the disadvantages of the process stem from the difficulties for its use on a larger scale and the need to use diluted nitric acid to achieve high efficacy.
- the presence of water in the amalgam can lead to the formation of hydroxides of the amalgamating metal which makes the process unsuitable for the treatment of contaminated mercury, for example with radioactive elements.
- the method is not able to adequately stabilize unstable forms of mercury in hazardous waste materials.
- the mercury reacts with the powdered sulfur and / or liquid sulfur (polysulfide) to form mercuric sulfide.
- Mercuric sulfide the most stable compound formed between mercury and sulfur, exists in two stable forms. The first is the tetrahedral cubic form (metacinabrium) of black color and the other stable form is the hexagonal, red form that is found in nature as cinnabar. Both forms are insoluble in water and acid solutions. In alkaline solutions with excess sulfur anions the HgS is solubilized according to the reaction: HgS + S 2 " -> HgS 2 2 ⁇ .
- HgS Another common method to form HgS is to dissolve the mercury in HCI, neutralize it to form an aqueous solution of HgCI 2 and then precipitate the mercuric sulfide by adding Na 2 S. This method cannot be applied on a large scale because the Mercuric chloride is slightly soluble in water and a secondary effluent with a certain amount of mercury originates.
- Soluble mercury can be present in materials such as those deposited in landfills, sediments, etc., it is often physically and economically impossible to attempt to eliminate mercury from these materials. Effluents containing mercury from these deposits can contaminate water supplies and land.
- US 4354942 describes a process for stabilizing in situ soluble mercury in deposits of mercury containing materials. The process comprises treating the deposits with an amount of stabilizer consisting of an inorganic sulfur compound (sulphides, alkali metal thiosulfates, alkaline earth metal thiosulfates, alkali metal dithionites and alkaline earth metal dithionites). Inorganic sulfur compounds react with soluble mercury to convert it into a water-insoluble mercury compound.
- HgS The direct reaction between elemental mercury and elemental sulfur to form HgS is widely known.
- the drawback of this procedure is that the reaction between the elementary S and the Hg is not total, that is, it can happen that after the reaction, a part of the elementary Hg remains as such, without being transformed into HgS.
- HgS is less leachable than elementary Hg and is A chemically stable product.
- surfactants can be used to disperse elemental mercury.
- a process which includes the steps of: combining an initial residue containing mercury with a polysulfide and with a sulfur-containing reactive compound, other than polysulfide, to form a composite material; and mixing the composite material with mercury or mercury residues in order to form mercuric sulfide. Because many mercury residues contain water, the sulfur-containing reactive compound reacts with the mercury in aqueous solution.
- sulfur carriers elemental sulfur, inorganic sulfur (alkali metal bisulfide, mercaptans, alkali metal sulfides) and / or mixtures thereof can be used.
- the polysulfides act as activators of the reaction between the sulfur-containing reactive compound and the unstable forms of mercury, and are preferably selected from the group of calcium polysulfides, sodium polysulfides and other alkaline earth polysulfides and mixtures thereof. These forms of polysulfides are highly soluble in water.
- the mixing stage is performed by intrusive mixing techniques, using a device that allows mixing a viscous material and expelling or ventilating any vaporized liquid. According to the authors, the product In the end, it can pass the Leaching Procedure for Toxic Characterization or TCLP test (Toxic Characterization Leach Procedure), and contain no more than 1000 ppm of elemental mercury and / or environmentally unstable forms of mercury species.
- the reaction of elemental sulfur with mercury is spontaneous and highly exothermic at room temperature and its velocity depends on the temperature.
- the release of thermal energy from the reaction can increase the operating temperature and, in turn, the reaction rate, thereby increasing the additional energy and consequently can lead to an uncontrolled reaction.
- Water and / or the loading agent are used to control the temperature during the mixing stage and to prevent the temperature from exceeding 100-120 ° C.
- the filler any microporous granulated material such as clays, cements, floors, etc. provides not only temperature control but also sufficient volume for efficient mixing.
- a method for stabilizing heavy metals, including mercury, is described in US691 1570, especially when these metals are dispersed within a particulate material (solid waste and soil).
- the process consists of forming an insoluble metal sulfide by stirring the various additives with the particulate material, blowing oxygen into the particulate material in order to favor that the sulfur-containing compounds form the insoluble metal sulfide.
- the metal reagent can be an elementary form of Zn, Sn, Cu, Ti, Pb or mixtures thereof.
- the sulfur-containing compounds may be sulfide or polysulfide, hydrogen sulfide, dimethylthiocarbamate, diethylthiocarbamate, sodium sulfide or sodium thiosulfate, calcium polysulphide.
- the excess of unreacted sulfide or polysulfide remains in the particulate material after insoluble metal sulfide has formed. Because the sulfide content is limited in many environmental regulations, the excess sulphide produced in the previous reaction is eliminated by reacting with the reactive metals contained in the particulate material. Iron is used for this, either metallic iron or some of its salts (chloride, sulfate ...) that react with excess sulfur forming insoluble sulphides.
- WO2006016076 describes a method for stabilizing metallic mercury by its reaction with sulfur in the solid state. The reaction takes place in a hermetically sealed reactor by adjusting the rotation, which allows working at a controlled pressure higher than atmospheric
- a mixture of liquid Hg and Hg residues (for example, liquid Hg contaminated with radionuclides) is mixed with an excess of a sulfur polymer cement and sulfur additives (sodium sulfide and / or Cyanex 471 x).
- the mixture is heated at 40 ° C for several hours until all the Hg has been transformed into HgS. Subsequently, the mixture is heated to 135 ° C, a new amount of sulfur polymer cement is added and a melt is obtained which, upon cooling, solidifies.
- HgS HgO and elemental Hg
- pyrite and troilite natural and synthetic sulphides
- This type of process is carried out in a "wet way", controlling the pH and in the presence or absence of air and using metal sulphides, such as pyrite, as S. carrier materials.
- metallic Hg is introduced into the polymer matrix prior to transformation into mercury sulphide (HgS), which gives the final product better physical-chemical properties (less leaching under aggressive conditions; better mechanical resistance to flexural fracture and compression and lower porosity, mainly). All this makes the final materials object of the present invention considered more stable in the short, medium and long term and, therefore, that the process developed has advantages for the safe and permanent storage of metallic Hg.
- HgS mercury sulphide
- the present invention provides a process for transforming metallic Hg into a chemical with less danger (less leachable under standardized international test conditions) and confining this product into a matrix made of a mixture of aggregates, elemental sulfur and a sulfur polymer. Therefore, the present invention relates to a liquid mercury stabilization process (hereinafter method of the invention) comprising: Liquid mercury stabilization process comprising a step (a) in which liquid mercury and sulfur are reacted elemental in stoichiometric conditions by means of a milling process, obtaining mercury sulfide (metacinabrium) as a reaction product.
- Liquid mercury stabilization process comprising a step (a) in which liquid mercury and sulfur are reacted elemental in stoichiometric conditions by means of a milling process, obtaining mercury sulfide (metacinabrium) as a reaction product.
- stabilization process means a physical-chemical method that also involves chemical immobilization by the formation of a stable compound or a non-water soluble compound. Stabilization reduces or eliminates the possibility of vaporization or leaching to the environment of a hazardous substance such as Hg under normal conditions.
- step (a) is carried out by any milling process known to a person skilled in the art.
- the grinding process is carried out in any ball mill.
- the milling process is carried out in a high-energy planetary mill, such as Pulverisette 6.
- the process described above further comprises a step (b) in which the product obtained in step (a) is added to a mixture comprising aggregates, elemental sulfur and a sulfur polymer, obtaining a polymeric cement of Sulfur as the final product.
- liquid mercury suitable for use in the process of the invention can come from any industrial process that generates it as waste or by-product.
- liquid mercury is a catalyst for the manufacture of chlorine and a metal that can be obtained in the recycling of batteries and accumulators, temperature measurement equipment, or gold mining waste, among others. Its treatment by the method of the invention eliminates its danger and allows its safe storage.
- the starting liquid mercury comes from the caustic chlorine industry, obtaining thus a sulfur polymer cement by the process of the invention.
- a sulfur polymer cement As described in the present invention, starting from liquid mercury it is possible to obtain a sulfur polymer cement whose properties will depend on the proportion of mercury sulfide in the mixture, the proportion of sulfur and sulfur polymer and the proportion of aggregates
- Equation 1 reflects the chemical reaction that occurs in step (a):
- the elemental sulfur used in step (a) to act as a mercury sulphide forming agent in said process is any type of elemental sulfur powder with a particle size ⁇ 60 ⁇ , if You can also use any elemental sulfur of a particle size larger than the one indicated, for which it would be necessary to grind it to a particle size smaller than the one indicated above.
- a commercial elemental sulfur from the desulfurization of petroleum derivatives is used.
- said milling is carried out in a ball mill at a speed of between 400 and 450 rpm for a time between 15 and 60 min. And more preferably, the grinding speed is 400 rpm for a time of 60 min.
- the weight ratio balls / reaction mixture of step (a) (Hg and S) is between 5.3 and 10.7. And more preferably, the weight ratio balls / reaction mixture of step (a) (Hg and S) is 5.4.
- Step (a) of the process of the invention can be controlled by various usual experimental techniques known to a person skilled in the art. The choice of appropriate techniques, as well as their implementation, is a routine task for the person skilled in the art. Thus, for example, the result obtained in the reaction of liquid mercury with sulfur can be studied by X-ray Diffraction (DRX), Scanning Electron Microscopy (MEB) and chemical analysis for the determination of mercury by atomic fluorescence spectrometry . Once the mercury sulphide is obtained, a stable sulfur polymer cement is obtained.
- DRX X-ray Diffraction
- MEB Scanning Electron Microscopy
- step (b) a mixture comprising aggregates, elemental sulfur and the mercury sulphide obtained in the stage is heated in an oven at a temperature between 155 and 165 ° C (to). Once the sulfur has melted, the temperature is lowered to about 130-150 ° C. The most preferred temperature is 140 ° C. Once this temperature has been reached, the sulfur polymer is incorporated into the hot mixture. The temperature is maintained at 140 ° C, stirring the mixture until the polymer is completely melted, which is achieved in a time between 5 and 10 min. Preferably, the total melting of the polymer takes place in about 6 min.
- sulfur polymer is meant, in the present invention, a chemically modified sulfur.
- the modification is necessary to avoid that in the cooling of the S, which has been heated to a temperature higher than 1 14 ° C, the species S (alpha), orthorhombic, that appears at about 94 ° C, is formed and the shape prevails S (beta) monoclinic, which is suitable for S to be transformed into polymeric forms and can be used to obtain sulfur cements.
- the modification can be made by combining sulfur with dicyclopentadiene (DCPD), cyclopentadiene (CPD), pentadiene, dipentene, organosilanes, glycol and petroleum, phosphoric acid and also by olefinic hydrocarbon polymers, which has been the method chosen herein.
- DCPD dicyclopentadiene
- CPD cyclopentadiene
- pentadiene dipentene
- organosilanes glycol and petroleum
- phosphoric acid phosphoric acid
- olefinic hydrocarbon polymers which has been the method chosen herein.
- aggregates is meant in the present invention a granulated material that differs from other materials by its chemical stability and its mechanical strength. They can be natural aggregates, such as sedimentary limestone rocks (limestone or dolomite), sand, gravel, or other rocks such as granite, basalt or quartzite among others. They can also be of artificial origin or come from recycling, such as construction and demolition waste.
- the aggregate mixture comprises gravel, with a grain size of less than 6.3 mm, in a proportion between 19% and 23% by weight with respect to the total weight of the mixture; sand, in a proportion between 38% and 47% by weight with respect to the total weight of the mixture; calcium carbonate, in a proportion between 6% and 8% by weight with respect to the total weight of the mixture; elemental sulfur, in a proportion of 10% to 15% by weight with respect to the total weight of the mixture; sulfur polymer, in a proportion of 1 to 1.5% by weight with respect to the total weight of the mixture; and mercury sulfide, in a proportion between 6% and 30% by weight with respect to the total weight of the mixture.
- Another preferred embodiment of the process also comprises a final stage in which the hot mixture obtained in step (b) is deposited in a mold to obtain a material with a suitable finish.
- the material is arranged on a vibrating table with a vibration frequency of 3000 rpm for a time ranging from 30 to 60 s, depending on the viscosity of the sample.
- the surface is smoothed and the stone material is allowed to cool to room temperature. It is unmold and stored at room temperature.
- the present invention is applied to confinement in safe matrices of metallic mercury from various industrial sectors (for example: chlorine manufacturing processes (caustic chlorine industries); mercury residues; mercury contaminated soils).
- Fig. 1 Shows the granulometric curve of the aggregate mixture used in the example of the invention.
- Fig. 2 Shows an X-ray diffraction spectrum of the reaction product between liquid mercury and elemental sulfur after 1 hour of grinding.
- Fig. 3 Shows microfotog scanning electron microscopy (MEB) raffles of the reaction product obtained after 1 hour of grinding [(a) appearance of a particle with metacinabrium surface coating, (b) appearance of a set of particles of irregular granular morphology, covered with metacinabrium crystals].
- Fig. 4 Shows the macrophage raffia of some of the sulfur polymer cements obtained after steps (a) and (b) of the process of the invention.
- the morphology of the reaction product is shown in Figure 3 (sections a and b). As can be seen, it is a preferably granular morphology with a superficial deposition of metacinabrium cubic habit particles.
- the TCLP protocol (EPA Method 131 1) was followed. To do this, three samples of 20 g each of the reaction product, obtained after 1 hour of grinding, were extracted with 400 ml of a mixture of acetic acid and sodium hydroxide. The samples were kept under stirring for 18 hours, after which they were filtered on a Millipore vacuum filter provided with a 47 mm pitch prefilter and a glass fiber filter with a pitch size of 0.7 ⁇ . The filtered solutions were acidified with nitric acid to pH ⁇ 2 and the mercury content was determined by analysis in a Leco AMA 254 equipment by the cold steam atomic absorption technique.
- the mercury sulfide obtained in the previous stage is added and then the sulfur polymer, stirring and stirring the mixture to facilitate its melting and homogenization of all the components, which is achieved in a time of approximately 6 minutes.
- the hot mixture turns into molds that are agitated on a vibrating table with a vibration frequency of 3000 rpm for a time ranging from 30 to 60 seconds, depending on the viscosity of the sample.
- the surface is smoothed and the monoliths are allowed to cool to room temperature. They are unmold and stored at room temperature.
- the molds used had dimensions of 40x40x160 mm 3 , dimensions that allow applying standard standards for the study of their physical-chemical properties.
- Variable amounts of mercury sulfide were mixed with the mixture of aggregates and sulfur.
- the mixtures were made by adding to them all 15% elemental sulfur (percentage by weight with respect to the total weight) and 1.5% sulfur polymer.
- the determination of leachable mercury content was performed following the TCLP protocol (US EPA Method 131 1). For this, three samples of 20 g each of the reaction product obtained after 1 hour of grinding were extracted with 400 ml of a mixture of acetic acid and sodium hydroxide. The samples are kept under stirring for 18 hours, after which they were filtered on a Millipore vacuum filter provided with a 47 mm step size prefilter and a glass fiber filter with a pitch size of 0.7 ⁇ . The filtered solutions were acidified with nitric acid to pH ⁇ 2 and the mercury content was determined by analysis in a Leco AMA 254 equipment by the cold steam atomic absorption technique. Table 3 shows the contents of Hg in the leachate from the manufactured sulfur polymer cements. All polymer cements containing mercury sulphide produce leachates with Hg contents below the value determined by the US EPA as the limit value of the Hg content in water (200 M g / I).
- the skeletal density, p s , and the real density, p r were determined by an AccuPyc 1330 helium pycnometer.
- the skeletal density was determined in pieces of the sulfur polymer cements and the real density, grinding the polymer cements until obtaining a particle size less than 50 ⁇ . The grinding was carried out in a Temag mill.
- the apparent density, p b was determined by measuring the volume of polymer particle cement shell (specific pore volume) using GeoPyc 1360 equipment for this purpose.
- Capillarity water absorption was determined following the LINEEN 480 Standard. Different samples of polymer cements were placed in a closed chamber with 55% relative humidity and a 5 cm thick layer of water within which the Cement specimens in an upright position, that is, resting on one of their sides. Each sample was weighed individually before being placed in the chamber. The specimens were cured for 28 days and the amount of water absorbed after immersion was determined for 10 min, 30 min, 1 h, 3 h, 6 h, 24 h, 72 h and 28 days. After 28 days, the samples were removed from the chamber, dried with paper to remove excess surface water and weighed, determining the variation in mass ( ⁇ ) and capillarity adsorption (W S ) with respect to the surface of each of the test specimens tested.
- ⁇ variation in mass
- W S capillarity adsorption
- the low-pressure water absorption was determined following the methodology adopted from the RILEM (International Union for Testing and Research Laboratories for Materials and Structures) test No. II (Water absorption under low pressure (pipe method)) of water absorbed per unit of surface at a specific time under a pressure equivalent to 10 cm of water column.
- the test simulates real situations where the pressure of the column represents the pressure produced by the collision of raindrops from rain to high speed (approx. 140 km / h) against the material under study.
- the samples of sulfur polymer cements containing mercury sulphide were placed in individual vessels of 1550 ml capacity containing a sufficient quantity of a solution of potassium hydroxide of a concentration equal to 5.6 g / l to cover the cubic specimens, placed in a spacer, with an excess of (25 ⁇ 5) mm.
- the test was performed in a perfectly conditioned curing chamber.
- the glasses were covered with a transparent plastic film for (21 ⁇ 0.1) days. After that time, the cubic specimens were removed from their respective vessels and dried in the air, on a laboratory table, until their weight was equal to ⁇ 2 g in relation to the initial weight of the specimens.
- each test tube was immersed again in the alkaline solution and after 21 days they were removed, air dried and weighed.
- a second immersion test was performed and the weight increases of each cubic test treated after the alkali test were calculated.
- the absorption coefficient (AR to ik), expressed in% in grams, can determined by calculating the relationship between the weights of each test tube after the test and the initial weight.
- Table 7 shows the results obtained. Polymeric sulfur cements containing mercury sulfide have very high alkali resistance.
- the salt spray chamber resistance has been carried out in accordance with the UNE-EN 14147: 2003 Standard. For this, an Ascott 450T salt spray accelerated aging chamber was used.
- the saline solution was prepared by dissolving 100g of NaCl (> 95% w / w) in per liter of deionized water, with an ionic conductivity of less than 20 ⁇ / ⁇ 2 .
- the chamber temperature was kept constant at 35 ⁇ 5 ° C.
- the test consisted of subjecting the sulfur polymer cements containing mercury sulphide and the reference polymer cement to 60 exposure cycles in the saline atmosphere of the chamber. Each cycle consists of an exposure to salt spray for 4 hours and drying of the specimens in the chamber for 8 h. At the end of the 60 cycles the specimens were removed from the chamber and immersed in deionized water to remove all deposited salt. The water was changed every day until the salt was completely removed, which is achieved when the conductivity of the solution in contact with the specimens does not exceed twice the characteristic value of the initial wash water. Then, the specimens were dried at a temperature of 70 ⁇ 5 ° C to constant mass. The results are expressed as mass loss (% mass).
- Table 8 shows the weight losses of the sulfur polymer cement samples containing mercury and reference sulphide, after the accelerated aging test in the salt spray chamber. Mass losses are less than 1% in all cases tested, which indicates that the sulfur polymer cements have very high resistance to the saline atmosphere.
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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ES10815022T ES2703424T3 (es) | 2009-09-09 | 2010-08-11 | Método de estabilización de mercurio líquido mediante cemento polimérico de azufre, a través de sulfuro de mercurio |
US13/395,268 US8580880B2 (en) | 2009-09-09 | 2010-08-11 | Method for stabilising liquid mercury using sulfur polymer cement, via mercury sulfide |
BR112012005381A BR112012005381A2 (pt) | 2009-09-09 | 2010-08-11 | método para estabilizar mercúrio líquido utilizando cimento de polímero de enxofre através de sulfureto de mercúrio |
JP2012528395A JP5745523B2 (ja) | 2009-09-09 | 2010-08-11 | 硫化水銀を介する、硫黄ポリマセメントを用いた液体水銀を安定化するための方法 |
EP10815022.8A EP2476649B1 (en) | 2009-09-09 | 2010-08-11 | Method for stabilising liquid mercury using sulfur polymer cement, via mercury sulfide |
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ESP200930672 | 2009-09-09 | ||
ES200930672A ES2355001B1 (es) | 2009-09-09 | 2009-09-09 | Procedimiento de estabilizacion de mercurio liquido mediante cemento polimerico de azufre, via sulfuro de mercurio |
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WO2011029970A2 true WO2011029970A2 (es) | 2011-03-17 |
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US (1) | US8580880B2 (es) |
EP (1) | EP2476649B1 (es) |
JP (1) | JP5745523B2 (es) |
BR (1) | BR112012005381A2 (es) |
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WO2016064615A1 (en) | 2014-10-24 | 2016-04-28 | The University Of Tulsa | Sulfur-limonene polysulfide |
CN104438285B (zh) * | 2014-11-06 | 2019-12-24 | 中国科学院生态环境研究中心 | 一种以硫为添加剂机械球磨无害化处理废汞触媒的方法 |
JP6628486B2 (ja) * | 2015-03-24 | 2020-01-08 | 特定非営利活動法人広島循環型社会推進機構 | 金属水銀処理方法 |
FR3037580B1 (fr) | 2015-06-17 | 2019-08-16 | Sarp Industries | Procede de stabilisation de mercure metallique |
EP3228610A1 (fr) | 2016-04-07 | 2017-10-11 | Seche Eco Industries | Procédé de traitement par immobilisation de mercure élémentaire contenu dans des déchets |
FR3053257B1 (fr) | 2016-06-29 | 2018-08-10 | Institut Francais Des Sciences Et Technologies Des Transports, De L'amenagement Et Des Reseaux | Procede d'immobilisation d'un dechet comprenant du mercure |
PL425150A1 (pl) * | 2018-04-09 | 2019-10-21 | Andrzej Janiczek | Metoda stabilizacji rtęci poprzez siarczek rtęci w betonie siarkowym |
WO2022175956A1 (en) * | 2021-02-21 | 2022-08-25 | Check-Cap Ltd. | Producing a radioactive substance for an intra-lumen imaging capsule |
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2009
- 2009-09-09 ES ES200930672A patent/ES2355001B1/es not_active Expired - Fee Related
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2010
- 2010-08-11 EP EP10815022.8A patent/EP2476649B1/en active Active
- 2010-08-11 WO PCT/ES2010/070547 patent/WO2011029970A2/es active Application Filing
- 2010-08-11 JP JP2012528395A patent/JP5745523B2/ja not_active Expired - Fee Related
- 2010-08-11 US US13/395,268 patent/US8580880B2/en not_active Expired - Fee Related
- 2010-08-11 ES ES10815022T patent/ES2703424T3/es active Active
- 2010-08-11 BR BR112012005381A patent/BR112012005381A2/pt not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
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EP2476649A4 (en) | 2013-04-24 |
JP5745523B2 (ja) | 2015-07-08 |
US8580880B2 (en) | 2013-11-12 |
EP2476649A2 (en) | 2012-07-18 |
BR112012005381A2 (pt) | 2016-03-29 |
WO2011029970A3 (es) | 2011-07-07 |
ES2703424T3 (es) | 2019-03-08 |
JP2013503729A (ja) | 2013-02-04 |
EP2476649B1 (en) | 2018-09-26 |
ES2355001A1 (es) | 2011-03-22 |
US20120322918A1 (en) | 2012-12-20 |
ES2355001B1 (es) | 2012-01-25 |
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