EP2934760A1 - Méthode de séparation de carbonate de calcium et de gypse - Google Patents
Méthode de séparation de carbonate de calcium et de gypseInfo
- Publication number
- EP2934760A1 EP2934760A1 EP13811473.1A EP13811473A EP2934760A1 EP 2934760 A1 EP2934760 A1 EP 2934760A1 EP 13811473 A EP13811473 A EP 13811473A EP 2934760 A1 EP2934760 A1 EP 2934760A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- granules
- gypsum
- calcium carbonate
- group
- sodium
- 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.)
- Withdrawn
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/006—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/01—Organic compounds containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/014—Organic compounds containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
Definitions
- the invention relates to a method for separating a slurry containing gypsum granules and calcium carbonate granules and an aqueous solution comprising at least one sodium salt, said method comprising a flotation separation step using a collector for Hetero-polar organic surfactant type gypsum granules. It also relates to the use of granules of calcium carbonate or gypsum granules treated according to the method of the present invention, in cement, or in civil engineering.
- the other crystalline species of calcium carbonate, such as aragonite, or vaterite, are less frequent in the water. nature, have solubility products slightly different but close.
- Calcium sulphate is more soluble in water: approximately 0.2 g of CaSO 4 per 100 g 3 ⁇ 4 0, and its solubility increased to a factor of about two in saline solution. Calcium sulphate is a setting modifier in cements and concretes. It is likely to cause swelling and embrittlement of building materials by delayed formation of ettringite if used in large quantities.
- gypsum is a good raw material for the realization of building materials such as panels or plaster tiles, especially after calcination to transform it into calcium sulphate hemihydrate which has hydraulic setting properties when it is put in. contact with water.
- flotation is one of the techniques used, especially in ore beneficiation. Flotation separates particles or granules from solids, taking advantage of the differences between their surface properties in an aqueous solution.
- the principle of flotation is the following: the solid granules are suspended in a liquid, in general the water, after a possible grinding more or less pushed.
- This solid-water mixture also called pulp, is conditioned with a chemical reagent called collector, whose role is to make the surface of the mineral to float, in order to give it a greater affinity for the gas phase than for the liquid phase. .
- the pulp thus packaged is introduced into reactors equipped with aerated stirrers (flotation cells) or air injectors (flotation column) or
- the hydrophobized granules attach to the surface of the bubbles that constitute a transport vector through their upward movement towards the free surface of the pulp. This gives a supernatant foam loaded solid called foam.
- the size of the bubbles (and in this the interfacial area liquid-air) and the life of the foam is modulated by the optional addition of a foaming agent.
- the entrained liquid is drained by gravity into the interior of the foam, which is collected by overflow.
- Foam and residual pulp are generally subjected to subsequent treatment such as optional washing, decantation and / or filtration, and optional drying, to collect the granules of overflowing solids and the granules of solid underflow, depending on whether the It is desired to use one or other of the solids obtained in wet or dry form.
- the flotation separation of soluble or partially soluble ores has been intensively studied, particularly for the separation of non-ferrous metal sulfides, metal oxides, phosphate ores, and silvite (KC1).
- sedimentary deposits of phosphate ores such as those of apatite Ca 5 (PO 4 ) 3 (F, OH)
- apatite Ca 5 (PO 4 ) 3 F, OH
- the flotation of the apatite ore then makes it possible to separate the apatite ore and the carbonate with the scum, and underflow into the residual pulp to remove quartz and silica.
- Sedimentary phosphates with a high carbonate content for example those in southern Florida and the region
- ionic surfactants having one or more carboxylic group, or sulfonate, or sulfate, or phosphonate, or phosphate, or hydroxamate constituted an effective collector for the separation of gypsum granules in a suspension containing gypsum granules and granules of carbonate of calcium in aqueous solution when it comprises at least one sodium salt at a sodium ion concentration of at least about 3 g / L
- nonionic surfactants of the polarizable alcohol type and in particular of Guerbet alcohols type did not constitute an effective collector for the separation of gypsum granules in a suspension containing granules of gypsum and granules of carbonate when they were used alone, but could be when they were associated with ionic surfactants mentioned above.
- the present invention relates to a method for separating a suspension containing gypsum granules and calcium carbonate granules and an aqueous solution, characterized in that the aqueous solution comprises at least one sodium salt and in that the aqueous solution has a sodium ion concentration of at least about 3 g / L, preferably at least about 10 g / L, preferably at least about 30 g / L, and that said method comprises a flotation separation step using a collector for the gypsum granules, the collector comprising at least one hetero-polar organic surfactant of the formula RX, wherein:
- R denotes a hydrocarbon chain comprising from 2 to 50 carbon atoms, preferably from 10 to 30 carbon atoms, preferably from 15 to 25 carbon atoms, and the hydrocarbon chain is chosen from: a linear saturated or unsaturated alkyl chain; a saturated or unsaturated branched alkyl chain,
- - X denotes at least one ionizable group chosen from the group consisting of: a carboxylic group, a sulphonate group, a sulphate group, a phosphonate group, or a phosphate group, or a hydroxamate group.
- a first advantage of the present invention is the selectivity obtained on the separation of the gypsum granules from a pulp consisting of a mixture of gypsum granules and calcium carbonate.
- a second advantage of the present invention is the good selectivity of the gypsum collectors even in the presence of a high ionicity and / or a high calcium content of the solution of the pulp to be treated.
- a third advantage of the present invention is the simplicity with which the granules of the two calcium minerals can be separated into two enriched enriched phases especially in the fields of cement and civil engineering.
- granule a particle of a solid
- glycopsum granule a solid particle generally comprising at least 80%, preferably at least 90% by weight of calcium sulfate dihydrate (CaSO 4 .2H 2 O),
- Calcium carbonate granule a solid particle generally comprising at least 80%, preferably at least 90% by weight of calcium carbonate (CaCO 3 ), generally present in the form of calcite,
- sodium salt a sodium salt partially soluble in the aqueous solution, such as sodium borate, sodium chloride, sodium sulphate, sodium sulphite, sodium nitrate, sodium nitrite, advantageously the chloride or sodium sulfate, more preferably sodium chloride,
- collector a chemical reagent rendering the surface of the granules hydrophobic and thereby increasing the affinity of the granule for the gaseous phase used in flotation
- pulp a suspension of solid granules in an aqueous solution
- residual pulp also known as “sterile” or “non-floated” or “underflow”: a pulp obtained under-poured from a flotation apparatus after a flotation operation,
- hydrocarbon chain an organic chain comprising carbon and hydrogen atoms and optionally one or more other atoms such as oxygen (O), sulfur (S), nitrogen (N), phosphorus (P),
- a hydrogenated or alkali metal group such as lithium, sodium, potassium, ..., preferably sodium or potassium, preferentially sodium, capable of losing the hydrogen or the corresponding alkali metal in the form of H +, Li +, Na +, K + ions, etc.
- - at least one ionic group selected from the group consisting of: a carboxylic group, a sulphonate group, a sulphate group, a phosphonate group, a phosphate group, a hydroxamate group, at least one carboxylic group (-COOH or - COOM with one of the alkali metals listed in the preceding paragraph), or at least one sulphonate group (-SO 2 -OH or -SO 2 -OM with one of the alkali metals listed in the preceding paragraph), or at least one sulphate group ( -O-SO 2 -OH or -O-SO 2 -OM with one of the alkali metals listed in the preceding paragraph), or a phosphonate group (-PO- (OH) 2 or -PO- (OM) 2 with M a alkali metals listed in the previous paragraph), or a phosphate group (-O-PO- (OH) 2 or -O-PO- (OM) 2 with one of the
- a range of values for a variable defined by a low limit, or a high limit, or by a low limit and a high limit, also includes the embodiments where the variable is selected respectively in the value range: excluding the low limit, or excluding the high limit, or excluding the low and high limits.
- Fig. 1 is a block diagram of one of the embodiments of the invention using a flotation cell 3.
- Fig.2 is a block diagram of one embodiment of the invention using a flotation cell 3, and complementary liquid-solid separation equipment such as decanters 6 and 13 and filters 10 and 17.
- FIG. 3 is a block diagram of one of the embodiments of the invention using a flotation cell 3, complementary liquid-solid separation equipment such as decanters 6 and 13 and filters 10 and 17, and contact reactors 23 and 26.
- FIG. 4 illustrates the percentage (%) of mass recovery, referred to as 'Recovery (%)', of gypsum granules, calcium carbonate, and apatite after flotation tests, at three concentrations of sodium oleate added to the flotation cell, described in Example 1.
- the present invention relates to a method for separating a suspension containing gypsum granules and calcium carbonate granules and an aqueous solution, characterized in that the aqueous solution comprises at least one sodium salt and in that the aqueous solution at a sodium ion concentration of at least about 3 g / L, preferably at least about 10 g / L, preferably at least about 30 g / L, and that said method comprises a flotation separation step using a collector for gypsum granules, the collector comprising at least one hetero-polar organic surfactant of formula RX, wherein:
- R denotes a hydrocarbon chain comprising from 2 to 50 carbon atoms, preferably from 10 to 30 carbon atoms, preferably from 15 to 25 carbon atoms, and the hydrocarbon chain is chosen from: a linear saturated or unsaturated alkyl chain; a saturated or unsaturated branched alkyl chain,
- - X denotes at least one ionizable group chosen from the group consisting of: a carboxylic group, a sulphonate group, a sulphate group, a phosphonate group, or a phosphate group, or a hydroxamate group.
- Nonionic surfactants of the polarizable alcohol type and in particular of the Guerbet alcohols type which are generally not influenced by the presence of sodium ions or of sodium and calcium ions, have not shown any efficacy for the separation of gypsum granules and calcium carbonate when they are used alone, but against these nonionic surfactants improve the selectivity of the separation of the two minerals when they are associated with the ionic surfactants mentioned above.
- selective flotation is meant herein a step of separation by flotation of a pulp, to obtain a foam overflow generally containing at least 60%, preferably 70%,
- the hetero-polar organic surfactant RX is chosen from the group consisting of: sodium or potassium oleate, sodium or potassium alkyl sulphonate, sodium or potassium alkyl sulphate, sulphosuccinamate of sodium or potassium, or a mixture thereof, preferably a sodium or potassium oleate.
- the collector may also comprise a nonionic surfactant such as an iso-alcohol or a Guerbet alcohol.
- the flotation separation step is performed with a flotation cell well known to those skilled in the mechanical agitation type or pneumatic type such as a flotation column.
- a flotation cell well known to those skilled in the mechanical agitation type or pneumatic type such as a flotation column.
- Such flotation cells are described for example in the encyclopedia "Techniques of the Engineer - Volume J3360 pages 1 to 22, flotation practical aspects - Paris, June 2012, incorporated by reference in the present description.
- the product recovered by pumping system at the bottom of the column constitutes the "non-floated" or "sterile". It corresponds to the aqueous solution freed from particles collected specifically by the bubbles. It may also contain hydrophilic particles that have not adhered to the bubbles.
- the flotation cells with mechanical agitation have a similar operation but the pulp is introduced by mechanical suction under the effect of the rotor in the intermediate part of the cell, the scum is collected in the upper part and the aqueous solution and residual "non float Are recovered at the bottom of the flotation cells.
- the heteropolar organic surfactant collector is introduced directly into the flotation cell near the bubble generator. This makes it possible to limit the consumption of the collector by the calcium ions in the liquid phase and better adsorption on the surface of the calcium gypsum granules.
- the collector may also be introduced directly into the flotation column at the pulp-foam interface, for example, so that the collector adsorbs on the mineral surface in the downflow.
- the calcium carbonate granules and the gypsum granules have a distribution.
- the granulo metric such that at least 90% by weight of the particles have a diameter less than 150 ⁇ , preferably less than 130 ⁇ , preferably less than 110 ⁇ and more preferably less than 90 ⁇ .
- the granules of calcium carbonate and the granules of gypsum have a granulometric distribution such that at least 10% by weight of the particles have a diameter greater than 0.1 ⁇ , preferably greater than 1 ⁇ , preferably greater than at 2 ⁇ .
- the amount of gypsum granules or calcium carbonate granules reported per unit volume of suspension (the pulp) is generally at least
- the weight ratio between granules of gypsum and calcium carbonate granules of the suspension is generally between 1: 3 and 3: 1, advantageously between 1: 2 and 2: 1.
- the surfactants mentioned above can operate over a wide pH range. Acidic pH of the suspension below 5 causes acid attack of the calcium carbonate granules by generating C0 2 . This release of C0 2 at pH too acidic is detrimental to good selectivity: because then the carbonate granules are covered with microbubbles of C0 2 which has the effect of driving the granules of calcium carbonate in an updraft and decrease the selectivity of the separation of the gypsum granules and calcium carbonate granules from the suspension.
- the suspension has a pH of at least 5, preferably at least 7, preferably at least 7.5, more preferably at least 8.
- the suspension has a pH advantageously of at most 13, more preferably at most 11, still more preferably at most 10.
- the suspension containing granules of gypsum and granules of calcium carbonate and an aqueous solution can be obtained for example by:
- the suspension containing granules of gypsum and granules of calcium carbonate present in the aqueous solution can also be obtained by reaction of a lime milk comprising at least one sodium salt, or a mixture of lime milk and a broth of calcium carbonate comprising at least one sodium salt with acid fumes resulting from the combustion of a sulfur-containing organic compound such as a coal, a lignite, a wood, an agricultural residue, an organic residue from the food industry, an organic residue from the paper industry, a sludge from a drinking water or wastewater treatment plant, an organic sludge from a biogas plant.
- a sulfur-containing organic compound such as a coal, a lignite, a wood, an agricultural residue, an organic residue from the food industry, an organic residue from the paper industry, a sludge from a drinking water or wastewater treatment plant, an organic sludge from a biogas plant.
- the surfactants mentioned above have also been effective in separating granules of gypsum and granules of calcium carbonates in aqueous solutions with a high content of soluble salts, in particular sodium salts. This is particularly advantageous for example for residual solutions for washing acid gases such as SO x (SO 2 , SO 3 , .7) made with seawater or brines using crushed calcium carbonate and / or CHL, or with concentrated sodium ion permeate from desalination unit of seawater by evaporation, by dialysis, or by reverse osmosis.
- acid gases such as SO x (SO 2 , SO 3 , .7) made with seawater or brines using crushed calcium carbonate and / or CHL, or with concentrated sodium ion permeate from desalination unit of seawater by evaporation, by dialysis, or by reverse osmosis.
- solubility of the sulphate ions will decrease inversely proportional to the calcium ion concentration, regulated by the solubility product of the gypsum and the corresponding activity coefficients.
- the present invention also relates to a method for separating gypsum granules and calcium carbonate granules in an aqueous solution, wherein the aqueous solution further comprises at least one calcium salt, and that the aqueous solution has a calcium ion concentration of at least about 0.5 g / L, preferably at least about 5 g / L, preferably at least about 10 g / L.
- calcium salt is meant a calcium salt partially soluble in the aqueous solution, such as calcium hydroxide, calcium chloride, calcium nitrate, calcium nitrite, preferably calcium chloride.
- the calcium salt (s) can be co-present with the sodium salt (s).
- Separations of granules of gypsum and calcium carbonate in mixed saline solutions of sodium and calcium salts having a concentration of soluble salts up to about 4 mol of sodium and / or calcium per liter give still excellent results of separation of the two types of granules according to the present invention.
- the gas used for flotation is a gas whose content of carbon dioxide (CO 2 ) is less than 10%, preferably less than 1%, and more preferably less than 10%. 0.5% by volume on dry gas.
- CO 2 carbon dioxide
- a flotation gas composed of air or nitrogen makes it possible to obtain recovery efficiencies in the foam (the float) of 71 to 88.degree. % yield of sulfate and 6 to 21% of carbonate yield corresponding to higher selectivity coefficients (selectivity between 12 and 95).
- the suspension containing gypsum granules and calcium carbonate granules is obtained either by adding lime milk in a saline solution comprising at least 0.5 g of sulphate ions per liter, then by carbonation of all or part of the milk of lime with carbon dioxide, either by reaction of a milk of lime comprising at least one sodium salt, or of a mixture of lime milk and a broth of calcium carbonate comprising at least one sodium salt with carbon dioxide or acid fumes from the combustion of an organic sulfur compound
- the carbonation step is preferably separated and prior to the flotation step.
- the flotation step is preferably carried out with a gas whose carbon dioxide content is limited according to the limits indicated above.
- the feed rate of the pulp in a flotation cell may range from 0 to a limit speed beyond which the bubbles are entrained with the under-poured calcium carbonate granules.
- feeding of the flotation cell that flow rates suitable to match surface speeds empty cask J of at least 0.1, preferably at least 0.2, preferably at least 0.5 cm / s.
- Speed The empty surface of the pulp feed rate corresponds to the volume flow rate per unit of time divided by the area of the maximum useful horizontal section of the flotation cell.
- the feed rates of the flotation cell are chosen so that the surface velocities in empty casing J a are at most 5.0, more advantageously at most 3.0, and even more
- the average superficial gas velocity in the portion of the flotation cell where the gas rises is generally at least 0.1, preferably at least 0.2, preferably at least 0.5 cm / s.
- the average superficial gas velocity in the part of the flotation cell where the gas rises is advantageously at most 5.0, more preferably at most 3.0, still more advantageously at most 1.7 cm / s.
- Most preferably the average superficial gas velocity in the portion of the flotation cell where the gas rises is at least 0.5 and at most 1.5 cm / s.
- the average superficial gas velocity in the portion of the flotation cell where the gas rises is defined as the volume flow rate of gas divided by the area of the average horizontal section in the portion of the flotation cell where gas and pulp are in contact.
- the flotation separation step is carried out with a mechanical agitation or pneumatic type flotation cell such as a flotation column, and the average surface gas velocity in the flotation cell is at least 0.1, preferably at least 0.2, preferably at least 0.5 cm / s and advantageously at most 5.0, more preferably at most 3.0, even more advantageously at most 1.7 cm / s, and most preferably at least less than 0.5 and not more than 1.5 cm / s.
- the dispersion of the gas in the flotation cell is chosen from the devices known in the art in order to generate in the flotation cell in general gas bubbles with a volume average diameter in general of at least 0.4 mm, advantageously from less 0.6 mm, more preferably at most 0.65 mm.
- the average volume bubble diameter is generally at most 2.5 mm, advantageously at most 1.2 mm, more preferably at most 1.0 mm.
- Medium volume bubble diameters of at least 0.65 mm and at most 0.95 mm are particularly suitable.
- obtaining granules of gypsum and granules of calcium carbonate in an aqueous solution is obtained by: a) adding lime milk in a saline solution comprising at least 0.5 g of sulfate ions per liter, and b) carbonation of all or part of the milk of lime with carbon dioxide, it is particularly advantageous to inject sufficient carbon dioxide into the saline solution comprising the lime milk so that the content of granules of slaked lime (Ca (OH) 2 ) relative to the weight of the granules of gypsum and calcium carbonate of the pulp is less than 5%, preferably less than 3%, more preferably less than 1% by weight.
- Ca (OH) 2 slaked lime
- the carbonation with carbon dioxide is carried out at a pH of about 7, preferably about 6.5, preferably about 6.0, more
- the pH of the mixture rises rapidly from about 0.1 to 2.5 pH units to reach pH values of between about 7.0 and about 9.5. This rise in pH is due to the presence of granules of calcium carbonate which is a mild alkali, and the presence of residual lime that is alkaline. The more the lime is completely carbonated, the more the pH of the broth at the end of the carbonation approaches the neutrality.
- This carbonation can be carried out with a carbon dioxide originating from fumes produced by the combustion of a sulfur-containing organic compound such as a coal, a lignite, a wood, an agricultural residue, an organic residue of the food industry, an organic residue of the paper industry, a sludge from a drinking water or wastewater treatment plant, an organic sludge from a biogas plant.
- a sulfur-containing organic compound such as a coal, a lignite, a wood, an agricultural residue, an organic residue of the food industry, an organic residue of the paper industry, a sludge from a drinking water or wastewater treatment plant, an organic sludge from a biogas plant.
- a sulfur-containing organic compound such as a coal, a lignite, a wood, an agricultural residue, an organic residue of the food industry, an organic residue of the paper industry, a sludge from a drinking water or wastewater treatment plant, an organic sludge from a biogas plant.
- such smoke contains a concentration of carbon dioxide
- obtaining granules of gypsum and granules of calcium carbonate in an aqueous solution is obtained by: a) adding lime milk in a saline solution comprising at least 0.5 g of sulfate ions per liter, and b) carbonation of all or part of the milk of lime with carbon dioxide, or in the case where the mixture of gypsum granule and calcium carbonate is obtained by washing sulphurous fumes with a lime milk, it is particularly advantageous to carry out carbonation and flotation in this order and not in the opposite or concomitant order.
- the present invention thus makes it possible to separate a mixture of granules of gypsum and granules of calcium carbonate present in an aqueous solution in two enriched phases respectively:
- the present invention also relates to the use of granules of calcium carbonate or gypsum granules derived from the method of the present invention: in cement works, or in civil engineering, or in road engineering, or for the manufacture of materials construction, or the manufacture of panels or plasterboard, or the manufacture of road aggregates, or the manufacture of backfill material to fill underground cavities, or the desulfurization of fumes.
- Fig. 1 is a block diagram of one of the embodiments of the invention using a flotation cell 3.
- a suspension 1 containing gypsum granules and calcium carbonate granules and a sodium aqueous solution is introduced into the flotation cell 3.
- the hetero-polar organic surfactant collector 2 is also introduced into the flotation cell 3.
- a phase 4 enriched in gypsum granules is collected overflow of the flotation cell 3.
- a phase 5 enriched in granules of Calcium carbonate is collected underflow from the flotation cell 3.
- Fig. 2 is a schematic diagram of one embodiment of the invention using a flotation cell 3, and separation equipment complementary liquid-solid such as decanters 6 and 13 and filters 10 and 17.
- a suspension 1 containing gypsum granules and granules of calcium carbonate and a sodium aqueous solution is introduced into the flotation cell 3.
- the organic surfactant collector hetero-polar 2 is also introduced into the flotation cell 3.
- a phase 4 enriched in gypsum granules is collected overflow of the flotation cell 3, and is introduced optionally diluted with water or mother liquors in a decanter and optionally introduced with a flocculant and / or an anti-foaming agent in a decanter 6.
- the settling water or the settling mother liquors 7 are collected in overflow from the decanter 6.
- a broth 8 enriched with granules of gypsum is then introduced. in a filter 10, and a washing water or washing mother liquor 9 is optionally used in the filter 10 to wash the granules of the broth 8 optionally washed.
- a filtered cake 12 enriched with gypsum granules is collected from the filter 10, as well as the filtration and optionally washing waters 11 which are collected from the filter.
- Phase 5 enriched in granules of calcium carbonate is collected underflow of the flotation cell 3.
- the phase 5 is introduced, optionally with a flocculent and / or an anti-foaming agent, into the decanter 13.
- the sodium water or settling mother liquors 14 are collected overflow from the settler 13.
- a broth 15 enriched in granules of calcium carbonate is then introduced into a filter 17, and a washing water or washing mother liquor 16 is (are ) optionally used at the filter 17 to wash the granules of the broth 15.
- a filtered cake 19 enriched with granules of calcium carbonate is collected from the filter 10, and the filtration water and optionally washing 18 which are collected from the filter 17.
- the filtration waters and optionally the washing waters 11 are recycled upstream of the decanter 6 to repulse the phase 4 (scum) before introduction into the decanting chamber.
- r 6 and thus organize a countercurrent to optimize the water balance of the method according to the invention.
- Fig. 3 is a block diagram of one embodiment of the invention using a flotation cell 3, complementary liquid-solid separation equipment such as decanters 6 and 13 and filters 10 and 17, and contact reactors 23 and 26.
- a saline solution 21 comprising at least 3 g of sodium ions per liter and 0.5 g of sulfate ions per liter is introduced into a contact reactor 23 with a milk of lime 22, forming in the contact reactor granules of gypsum .
- the broth 24 obtained is then introduced into a contact reactor 26 with a gas comprising carbon dioxide (CO 2 ) in order to carbonate the optional residual calcium hydroxide present in the broth 24 collected from the contact reactor 23 to form granules of calcium carbonate.
- a suspension 1 containing gypsum granules and calcium carbonate granules and an aqueous solution is then introduced into a flotation cell 3 for processing according to one embodiment of the method of the present invention described in FIG. 2.
- Example 1 (not in accordance with the invention).
- a hetero-polar organic surfactant sodium oleate was added to the suspension to be floated in 3 different amounts to obtain concentrations of 1 ⁇ 10 -5 , 5 ⁇ 10 -5 , and 10 ⁇ 10 -5 (10 -4 ) mol / L in the suspension. to float.
- the flotation cell was operated at a speed of 1750 rpm to inject air into the flotation cell for a period of 5 minutes.
- Fig. 4 reports the% mass recovery, noted as 'Recovery ()', of gypsum granules, calcium carbonate, and apatite at the end of each flotation test for three concentrations of sodium oleate added to the cell. flotation before the actual flotation operation.
- Example 2 (in accordance with the invention) the tests of Examples 2 to 5 were carried out in two different pilot flotation columns with however a similar operating scheme and procedures. The tests were carried out using a brine whose sodium content (in the form of dissolved sodium chloride) was at least 3 g / l and up to 23 g / l (1 mol / l). The calcium content (in the form of dissolved gypsum and soluble calcium chloride) was at least 0.5 g / L and up to 40 g / L (1 mol / L).
- the first column used measures 3.5 meters in height and has a diameter of 75 mm ensuring a feed rate of 0.01 to 0.5 m / h.
- the second column used is an industrial pilot of 10 m height and 300 mm diameter, ensuring a feed rate of up to 5 m / h.
- This second flotation column was only used with sodium oleate at concentrations ranging from 0.5 to 10 ppm.
- the results of tests on this second column were comparable to the results obtained on the first column under the equivalent operating conditions (amount of flotation agent, surface velocities of flotation air and pulp feed rate.
- the different points of introduction of the collector into the columns were tested starting from the introduction directly in the bubble generator and two different levels of the column.
- the feed rates of the pulp in this example were varied to achieve downwardly directed pulp surface velocities ranging from 0.5 cm to 1.7 cm / sec.
- the air supply flow rates were adjusted to obtain superficial velocities J g rising gas between 0.5 to 1.9 cm / s.
- the water yields have the same definition as that of the solids, namely: ratio between the weight of the water in the foam and the sum of the weights of the water in the foam plus that of the waste rock.
- the weight of the water of the floated phase is obtained by difference of the weight of the floated phase to which is subtracted the weight of the granules of gypsum and calcium carbonate and the weight of the dissolved salts.
- the fluxes of material were thus calculated by timing of each intake and weighing of the collected samples, component flows by component, also, thanks to the chemical analyzes.
- the sulphate analysis for determining the separation efficiency of the gypsum between the floated phase and the unfloated phase is carried out by acid dissolution of the solids and then gravimetry of the sulphate by precipitation of BaSO 4 with BaCl 2 .
- the carbonate analysis for the determination of the separation efficiency of calcium carbonate between the floated phase and the unfloated phase was carried out on the filtered solids (floated and sterile), and dried in study at 80 ° C and then ground.
- the carbonate analysis was carried out by gravimetry of C0 2 contained in the solids by a standard measurement of the ACA (Absorption Carbonate Analysis) type.
- the solids are attacked with concentrated hydrochloric acid (9N).
- the mass of dry matter in floats and not floated is calculated according to:
- the yield therefore indicates the portion recovered in the foam even when we talk about the yield of carbonate.
- the yield of the sulphates in the waste rock is calculated according to the formula below but taking the flow of the sulphates in the sterile ⁇ bso 4 ⁇ sterile. Carbonate yields are calculated in the same way.
- the selectivity S of the flotation separation process is calculated from the chemical analyzes carried out and the contents of carbonates and sulphates in the foams and waste products according to the following formula: sterile foams
- Example 2 The results of Example 2 on column 1 75 mm in diameter are shown in Table 1, separation tests carried out with a surfactant of sodium oleate type at 20 ppm concentration.
- alkyl sulphate (R-S0 4 2- ): Flotinor S 072 (Clariant)
- Aero 845N (Cytec) composed of Tetrasodium N- (1,2-dicarboxyethyl) n-octadecyl sulfosuccinamate, having three carboxylic groups and a sulfonate group.
- Procol CA540 (Allied Colloid Ltd) composed of N- (3-carboxylato-1-oxo-3-sulfonatopropyl) -N-octadecyl-DL-tetrasodium aspartate non-ionic surfactants of Guerbet alcohol type with 12 or 16 carbon atoms: Isofol 12, denoted ISF12 and Isofol 16, denoted ISF 16 (Sasol Olefins & Surfactants).
- Table 2 (Example 3) groups together anionic surfactant collector tests used alone, of the carboxylic type (oleate and sodium laurate), of the alkyl sulphate type (dodecyl sulphates), of the mixed carboxylic and sulphonate (sulpho succinamate) type.
- Table 3 (Example 4) groups together anionic surfactant type collector tests used in combination with anionic surfactants or with nonionic surfactants, always in a 1: 1 mass ratio for each collector.
- sodium dodecyl sulphate shows a slightly lower separation yield of the gypsum, 72-76%, and a selectivity lower than that obtained with sodium oleate
- dodecyl sulphate from 22 to 60 ppm for sulphosuccinamate is also greater than with sodium oleate whose optimal results are obtained with consumptions of between 0.8 and 3.0 ppm.
- nonionic reagents such as iso-alcohols and Guerbet alcohols were tested, as well as a cationic collector, Cataflot from CECA.
- Example 3 Flotation tests at various surfactant collectors, pulp and air supply rates, collector concentration in relation to the pulp, and various points of introduction of the collector (pump: at the of the recirculating pump of the pulp in the column in which the flotation gas is introduced, high CL: between foam-pulp interface and the feed point of the pulp)
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1262309A FR2999455B1 (fr) | 2012-12-19 | 2012-12-19 | Methode de separation de carbonate de calcium et de gypse |
PCT/EP2013/077062 WO2014095980A1 (fr) | 2012-12-19 | 2013-12-18 | Méthode de séparation de carbonate de calcium et de gypse |
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EP2934760A1 true EP2934760A1 (fr) | 2015-10-28 |
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EP13811473.1A Withdrawn EP2934760A1 (fr) | 2012-12-19 | 2013-12-18 | Méthode de séparation de carbonate de calcium et de gypse |
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US (1) | US20150328645A1 (fr) |
EP (1) | EP2934760A1 (fr) |
CN (1) | CN105307774B (fr) |
FR (1) | FR2999455B1 (fr) |
WO (1) | WO2014095980A1 (fr) |
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CA2959949C (fr) | 2014-09-18 | 2023-02-14 | Akzo Nobel Chemicals International B.V. | Utilisation d'alcools ramifies et d'alcoxylates de ceux-ci en tant que collecteurs secondaires |
CN106179771B (zh) * | 2016-07-18 | 2019-03-05 | 攀钢集团攀枝花钢铁研究院有限公司 | 钙法提钒尾渣的回收利用方法 |
US11479472B2 (en) | 2019-01-24 | 2022-10-25 | Elixsys, Inc. | Systems and methods to recover value-added materials from gypsum |
US11148956B2 (en) | 2019-01-24 | 2021-10-19 | Elixsys, Inc. | Systems and methods to treat flue gas desulfurization waste to produce ammonium sulfate and calcium carbonate products |
CN111111929B (zh) * | 2019-12-30 | 2021-10-15 | 河北中科同创科技发展有限公司 | 一种碱渣预处理分离碳酸钙的方法 |
CN115397802A (zh) * | 2020-02-14 | 2022-11-25 | 索尔维公司 | 用于矿物回收的新的起泡剂及其制备和使用方法 |
Citations (1)
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US2340613A (en) * | 1940-03-04 | 1944-02-01 | Du Pont | Salt purification |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
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US2040187A (en) * | 1934-05-11 | 1936-05-12 | Ernest H Rose | Process for separating solids by flotation |
US2255139A (en) * | 1939-07-03 | 1941-09-09 | Separation Process Company | Flotation of calcium carbonate ores |
US4043902A (en) * | 1975-06-06 | 1977-08-23 | American Cyanamid Company | Tri-carboxylated and tetra-carboxylated fatty acid aspartates as flotation collectors |
US4351668A (en) * | 1981-03-09 | 1982-09-28 | Cominco Ltd. | Flotation of Cu and Pb sulfide concentrates containing carbonates |
JPS59142895A (ja) * | 1983-02-01 | 1984-08-16 | Dowa Mining Co Ltd | 含亜鉛溶液の中和処理法 |
US4995965A (en) * | 1988-06-13 | 1991-02-26 | Akzo America Inc. | Calcium carbonate beneficiation |
CN100384737C (zh) * | 2004-06-09 | 2008-04-30 | 华东理工大学 | 低硫酸钙含量的氯化钾生产方法 |
US8092686B2 (en) * | 2004-12-23 | 2012-01-10 | Georgia-Pacific Chemicals Llc | Modified amine-aldehyde resins and uses thereof in separation processes |
EP1944088A1 (fr) * | 2007-01-12 | 2008-07-16 | Omya Development Ag | Procédé de purification des minéraux en fonction du carbonate de calcium par flottation dans la présence de méthosulfate d'imidazollum quaternaire |
US8403146B2 (en) * | 2008-07-02 | 2013-03-26 | Georgia-Pacific Chemicals Llc | Collectors |
CN101723409B (zh) * | 2009-12-18 | 2011-09-07 | 中蓝连海设计研究院 | 用劣质光卤石制取氯化钾的方法 |
JP5528130B2 (ja) * | 2010-01-21 | 2014-06-25 | 太平洋セメント株式会社 | カルシウム成分及び鉛成分を含有する微粉末の処理方法並びに処理システム |
CN102815725A (zh) * | 2012-07-18 | 2012-12-12 | 中蓝连海设计研究院 | 利用含硫酸钙的光卤石矿制取氯化钾的工艺 |
US9545636B2 (en) * | 2013-04-30 | 2017-01-17 | Newmont Usa Limited | Method for processing mineral material containing acid-consuming carbonate and precious metal in sulfide minerals |
-
2012
- 2012-12-19 FR FR1262309A patent/FR2999455B1/fr not_active Expired - Fee Related
-
2013
- 2013-12-18 WO PCT/EP2013/077062 patent/WO2014095980A1/fr active Application Filing
- 2013-12-18 EP EP13811473.1A patent/EP2934760A1/fr not_active Withdrawn
- 2013-12-18 US US14/652,963 patent/US20150328645A1/en not_active Abandoned
- 2013-12-18 CN CN201380072243.XA patent/CN105307774B/zh not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2340613A (en) * | 1940-03-04 | 1944-02-01 | Du Pont | Salt purification |
Also Published As
Publication number | Publication date |
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FR2999455B1 (fr) | 2016-07-15 |
CN105307774A (zh) | 2016-02-03 |
WO2014095980A1 (fr) | 2014-06-26 |
CN105307774B (zh) | 2018-02-23 |
FR2999455A1 (fr) | 2014-06-20 |
US20150328645A1 (en) | 2015-11-19 |
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