EP0989965A1 - Encapsulation de dechets dangereux - Google Patents

Encapsulation de dechets dangereux

Info

Publication number
EP0989965A1
EP0989965A1 EP98923926A EP98923926A EP0989965A1 EP 0989965 A1 EP0989965 A1 EP 0989965A1 EP 98923926 A EP98923926 A EP 98923926A EP 98923926 A EP98923926 A EP 98923926A EP 0989965 A1 EP0989965 A1 EP 0989965A1
Authority
EP
European Patent Office
Prior art keywords
encapsulating
composition
slurry
magnesium oxide
calcium carbonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP98923926A
Other languages
German (de)
English (en)
Other versions
EP0989965A4 (fr
Inventor
Dino Rechichi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dolomatrix International Ltd
Original Assignee
Periclase Pty Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AUPO7055A external-priority patent/AUPO705597A0/en
Priority claimed from AUPO9270A external-priority patent/AUPO927097A0/en
Priority claimed from AUPO9269A external-priority patent/AUPO926997A0/en
Application filed by Periclase Pty Ltd filed Critical Periclase Pty Ltd
Priority claimed from PCT/AU1998/000408 external-priority patent/WO1998054107A1/fr
Publication of EP0989965A1 publication Critical patent/EP0989965A1/fr
Publication of EP0989965A4 publication Critical patent/EP0989965A4/fr
Ceased legal-status Critical Current

Links

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
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/20—Agglomeration, binding or encapsulation of solid waste
    • B09B3/25—Agglomeration, binding or encapsulation of solid waste using mineral binders or matrix
    • 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
    • A62D3/36—Detoxification by using acid or alkaline reagents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/20—Agglomeration, binding or encapsulation of solid waste
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • 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
    • C04B28/02—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 hydraulic cements other than calcium sulfates
    • C04B28/10—Lime cements or magnesium oxide cements
    • C04B28/105—Magnesium oxide or magnesium carbonate cements
    • 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
    • C04B7/00—Hydraulic cements
    • C04B7/24—Cements from oil shales, residues or waste other than slag
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28—Treating solids
    • G21F9/30—Processing
    • G21F9/301—Processing by fixation in stable solid media
    • G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
    • G21F9/304—Cement or cement-like matrix
    • 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
    • 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
    • A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/02—Combined processes involving two or more distinct steps covered by groups A62D3/10 - A62D3/40
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0067—Function or property of ingredients for mortars, concrete or artificial stone the ingredients being formed in situ by chemical reactions or conversion of one or more of the compounds of the composition
    • 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

  • This invention relates to settable compositions which can encapsulate hazardous waste materials and relates particularly, though not exclusively, to a method of encapsulating hazardous waste materials including heavy metals such as arsenic, nickel, chromium residues and mercury as well as radioactive materials.
  • Arsenic and arsenic containing compositions have been widely used in Australia as sheep and cattle dips, and have also been used in pesticides.
  • Mercury and mercury containing compositions have also been widely used in Australia and other countries. With the phasing out of arsenic and mercury compounds (due to their toxicity), a large stockpile of waste arsenic and mercury components exists.
  • Organo nickel and chromium, and nickel and chromium containing compositions are widely used in Australia and other countries.
  • Metal plating and anodising processes use these compounds, and the processes generate waste nickel and chromium residues which are quite concentrated and are stored in drums. The residue is hazardous and toxic and a large stockpile of waste nickel and chromium components exists.
  • the above mentioned hazardous waste materials and toxic components are housed in drums which have a limited life.
  • the components in the drum are typically in the form of a contaminated liquid or sludge which is almost impossible to safely encapsulate.
  • the sludge contains a variety of contaminants such as rust from the drum, waste particles, solids, and a variety of liquids.
  • Radioactive materials and components are also hazardous substances. Apart from their use as fuel for nuclear reactors, radioactive materials also have medical applications and other industrial applications. For example, radioisotopes are used in the medical field for the diagnosis and treatment of various types of illness. In some industries, for example in the mining industry, a radioactive source is used in certain types of instruments for measuring, for example, the thickness of materials. However, one of the problems associated with using radioactive materials is finding a socially and environmentally acceptable method of disposing of the radioactive waste materials. Various proposals have been put forward for encasement or encapsulation of radioactive materials which can than be safely disposed of by burial in uninhabited regions of the Earth.
  • the present invention is directed to a method by which hazardous waste materials or components thereof can be encapsulated, even if the materials are contaminated with other impurities.
  • a method of encapsulating a hazardous waste material or component thereof comprising: adding the hazardous waste material to a settable composition, the composition comprising a calcium carbonate and a caustic magnesium oxide, forming a slurry, and allowing the slurry to set to encapsulate the waste material or components thereof.
  • a method of encapsulating an arsenic component selected from the group consisting of arsenic, sodium arsenite, arsenic trioxide or arsenic pentoxide comprising: adding to the arsenic component a sulphate, an iron chloride and /or an alkaline agent, and water to form a slurry, mixing the slurry with a settable composition, the composition comprising a calcium carbonate and a caustic magnesium oxide, and allowing the composition to set to encapsulate the arsenic component.
  • the sulphate which is added to the slurry is preferably an aluminium sulphate.
  • the alkaline agent is preferably a carbonate such as calcium carbonate.
  • the iron chloride can comprise ferric chloride.
  • Suitable ranges include:
  • Arsenic component 100 weight units (e.g. grams), Sulphate - 10 - 80 weight units, more preferably about 50 weight units, Alkaline agent (e.g. calcium carbonate) - 10 - 80 weight units. Ferric chloride (if present) - 5 - 50 weight units.
  • a method of encapsulating mercury or components thereof comprising: adding the mercury or components thereof to a settable composition, the settable composition comprising a calcium carbonate and a caustic magnesium oxide, forming a slurry, and allowing the slurry to set to encapsulate the mercury or components thereof.
  • the mercury waste is typically stored as a sludge.
  • One source of mercury waste is from Clarriflocculator sludge, or Brine sludge. This sludge contains between 100-200mg of mercury per kilogram of sludge, as well as water, dust/soil, and other impurities, which makes encapsulation in concrete unsatisfactory.
  • Suitable ranges for the method include:
  • a method of encapsulating nickel and chromium or components thereof comprising: adding the nickel and chromium or components thereof to a settable composition, the settable composition comprising a calcium carbonate and a caustic magnesium oxide, forming a slurry, and allowing the slurry to set to encapsulate the nickel and chromium and components thereof.
  • the nickel and chromium waste is typically stored as a thick liquid or sludge.
  • One source of nickel and chromium waste is from the metal plating and anodising industry.
  • This liquid can contain between lOmg - 28,000(?) mg of nickel and about lOmg - 200,000(?) mg chromium per kilogram of liquid, as well as water, dust/soil, and other impurities, which makes encapsulation in concrete unsatisfactory.
  • a filler can be used.
  • the filler can include an ash, but other fillers are envisaged.
  • the filler can comprise between 10 - 90% of the set composition, and more preferably between 40 - 60%
  • Suitable non-limiting ranges for the method include: Nickel and chromium containing liquid - 150ml,
  • a method of encapsulating radioactive materials comprising: adding the radioactive materials to a settable composition, the settable composition comprising a calcium carbonate and a caustic magnesium oxide, forming a slurry, and allowing the slurry to set to encapsulate the radioactive material therein.
  • the method of encapsulation according to the invention is particularly suited to low to mid level radioactive material, for example, monazite.
  • the radioactive material is added to the settable composition in the form of a powder.
  • the radioactive material or components thereof are ground to a particle size in the range from O.Ol ⁇ m to 5.0mm, more preferably the particle size falls within the range OJ ⁇ m to 1.0mm.
  • the settable composition further comprises lead or a lead compound such as, for example, lead oxide. It is thought that the lead in the composition assists in absorbing the radiation from the radioactive material. Suitable non-limiting ranges for the method include: Radioactive material - 1000 grams, Settable composition - 700 to 2200 grams, Lead oxide - 300 to 1500 grams Water - 500 to 900 ml.
  • caustic magnesium oxide includes a magnesium composition which comprises magnesium carbonate and a decarbonated magnesium.
  • the term also covers a magnesium carbonate which has been treated, for instance, by heating, to liberate carbon dioxide, thereby forming a composition which is partially calcined.
  • the exact structure of the composition and of the caustic magnesium oxide is not known, but the term will be used to include the structure formed by heating magnesium carbonate to partially decarbonate it, especially at the temperature ranges described.
  • the composition of calcium carbonate and caustic magnesium oxide can be formed by treating dolomite.
  • Dolomite is a calcium magnesium carbonate found in nature.
  • a true dolomite comprises about 54% calcium carbonate and 43% magnesium carbonate.
  • Natural dolomites contain impurities of various differing types which can include alumina, iron and silica.
  • the percentage of the calcium and magnesium carbonate can vary in dolomites. For instance, dolomite containing 65% calcium carbonate and 30% magnesium carbonate is called a low magnesium dolomite. Conversely, a dolomite containing 60% magnesium carbonate and 30% calcium carbonate is called a high magnesium dolomite.
  • dolomite will cause carbon dioxide to be liberated, and the rate of liberation of carbon dioxide can be controlled and varied to provide fully or partially calcined dolomites. If the dolomite is heated at 1,500°C, all the carbonate is liberated as carbon dioxide and a mixture of calcium oxide and magnesium oxide is left. These oxides are well known as for use in refractory material, but the oxides are not suitable for a cementitious material.
  • dolomite is heated at a lower temperature, not all of the carbonate decomposes to liberate carbon dioxide. Indeed, it is noted that the heating can be controlled such that the magnesium carbonate preferentially releases carbon dioxide over the calcium carbonate.
  • heating at a temperature range of typically between 500 - 800°C will cause preferential decomposition of the magnesium carbonate.
  • dolomite By controlling the preferential decomposition, dolomite can be treated to form a settable composition by the dolomite into a composition comprising a caustic magnesium oxide.
  • the preferential decomposition of dolomite can be enhanced by additives such as inorganic salts.
  • a suitable salt is a metal sulphate such as aluminium sulphate or magnesium sulphate which can be added from 0.1% - 5% prior to heating.
  • the salt appears to preferentially decrease the decarbonisation temperature of MgC0 3 without substantially affecting the higher decarbonisation temperature of CaC0 3 .
  • the salt can increase the differential temperature from 100°C to 200°C.
  • the caustic magnesium oxide has between 0.1% - 50% of the carbon dioxide retained within the magnesium carbonate, and preferably between 23% - 28%.
  • the structure may comprise a mix of calcium carbonate, magnesium oxide, and magnesium carbonate.
  • the amount of carbon dioxide retained in the composition has an effect on various parameters such as hardness, and setting rate. Between 20% - 30% retained carbon dioxide offers a suitable set rate for many applications. Increasing the amount of carbon dioxide decreases the set rate, and decreasing the amount of carbon dioxide increases the set rate.
  • the composition can also be prepared synthetically by mixing or blending calcium carbonate with preformed caustic magnesium oxide.
  • the caustic magnesium oxide can be prepared by subjecting heat to partially drive off carbon dioxide until the desired level of calcination is obtained.
  • a natural dolomite may be heated in the manner described above to provide a composition comprising calcium carbonate and caustic magnesium oxide, and if the natural dolomite is magnesium deficient (for instance, a low magnesium dolomite), additional caustic magnesium oxide can be added to the mixture.
  • a low magnesium dolomite ore containing 65% calcium carbonate and 30% magnesium carbonate plus impurities can be calcined so that the magnesium converts to partially calcined caustic magnesium oxide but essentially where between 2% - 20% of the original entrained carbon dioxide within the magnesium is retrained.
  • compositions for use as cement having any required predetermined weight or percentage of the blended materials.
  • the particle size of the composition can be varied if desired.
  • a suitable particle size of 50 - 70 micron with 90% passing through a 60 micron sieve allows the composition to be used in a variety of applications.
  • the composition can be ground to the particle size if required and this can be done before or after treatment.
  • Other particle size ranges are also envisaged such as from 10 - 1000 microns.
  • a range of 10% - 90% caustic magnesium oxide and 90% - 10% calcium carbonate can be used, with a preferred mix being 60% - 70% magnesium and 30% - 40% calcium.
  • one tonne of dolomite will contain 650 kilograms (kg) of calcium carbonate (CaC0 3 ) and 300kg of magnesium carbonate (MgC0 3 ) plus 5% impurities.
  • the magnesium carbonate will contain 156:57kg of C0 2 .
  • the calcined weight of the dolomite will now be 851:26kg which will include 650kg of calcium carbonate plus 143:3kg of magnesia oxide and 50kg of impurities.
  • CaC0 3 650kg/Mg0 143:43kg + 7:8285kg + impurities 50kg 851:26.
  • Dolomite 1000kg 650kg CaC0 3 before calcination 300kg MgC0 3 + 50kg impurities
  • the composition can be formulated as a dry fine powder (that is similar to the Portland Cement powder).
  • compositions can be based on the calcined magnesites and dolomites directly from the magnesium industry. These are predominantly magnesium oxide (typically over 90%) with calcium oxide (ranging 3-18%) and containing a low amount of (0-5%) carbon dioxide. This commercial form of caustic magnesium oxide may even contain dead burnt calcium oxide or dead burnt magnesium oxide but is still useful in the encapsulation process although it is not specifically calcined for encapsulation.
  • the additive or additives may accelerate the formation of strong binding agents, and may assist in the recrystallisation of the composition to make it set.
  • various added fillers which can include organic fillers, inorganic fillers, solid and liquid fillers, radioactive fillers, toxic fillers, and the like) can be trapped in the set matrix.
  • One additive can comprise a sulphate which may be added at rates of between 0.01% up to 20%, more typically 0.01% up to 10%.
  • a suitable sulphate can comprise sulphuric acid, or a metal sulphate such as magnesium sulphate or aluminium sulphate.
  • Another desirable additive is one which act as a source of carbonation in the composition to assist in the setting process.
  • a carbonate which can decompose or react to liberate carbon dioxide is preferred.
  • One suitable additive can be a metal carbonate such as sodium carbonate.
  • Another suitable additive can include a carboxylic or polycarboxylic acid which can react to liberate carbon dioxide.
  • Another advantage of sodium carbonate is that it will carbonate any completely oxidised fillers which may be used (for instance coal ash).
  • additives may include citric acid, lemon acid, acetic acid, glycolic acid, oxalic acid, other di or poly carboxylic acids, or other acidifying agents.
  • Possible substitutes for the citric acid include tartaric acid, Salicylic acid, ethylenediamine tetra acetic acid (EDTA) or other tetra acids.
  • EDTA ethylenediamine tetra acetic acid
  • These additives may be added at between 0.01% - 10%, more typically 0.01% to 5%. If the additives (such as citric acid or lemon acid) are solids, they are suitably pre-ground and powdered to enable them to be efficiently blended with the remainder of the composition. A grind size ⁇ 250 mesh can be used.
  • the aluminium sulphate may be commercially available aluminium sulphate having a hydration figure of 14. Of course, higher or lower hydrated aluminium sulphates can also be used with the appropriate weight adjustments.
  • Another acidifying agent may comprise sulphuric acid and this may be added to the water mixture in up to 5% by weight.
  • the additives include aluminium sulphate and a citric acid (or equivalent acid such as glycolic acid or acetic acid). Additionally, a salt such as sodium chloride can be provided.
  • the additives can be premixed and added to the composition.
  • the amount of premix added can vary for instance from about 3% - 10% or more. It appears that when fillers of small size (for example below 70 micron) are used, the amount of premix added should be larger (about 10%), while fillers of larger size allow less premix to be added (e.g. 3% - 7%).
  • the premix comprises (a) aluminium sulphate, (b) an organic acid and (c) a salt, it is preferred that (a) is present between 40% - 80%; (b) is present between 10% - 60% and (c) is present between 1% - 20%.
  • ingredient (a) provides early strength to the set composition, and may assist in the formation of brucite (Mg(OH) 2 ), and a gelatinous polymer of aluminium hydroxide, both which help with initial bonding of the composition. It also appears that (a) provides water proofing properties.
  • Ingredient (b) for instance citric acid, appears to assist in the carbonisation of MgO and Mg(OH) 2 to recrystallise the composition into a set material.
  • the acid may also act as a ligand to form complexes around the fillers (for instance metal ions) helping to trap them in the setting or set matrix.
  • the carbonisation process can continue over a long period of time which can provide long lasting strength to the set material.
  • Ingredient (c) appears to assist in achieving an early strength to the composition.
  • EXAMPLE 1 Sodium Arsenite lOOg, aluminium sulphate 50g, ferric chloride 20g, calcium carbonate 50g and water 300ml are slurried together and left to stand for 10 minutes during which separation of the metal occurred and flocculation was observed. This slurry was added to a slurry of a settable composition which contained 400g of calcium carbonate and caustic magnesium oxide, 400g of a filer (ash - to soak up excesss water), and 160gm of a mixture of 50g aluminium sulphate, lOOg citric acid and lOg soda ash. The thickness of the total mixture could be adjusted by addition of water to form a mouldable composition which can have a slump value of between 80 - 120 (i.e. about that of a cement slurry). The total mixture was poured into moulds and set.
  • a Leach rate analysis showed an arsenic leach of 2Jppm which was much less than the allowed limit of 5.0ppm.
  • EXAMPLE 2 Powdered arsenic lOOg, aluminium sulphate 50g, ferric chloride 20g, calcium carbonate 50g and water 300ml are slurried together and left to stand for 10 minutes during which separation of the metal occurred and flocculation was observed. This slurry was added to a slurry of a settable composition which contained 400g of calcium carbonate and caustic magnesium oxide, 400g of a filler (ash - to soak up excess water), and 160g of a mixture of 50g aluminium sulphate, lOOg citric acid and lOg soda ash. The thickness of the total mixture could be adjusted by addition of water to form a mouldable composition which can have a slump value of between 80 - 120 (i.e. about that of a cement slurry). The total mixture was poured into moulds and set.
  • a Leach rate analysis showed an arsenic leach of 4Jppm which was less than the allowed limit of 5.0ppm.
  • Arsenic Trioxide lOOg, aluminium sulphate 50g, ferric chloride 20g, calcium carbonate 50g and water 300ml are slurried together and left to stand for 10 minutes during which separation of the metal occurred and flocculation was observed.
  • This slurry was added to a slurry of a settable composition which contained 400g of calcium carbonate and caustic magnesium oxide, 400g of a filler (ash - to soak up excess water), and 160g of a mixture of 50g aluminium sulphate, lOOg citric acid and lOg soda ash.
  • the thickness of the total mixture could be adjusted by addition of water to form a mouldable composition which can have a slump value of between 80 - 120 (i.e. about that of a cement slurry). The total mixture was poured into moulds and set.
  • a Leach rate analysis showed an arsenic leach of 4Jppm which was much less than the allowed limit of 5.0ppm.
  • EXAMPLE 4 Arsenic Pentoxide 100g, aluminium sulphate 50g, ferric chloride 20g, calcium carbonate 50g and water 300ml are slurried together and left to stand for 10 minutes during which separation of the metal occurred and flocculation was observed. This slurry was added to a slurry of a settable composition which contained 400g of calcium carbonate and caustic magnesium oxide, 400g of a filler (ash - to soak up excess water), and 160g of a mixture of 50g aluminium sulphate, lOOg citric acid and lOg soda ash. The thickness of the total mixture could be adjusted by addition of water to form a mouldable composition which can have a slump value of between 80 - 120 (i.e. about that of a cement slurry). The total mixture was poured into moulds and set. A Leach rate analysis showed an arsenic leach of 4Jppm which was much less than the allowed limit of 5.0ppm.
  • EXAMPLE 5 Powdered Arsenic lOOg, aluminium sulphate 50g, calcium carbonate 20g and water 150ml are slurried together and left to stand for 10 minutes during which separation of the metal occurred and flocculation was observed. This slurry was added to a slurry of a settable composition which contained 200g of calcium carbonate and caustic magnesium oxide, 400g of a filer (ash - to soak up excess water), and lOOg of a mixture of 30g aluminium sulphate, 60g citric acid and lOg soda ash. The thickness of the total mixture could be adjusted by addition of water to form a mouldable composition which can have a slump value of between 80 - 120 (i.e. about that of a cement slurry). The total mixture was poured into moulds and set.
  • a Leach rate analysis showed an arsenic leach of l.Oppm which was much less than the allowed limited of 5.0ppm.
  • the brine sludge contains between 100 - 200mg of mercury per kilogram of sludge.
  • the sludge additionally contains 10 - 29% calcium carbonate, 1 - 9% magnesium hydroxide, 10 - 29% sodium chloride, 1 - 9% soil /dust and 30 - 60% water.
  • the sludge is a waste produce from brine purification.
  • the sludge is an odourless brown sludge insoluble in water.
  • the sludge has a pH of 11.6 and a specific gravity of 1.29.
  • EXAMPLE 7 150ml of an undiluted fully concentrated nickel and chromium containing residue (containing 360mg p/ litre chromium and 28,000mg p/ litre nickel), 400ml water, 150g calcium carbonate and 40g of aluminium sulphate are mixed together to form a slurry. To the slurry is added 300g of calcium carbonate and caustic magnesium oxide, 60g of aluminium sulphate, 34g of citric acid, 6g of soda ash, 1kg of filler (powerhouse ash) and an additional 50ml of water. The thickness of the total mixture can be adjusted with water to form a mouldable composition. The mixture is poured into moulds and left to cure for T.C.L.P. tests (Toxic Characteristic Leachate Procedures). After 30 days of testing, a leach rate of below 0.2 parts p /million was established showing that the encapsulated product is suitable for storage in an unlined tip.
  • T.C.L.P. tests Toxic Character
  • EXAMPLE 8 150ml of an undiluted fully concentrated nickel and chromium containing residue (containing 3Jmg p/ litre chromium and lJOOmg p/ litre nickel), 400ml water, 150g calcium carbonate and 40g of aluminium sulphate are mixed together to form a slurry. To the slurry is added 300g of calcium carbonate and caustic magnesium oxide, 60g of aluminium sulphate, 34g of citric acid and 6g of soda ash, 1kg of filler (powerhouse ash) and an additional 50ml of water. The thickness of the total mixture can be adjusted with water to form a mouldable composition. The mixture is poured into moulds and lets to cure for T.C.L.P. tests (Toxic Characteristic Leachate Procedures). After 30 days of testing, a leach rate of below 0.2 parts p /million was established showing that the encapsulated product is suitable for storage in an unlined tip.
  • T.C.L.P. tests To
  • Radioactive Monazite Tests were conducted using a powdered sample of the mineral monazite.
  • Monazite is a monoclinic phosphate of the rare earth elements containing the cerium groups (Ce, La, Y, Th) P04, as well as some uranium and thorium.
  • Monazite is relatively abundant in beach sands, and is one of the principal sources of rare earth minerals and thorium.
  • Thorium is used as a radioactive source in scientific instruments.
  • Rare earth compounds are used in various manufacturing processes, including the manufacturing of glass and certain metals.
  • the monazite particle size can be from dust (approx. OJ ⁇ m) up to particles of approximately 1.0mm, ideally.
  • the lead tailings, caustic magnesium oxide and calcium carbonate were all preground to approximately llO ⁇ m, ie. 90% passed through a 150 ⁇ m sieve.
  • the radioactivity of the encapsulated monazite mixture was measured to be 44.60 ⁇ 0.20 becquerels per gram thorium and 5.06 ⁇ 0.21 becquerels per gram uranium.
  • a leach rate analysis was carried out at 14 days and 28 days to determine the leachable uranium and thorium. At 14 days the leachable uranium was less than 0.05 micrograms per litre and the leachable thorium was 0.25 micrograms per litre. At 28 days the leachable uranium was 0.05 micrograms per litre and the leachable thorium was 0.45-0.50 micrograms per litre.
  • Gamma spectroscopy was carried out on the TCLP solutions to determine the levels of radioactive uranium and thorium at 14 and 28 days.
  • the leachable uranium radioactivity was below detectable levels or equivalent to ⁇ 1 part per million and the leachable thorium radioactivity was 0.034 ⁇ 0.007 becquerels per gram.
  • the leachable uranium radioactivity was below detectable levels or equivalent to ⁇ 1 per million and the leachable thorium radioactivity was below detectable levels or equivalent to ⁇ 2 parts per million.
  • EXAMPLE 10 500 grams of monazite, of radioactivity 246 becquerels per gram thorium and 28J becquerels per gram uranium, 450 grams of caustic magnesium oxide and a mixture of 360 grams of lead tailings (ex Mt. Isa) and 240 grams calcium carbonate were thoroughly dry mixed with 100 grams of aluminium sulphate and 25 grams of citric acid. To this was added 310 mLs of water to form a thick rapidly setting paste. The thickness of the total mixture could be adjusted by the addition of water to form a mouldable composition. The total mixture was poured into moulds and allowed to set.
  • the radioactivity of the encapsulated monazite mixture was measured to be 70.20 ⁇ 0.30 becquerels per gram thorium and 8.01 ⁇ 0.31 becquerels per gram uranium.
  • a leach rate analysis was carried out at 14 days and 28 days to determine the leachable uranium and thorium. At 14 days the leachable uranium was less than 0.05 micrograms per litre and the leachable thorium was 0J5 micrograms per litre. At 28 days the leachable uranium was 0.05 micrograms per litre and the leachable thorium was 0J5-0.45 micrograms per litre.
  • Gamma spectroscopy was carried out on the TCLP solutions to determine the levels of radioactive uranium and thorium at 14 and 28 days.
  • the leachable uranium radioactivity was below detectable levels or equivalent to ⁇ 1 part per million and the leachable thorium radioactivity was below detectable levels or equivalent to ⁇ 2 parts per million.
  • the leachable uranium radioactivity was below detectable levels or equivalent to ⁇ 1 part per million and the leachable thorium radioactivity was 0.038 ⁇ 0.007 becquerels per gram.
  • EXAMPLE 11 800 grams of monazite, of radioactivity 246 becquerels per gram thorium and 28.1 becquerels per gram uranium, 400 grams of caustic magnesium oxide and a mixture of 300 grams of lead tailings (ex Mt. Isa) and 200 grams calcium carbonate were thoroughly dry mixed with 100 grams of aluminium sulphate and 25 grams of citric acid. To this was added 400 mLs of water to form a thick rapidly setting paste. The thickness of the total mixture could be adjusted by the addition of water to form a mouldable composition. The total mixture was poured into moulds and allowed to set.
  • the radioactivity of the encapsulated monazite mixture was measured to be 104.0 ⁇ 0.41 becquerels per gram thorium and 12.0 ⁇ 0.42 becquerels per gram uranium.
  • a leach rate analysis was carried out at 14 days and 28 days to determine the leachable uranium and thorium.
  • the leachable uranium was 0.05 micrograms per litre and the leachable thorium was 0.25 micrograms per litre.
  • the leachable uranium was 0J0 micrograms per litre and the leachable thorium was 1.10-1.40 micrograms per litre.
  • Gamma spectroscopy was carried out on the TCLP solutions to determine the levels of radioactive uranium and thorium at 14 and 28 days.
  • the leachable uranium radioactivity was below detectable levels or equivalent to ⁇ 1 part per million and the leachable thorium radioactivity was below detectable levels or equivalent to ⁇ 2 parts per million.
  • the leachable uranium radioactivity was below detectable levels or equivalent to ⁇ 1 part per million and the leachable thorium radioactivity was 0.038 ⁇ 0.007 becquerels per gram.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Inorganic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un procédé d'encapsulation de déchets dangereux renfermant des métaux lourds, tels que des résidus d'arsenic, de mercure, de nickel et de chrome, ainsi que des matières radioactives. Le procédé consiste à ajouter le déchet dangereux à une composition durcissable, à former une suspension, et à laisser durcir la suspension afin d'encapsuler le déchet. La composition durcissable est une composition de ciment fluide, en poudre contenant du carbonate de calcium et un oxyde caustique de magnésium. Des tests réalisés sur les déchets encapsulés indiquent que pratiquement aucun déchet dangereux n'est lixivié hors de la composition durcie présentant un aspect semblable au béton.
EP98923926A 1997-05-29 1998-05-29 Encapsulation de dechets dangereux Ceased EP0989965A4 (fr)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
AUPO7055A AUPO705597A0 (en) 1997-05-29 1997-05-29 Settable compositions for encapsulating arsenic
AUPO705597 1997-05-29
AUPO927097 1997-09-18
AUPO9270A AUPO927097A0 (en) 1997-09-18 1997-09-18 Settable compositions for encapsulating mercury
AUPO9269A AUPO926997A0 (en) 1997-09-18 1997-09-18 Settable compositions for encapsulating organo nickel and chromium
AUPO926997 1997-09-18
AUPO315898 1998-04-22
AUPO315898 1998-04-22
PCT/AU1998/000408 WO1998054107A1 (fr) 1997-05-29 1998-05-29 Encapsulation de dechets dangereux

Publications (2)

Publication Number Publication Date
EP0989965A1 true EP0989965A1 (fr) 2000-04-05
EP0989965A4 EP0989965A4 (fr) 2000-11-02

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KR (1) KR100768263B1 (fr)
IL (1) IL133161A0 (fr)
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JP7265267B6 (ja) * 2017-06-29 2023-05-19 ザ ロイヤル インスティチューション フォー ジ アドヴァンスメント オブ ラーニング／マギル ユニヴァーシティ 有害物質の安定化
CN110818382A (zh) * 2019-11-14 2020-02-21 东莞市建佳再生资源回收有限公司 环保砖及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1160029A (en) * 1967-01-10 1969-07-30 Herbert Mayer A New and Improved Cement Composition
EP0355507A1 (fr) * 1988-08-17 1990-02-28 Siemens Aktiengesellschaft Procédé pour solidifier des concentrés d'eaux usées
WO1992018437A1 (fr) * 1991-04-10 1992-10-29 Ramseyer Beverly J Systeme de conditionnement pour dechets dangereux
US5249889A (en) * 1992-04-27 1993-10-05 Great Lakes/Enviroland, Inc. Soil-less method for the reclamation of disturbed areas
DE19529850A1 (de) * 1995-08-12 1997-02-13 Kali Umwelttechnik Gmbh K Utec Verfahren zur Verbesserung der Fließ- und Abbindeeigenschaften von mineralischen Pumpversatzmischungen für Hohlräume in Salzgesteinen
WO1997020784A1 (fr) * 1995-12-05 1997-06-12 Periclase Pty. Ltd. Composition prete a durcir et utilisations de cette composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2320266A1 (fr) 1975-08-06 1977-03-04 Quienot Jean Procede de solidification de dechets de nature et origine diverses
CH678018A5 (fr) 1988-10-18 1991-07-31 Salzburger Stadtwerke Ag
US5732367A (en) 1990-03-16 1998-03-24 Sevenson Environmental Services, Inc. Reduction of leachability and solubility of radionuclides and radioactive substances in contaminated soils and materials
US5037479A (en) 1990-04-20 1991-08-06 Rmt, Inc. Method for reduction of heavy metal leaching from hazardous waste under acidic and nonacidic conditions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1160029A (en) * 1967-01-10 1969-07-30 Herbert Mayer A New and Improved Cement Composition
EP0355507A1 (fr) * 1988-08-17 1990-02-28 Siemens Aktiengesellschaft Procédé pour solidifier des concentrés d'eaux usées
WO1992018437A1 (fr) * 1991-04-10 1992-10-29 Ramseyer Beverly J Systeme de conditionnement pour dechets dangereux
US5249889A (en) * 1992-04-27 1993-10-05 Great Lakes/Enviroland, Inc. Soil-less method for the reclamation of disturbed areas
DE19529850A1 (de) * 1995-08-12 1997-02-13 Kali Umwelttechnik Gmbh K Utec Verfahren zur Verbesserung der Fließ- und Abbindeeigenschaften von mineralischen Pumpversatzmischungen für Hohlräume in Salzgesteinen
WO1997020784A1 (fr) * 1995-12-05 1997-06-12 Periclase Pty. Ltd. Composition prete a durcir et utilisations de cette composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9854107A1 *

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KR20060009393A (ko) 2006-01-31
EP0989965A4 (fr) 2000-11-02
TW503226B (en) 2002-09-21
KR100768263B1 (ko) 2007-10-18
IL133161A0 (en) 2001-03-19

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