WO2010097446A1 - Process for preparing a magnesite-enriched magnesium carbonate precipitate - Google Patents
Process for preparing a magnesite-enriched magnesium carbonate precipitate Download PDFInfo
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- WO2010097446A1 WO2010097446A1 PCT/EP2010/052434 EP2010052434W WO2010097446A1 WO 2010097446 A1 WO2010097446 A1 WO 2010097446A1 EP 2010052434 W EP2010052434 W EP 2010052434W WO 2010097446 A1 WO2010097446 A1 WO 2010097446A1
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- bicarbonate
- magnesium
- carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
Definitions
- the present invention provides a process for preparing a magnesite-enriched magnesium carbonate precipitate and the use of a sodium bicarbonate and or potassium bicarbonate electrolyte to precipitate magnesite-enriched magnesium carbonate.
- carbon dioxide may be sequestered by mineral carbonation.
- orthosilicates or chain silicates can be relatively easy reacted with carbon dioxide to form carbonates and can thus suitably be used for carbon dioxide sequestration.
- magnesium orthosilicates suitable for mineral carbonation are olivine, in particular forsterite, and monticellite .
- suitable chain silicates are minerals of the pyroxene group, in particular enstatite.
- WO02/085788 for example, is disclosed a process for mineral carbonation of carbon dioxide wherein particles of silicates selected from the group of ortho-, di-, ring, and chain silicates, are dispersed in an aqueous electrolyte solution and reacted with carbon dioxide .
- silicates selected from the group of ortho-, di-, ring, and chain silicates
- aqueous electrolyte solution aqueous electrolyte solution
- Magnesium silicate hydroxide minerals such as for example serpentine and talc, are sheet silicates and are more difficult to convert into carbonates, i.e. the reaction times for carbonation are much longer.
- Such sheet silicate hydroxides need to undergo a heat treatment or activation at elevated temperatures prior to the reaction with carbon dioxide.
- WO2007060149 a process is described for activating serpentine by conversion to olivine, wherein the serpentine is contacted with a hot synthesis gas.
- the resulting activated mineral can be used to react with carbon dioxide.
- Natural minerals suitable for carbonation can be found in abundance and should theoretically provide enough storage facility to sequestrate all the carbon dioxide produced worldwide. When a carbon dioxide sequestration process is located near a mineral production site, the transport cost are low, since the mineral carbonate formed could be stored in used mining pits. However, exploitable mineral resources are generally located far from the place where the carbon dioxide is produced and where it would preferentially be sequestrated. This can lead to high transportation cost for both the reactant mineral and the formed magnesium carbonate, optionally including any remaining depleted mineral, affecting the industrial applicability of the process .
- magnesium carbonate may exist in several forms including those that are hydrated. For example when magnesium carbonate is precipitated from aqueous magnesium bicarbonate or magnesium hydroxide solution, depending on the temperature and pressure, several hydrated or non-hydrated magnesium carbonate precipitates are formed. According to D. Langmuir, Stability of carbonates in the system MgO-CO 2 -H 2 O,
- the present invention provides a process for preparing a magnesite-enriched magnesium carbonate precipitate, comprising the steps of:
- a magnesium carbonate precipitate is obtained, which is enriched in magnesite. As a result less water is incorporated in the magnesium carbonate precipitate and therefore the weight of the precipitate is reduced per unit volume and more carbon dioxide may sequestrated per magnesium ion.
- a magnesite-enriched magnesium carbonate precipitate is prepared.
- Reference herein to a magnesite-enriched magnesium carbonate precipitate is to a magnesium carbonate precipitate comprising above 30 mol% of magnesite, preferably at least 60% of magnesite, more preferably at least 80% of magnesite based on the total number of moles of magnesite, hydromagnesite and nesquehonite in the magnesium carbonate precipitate.
- the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate may comprise any concentration of dissolved magnesium carbonate, it will be appreciated that it cannot comprise more dissolved magnesium carbonate than the solubility of magnesium bicarbonate in the aqueous solution at a given temperature and pressure.
- the concentration at any temperature below 120 0 C should be higher than the solubility of magnesium bicarbonate in the aqueous solution on or above 120 0 C.
- the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate preferably comprises at least one electrolyte that is dissolved sodium bicarbonate.
- the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate preferably comprises in the range of from 0.01 to 1 mol/1, more preferably 0.05 to 0.5 mol/1 of sodium bicarbonate and/or potassium bicarbonate.
- the latter range of sodium bicarbonate and/or potassium bicarbonate is particularly preferred as it requires much less sodium bicarbonate and/or potassium bicarbonate to be provided to the aqueous solution. As a result less electrolyte needs to be provided, recovered and/or recycled while the solubility of magnesium bicarbonate is maximised.
- step (b) of the process according to the invention the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate (also referred to as aqueous solution) is heated to induce bicarbonate decomposition.
- the dissociation products are precipitated magnesium carbonate, carbon dioxide and water.
- the sodium and/or potassium cations remain predominately dissolved as dissolved sodium and/or potassium bicarbonate salts due to the higher solubility of these salts compared to magnesium bicarbonate.
- no other sodium or potassium salts are added to the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate (also referred to as aqueous solution) is heated to induce bicarbonate decomposition.
- the aqueous bicarbonate solution is heated to a temperature in the range of from 120 0 C or higher, preferably of from 120 to 180 0 C, even more preferably 125 to 160°C, still more preferably of from 140 to 160 0 C.
- the aqueous solution is heated in step (b) under a carbon dioxide-comprising atmosphere having a carbon dioxide partial pressure of at least 0.2 bara.
- the aqueous solution is heated in step (b) under a carbon dioxide-comprising atmosphere having a carbon dioxide partial pressure of in the range of from 0.2 to 75 bara, more preferably 1 to 50 bara, even more preferably 1.1 to 40 bara.
- the carbon dioxide-comprising atmosphere may comprise any concentration of carbon dioxide, as long as the concentration is sufficient to provide the required carbon dioxide partial pressure as described herein above at the chosen overall pressure of the carbon dioxide-comprising atmosphere.
- the carbon dioxide-comprising atmosphere is an essentially pure carbon dioxide atmosphere, not taking steam into account.
- the overall pressure of the carbon dioxide-comprising atmosphere is at least 1.0 bara, preferably at least 1.1 bara more preferably in the range of from 1.1 to 200 bara.
- a magnesite-enriched magnesium carbonate precipitate is obtained.
- magnesium carbonate precipitate may also comprise hydromagnesite and/or nesquehonite .
- the initial precipitate obtained in step (b) may comprise significant amounts of hydromagnesite.
- step (b) the aqueous solution is maintained at the temperature and pressure conditions of step (b) for a time period of in the range of from 1 minute to 20 hours, preferably of from 1 hour to 10 hours, more preferably 3 to 7 hours, at least part of the hydromagnesite in the magnesium carbonate precipitate is converted to magnesite. Therefore, when performing the process according to the invention using low electrolyte concentration it is preferable to maintain, following step (b) , the aqueous solution at the temperature and pressure conditions of step (b) for a time period of in the range of from 1 minute to 20 hours, preferably of from 30 minutes to 10 hours, more preferably 1 to 7 hours .
- the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate provided in step (a) is obtained by a process which includes at least contacting an aqueous slurry of magnesium silicate mineral with carbon dioxide to convert the magnesium silicate mineral into an aqueous solution comprising dissolved magnesium bicarbonate .
- Suitable silicate minerals may have different structures.
- silicates may be composed of orthosilicate monomers, i.e. the orthosilicate ion SiOz [ ⁇ " which has a tetrahedral structure. Orthosilicate monomers form oligomers by means of 0-Si-O bonds at the polygon corners.
- the Q s notation refers to the connectivity of the silicon atoms.
- the value of superscript s defines the number of nearest neighbour silicon atoms to a given Si.
- Orthosilicates also referred to as nesosilicates, are silicates which are composed of distinct orthosilicate tetrathedra that are not bonded to each other by means of
- 0-Si-O bonds QO structure
- Other structures include chain silicates, also referred to as inosilicates, which might be single chain (Si ⁇ 32 ⁇ as unit structure, i.e. a (Q ⁇ ) n structure) or double chain silicates ( (Q3Q2) ⁇ structure) .
- chain silicates also referred to as inosilicates, which might be single chain (Si ⁇ 32 ⁇ as unit structure, i.e. a (Q ⁇ ) n structure) or double chain silicates ( (Q3Q2) ⁇ structure)
- sheet silicate hydroxides also referred to as phyllosilicates, which have a sheet structure (Q ⁇ ) n .
- orthosilicates or chain silicates can be relatively easy reacted with carbon dioxide to form carbonates and can thus suitably be used for carbon dioxide sequestration.
- magnesium orthosilicates suitable for mineral carbonation include olivine, in particular forsterite.
- suitable chain silicates are minerals of the pyroxene group, in particular wollastonite .
- magnesium silicate hydroxide minerals for example serpentine
- sheet silicates are more difficult to convert into carbonates, i.e. the reaction times for carbonation are much longer.
- Such sheet silicate hydroxides need to undergo a heat treatment or activation at elevated temperatures prior to the reaction with carbon dioxide.
- the serpentine mineral is at least partly converted into its corresponding ortho- or chain silicate mineral, silica and water.
- the activation of silicate hydroxide minerals may include a conversion of part of the silicate hydroxide minerals into an amorphous sheet silicate hydroxide mineral derived compound.
- the carbon dioxide, which is contacted with the aqueous slurry is preferably provided as a carbon dioxide-comprising gas.
- the carbon dioxide-comprising stream may be contacted with an aqueous slurry comprising magnesium silicate mineral, preferably magnesium silicate mineral particles.
- the carbon dioxide partial pressure in the carbon dioxide-comprising gas that is contacted with the aqueous slurry is at least 0.01 bar, more preferably the carbon dioxide partial pressure is in the range of from 0.01 bar to 0.5, even more preferably 0.1 bar to 0.2 bar at Standard Temperature and Pressure conditions of 0 0 C and 1 bar.
- Such carbon dioxide partial pressures allow for the direct capture of carbon dioxide from dilute carbon dioxide-comprising gases, without the need for a pre-treatment of the dilute gas in order to increase the carbon dioxide partial pressure.
- Reference herein to leaching is to a conversion of the silicate mineral wherein at least part of the magnesium of calcium is removed from the mineral and dissolved in the aqueous medium as magnesium or calcium cations.
- Reference herein to the extent of leaching is to the mole% of magnesium and/or calcium leached from the mineral, based on the total number of moles of magnesium and/or calcium present in the original mineral.
- the carbon dioxide-comprising gas stream is contacted with the aqueous slurry comprising magnesium silicate mineral particles under low temperature and low carbon dioxide partial pressure conditions.
- the carbon dioxide-comprising gas stream is contacted with the aqueous slurry comprising magnesium or calcium- comprising silicate particles at a temperature in the range of from 1 to 100 0 C, more preferably 10 to 60 0 C, even more preferably 15 to 50 0 C and at a carbon dioxide partial pressure in the range of from 0.01 to 35 bara, more preferably 0.05 to 25 bara, even more preferably 0.1 to 10 bara.
- step (a) the solubility of the bicarbonate is maximised, and thus as a consequence so is the extent of leaching which may be achieved. Due to the low carbon dioxide partial pressure requirements there is no need to pressurise the carbon dioxide-comprising gas prior to contacting it with the aqueous slurry. It will be appreciated that in case the temperature of the carbon dioxide-comprising gas is to high it can advantageously be cooled by heat-exchange with another process stream. In case magnesium silicate mineral particles are use they preferably have an average particle size in the range of from 0.1 ⁇ m to 5 cm, more preferably 0.5 to 500 ⁇ m.
- Reference herein to average diameter is to the volume medium diameter D(v,0.5), meaning that 50 volume% of the particles have an equivalent spherical diameter that is smaller than the average diameter and 50 volume% of the particles have an equivalent spherical diameter that is greater than the average diameter.
- the equivalent spherical diameter is the diameter calculated from volume determinations, e.g. by laser diffraction measurements.
- the mineral particles In order to reach optimal leaching of the magnesium and/or calcium cations from the mineral particles it is preferred that the mineral particles have an average particle size of 50 ⁇ m or less, more preferably 15 ⁇ m or less.
- the at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate may be added to the aqueous slurry before or during contacting with the carbon dioxide-comprising gas or preferably is added to the aqueous solution comprising dissolved magnesium bicarbonate .
- the at least one electrolyte may be provided as a solid sodium bicarbonate and/or potassium bicarbonate, which is to be dissolved, or in the form of an aqueous solution of the sodium bicarbonate and/or potassium bicarbonate .
- the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate provided in step (a) is in the form of an aqueous slurry comprising the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate and additionally magnesium silicate mineral.
- This aqueous slurry may be directly obtained from the process for obtaining the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate provided in step (a) .
- During the dissociation of the bicarbonate carbon dioxide is formed.
- the concentration of dissolved carbon dioxide in the aqueous solution remains high allowing additional leaching of magnesium or calcium from the magnesium silicate mineral during the dissociation of the bicarbonate and precipitation of the magnesium carbonate, thus a further increase the extent of leaching may be achieved.
- any magnesium silicate mineral may be used to obtain the the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate provided in step (a) .
- the magnesium silicate mineral may for example be a mixed silicate-oxide compound and/or a mixed silicate-oxide-hydroxide compound.
- the magnesium and/or calcium-comprising silicate mineral may be in its hydrated form.
- Reference herein to magnesium silicate is to silicates comprising magnesium. Part of the magnesium may be replaced by other metals, for example iron, aluminium or manganese.
- suitable magnesium silicate minerals are natural occurring magnesium silicate minerals, e.g. olivine or serpentine, and industrial waste streams such as steel slag, paper bottom ash, or coal fly ash.
- the magnesium silicate mineral is an olivine or serpentine, albeit after activation.
- Serpentine is most preferred due to its natural abundance. Serpentine is a general name applied to several members of a polymorphic group of minerals having comparable molecular formulae, i.e. (Mg, Fe) 3Si2 ⁇ 5 (OH) 4 or
- Serpentine with a high magnesium content i.e. serpentine that has no Fe or deviates little from the composition Mg3Si2 ⁇ 5 (OH) 4 is preferred since a possible resulting mineral after activation is has a chemical composition resembling an olivine, which has the composition Mg2Si ⁇ 4 and can sequester more carbon dioxide than olivine with a substantial amount of magnesium replaced by iron.
- Olivine is a general name applied to several members of a polymorphic group of minerals having comparable molecular formulae, i.e. Mg2Si ⁇ 4 or (Mg, Fe) 2Si ⁇ 4, depending on the iron content.
- sheet silicate minerals such as serpentine require a heat treatment or activation prior to being contacted with the carbon dioxide- comprising gas.
- Activation of serpentine minerals for mineralisation purposes has been described in for instance EP1951424.
- the activation is performed by contacting the mineral with hot synthesis gas.
- hot gasses may be used such as for instance hot flue gas.
- such an activation is performed in a fluidized bed reactor, in particular in a fluidized bed reactor, wherein a combustible fuel is provided together with a molecular oxygen-comprising gas, for instance natural gas and air, and the combustible gas is combusted inside the fluidized bed.
- a combustible fuel is provided together with a molecular oxygen-comprising gas, for instance natural gas and air, and the combustible gas is combusted inside the fluidized bed.
- the carbon dioxide-comprising gas may be pure carbon dioxide or a mixture of carbon dioxide with one or more other gases.
- the carbon dioxide is a dilute carbon dioxide-comprising gas. It is an advantage of the present invention that such dilute carbon dioxide- comprising gases may be used without the need to for pre- treatment, i.e. pre-concentrating (for instance by an amine absorption process) , pre-pressurising or preheating.
- suitable dilute carbon dioxide- comprising gases include flue gas, synthesis gas or the effluent of a water-gas-shift process.
- Reference herein to synthesis gas is to a gas comprising at least hydrogen, carbon monoxide and optionally carbon dioxide.
- the carbon monoxide content of synthesis gas may be reduced by a water-gas-shift process wherein carbon monoxide is converted with water to hydrogen and carbon dioxide .
- the invention provides the use of a sodium bicarbonate and or potassium bicarbonate electrolyte to precipitate magnesite-enriched magnesium carbonate from an aqueous solution of magnesium bicarbonate .
- the invention is illustrated by the following non- limiting examples. Example 1
- An aqueous solution comprising dissolved magnesium bicarbonate and optionally dissolved sodium bicarbonate was prepared by contacting an aqueous slurry of activated serpentine (approximately 75 to 80 dehydroxylated) with carbon dioxide.
- the obtained aqueous slurry comprising dissolved magnesium bicarbonate was used to prepare a magnesium carbonate precipitate.
- the magnesium carbonate precipitate was formed by heating the aqueous solution under a carbon dioxide-comprising atmosphere. The precipitate was analysed after 3 hours.
- the composition of the magnesium carbonate precipitate was analysed using X-ray diffraction (XRD) .
- Table 1 The use of temperatures below 120 0 C results in a predominately hydromagnesite precipitate. In addition it is shown that also at low electrolyte concentrations a magnesite-enriched magnesium carbonate precipitate can be obtained.
- An aqueous solution comprising dissolved magnesium bicarbonate and dissolved sodium bicarbonate was prepared by contacting an aqueous slurry of activated serpentine (approximately 75 to 80 dehydroxylated) with carbon dioxide. Sodium bicarbonate was added to the aqueous slurry to provide a sodium bicarbonate concentration of 0.1 mol/1 (based on the liquid content) . The obtained aqueous slurry comprising dissolved magnesium bicarbonate was used to prepare a magnesium carbonate precipitate.
- the magnesium carbonate precipitate was formed by heating the aqueous solution under a carbon dioxide-comprising atmosphere (total pressure 5.6 bara, carbon dioxide partial pressure 2 bara) .
- the aqueous slurry together with the obtained precipitate were maintained at the elevated temperature under the carbon dioxide atmosphere for 5 hours.
- the composition of the magnesium carbonate precipitate was analysed using thermographimetric analysis (TGA combined with mass spectrometry (MS) . From the measured ratio of carbon dioxide and water, the composition of the precipitate was determined. The composition of composition of the precipitate was followed in time. The composition of the precipitate is shown in table 2. It will be clear that maintaining the aqueous solution under the conditions according to the invention for an extended time results in an increased magnesite content of the magnesium carbonate precipitate.
- Table 2 It will be clear that maintaining the aqueous solution under the conditions according to the invention for an extended time results in an increased magnesite content of the magnesium carbonate precipitate.
- a model experiment was done by preparing an aqueous magnesium carbonate solution by contacting an aqueous brucite (MgOH 2 ) solution with an carbon dioxide atmosphere. Sodium bicarbonate was added to the aqueous solution to provide a sodium bicarbonate concentration of 0.1 mol/1. The aqueous solution was heated to 140 0 C and magnesium carbonate precipitation commenced. The aqueous solution together with the obtained precipitate were maintained at the elevated temperature under carbon dioxide for 7 hours. The composition of the magnesium carbonate precipitate was analysed as described under example 2. At the start of the experiment the precipitate contained seven times more hydromagnesite than magnesite. After 7 hours no hydromagnesite could be detected in the precipitate only magnesite was found.
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Abstract
The invention provides a process for preparing a magnesite-enriched magnesium carbonate precipitate, comprising the steps of : (a) providing an aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate; (b) heating the aqueous solution to a temperature of at least 120° C under an carbon dioxide-comprising atmosphere having a carbon dioxide partial pressure of at least 0.2 bara to obtain a magnesite-enriched magnesium carbonate precipitate In another aspect the invention provides the use of a sodium bicarbonate and or potassium bicarbonate electrolyte to precipitate magnesite-enriched magnesium carbonate from an aqueous solution of magnesium bicarbonate.
Description
PROCESS FOR PREPARING A MAGNESITE-ENRICHED MAGNESIUM
CARBONATE PRECIPITATE
The present invention provides a process for preparing a magnesite-enriched magnesium carbonate precipitate and the use of a sodium bicarbonate and or potassium bicarbonate electrolyte to precipitate magnesite-enriched magnesium carbonate.
It is known that carbon dioxide may be sequestered by mineral carbonation. In nature, stable carbonate minerals and silica are formed by a reaction of carbon dioxide with natural magnesium silicate minerals: MgxSiy0x+2y + XCO2 ■=> xMgCO3 + ySiθ2
It is known that orthosilicates or chain silicates can be relatively easy reacted with carbon dioxide to form carbonates and can thus suitably be used for carbon dioxide sequestration. Examples of magnesium orthosilicates suitable for mineral carbonation are olivine, in particular forsterite, and monticellite . Examples of suitable chain silicates are minerals of the pyroxene group, in particular enstatite.
In WO02/085788, for example, is disclosed a process for mineral carbonation of carbon dioxide wherein particles of silicates selected from the group of ortho-, di-, ring, and chain silicates, are dispersed in an aqueous electrolyte solution and reacted with carbon dioxide . Magnesium silicate hydroxide minerals, such as for example serpentine and talc, are sheet silicates and are more difficult to convert into carbonates, i.e. the reaction times for carbonation are much longer. Such sheet silicate hydroxides need to undergo a heat
treatment or activation at elevated temperatures prior to the reaction with carbon dioxide.
In WO2007060149, a process is described for activating serpentine by conversion to olivine, wherein the serpentine is contacted with a hot synthesis gas. The resulting activated mineral can be used to react with carbon dioxide.
Natural minerals suitable for carbonation can be found in abundance and should theoretically provide enough storage facility to sequestrate all the carbon dioxide produced worldwide. When a carbon dioxide sequestration process is located near a mineral production site, the transport cost are low, since the mineral carbonate formed could be stored in used mining pits. However, exploitable mineral resources are generally located far from the place where the carbon dioxide is produced and where it would preferentially be sequestrated. This can lead to high transportation cost for both the reactant mineral and the formed magnesium carbonate, optionally including any remaining depleted mineral, affecting the industrial applicability of the process .
It is known that magnesium carbonate may exist in several forms including those that are hydrated. For example when magnesium carbonate is precipitated from aqueous magnesium bicarbonate or magnesium hydroxide solution, depending on the temperature and pressure, several hydrated or non-hydrated magnesium carbonate precipitates are formed. According to D. Langmuir, Stability of carbonates in the system MgO-CO2-H2O,
Journal of Geology, vol. 73, 1965, p.730-754, at carbon dioxide pressures in the range of from 0.1 to 10 atm, depending on the temperature, three magnesium carbonate
phases are distinguished. Between 10 and 25 0C, nesquehonite (MgCO3.3H2O) is the dominant magnesium carbonate phase. At temperatures between 25 and 600C, hydromagnesite (3MgCO3.Mg (OH) 2.3H2O) . Above 600C, magnesite (MgCO3) is dominantly formed. Where magnesite contains only magnesium and carbonate, the other two also contain significant amounts of water bound in the crystal structure. This results in a higher weight per volume. In addition in the formation hydromagnesite only three carbon molecules are sequestrated per four magnesium ions, where magnesite is formed with a carbon dioxide to magnesium ratio of 1.
Recent studies of mineral carbonation processes have focused on maximising the amount of carbon dioxide, which can be sequestrated per unit of mineral. In for instance Gerdemann et al . (Gerdemann, S.J., W. K. O'Connor, Dahlin, D. C, Penner, L. R. and H. Rush, 2007, Ex situ mineral carbonation. Environ. Sci. Technol. 41, 2587-2593) a batch process is described, wherein in an autoclave at supercritical conditions - high CO2 pressures (115 bara) and temperatures (185°C), and with high electrolyte concentrations (a mixture of electrolytes, 0,64 M sodium bicarbonate and 1 M sodium chloride) an activated serpentine mineral is carbonated. According to Gerdemann, the described process results in a high conversion of the mineral and thus a high carbon dioxide sequestration per unit mineral .
In order to minimise the weight and volume of the precipitated magnesium carbonates while maintaining maximum carbon dioxide sequestration it is desirable to precipitate predominantly magnesite and reduce the amounts of hydromagnesite and nesquehonite formed.
There is a need in the art for a carbon dioxide sequestration process based on mineral carbonation, wherein the precipitated magnesium carbonate is enriched in magnesite. It has now been found that is possible to sequestrate carbon dioxide by mineral carbonation, while producing a precipitated magnesium carbonate, which is enriched in magnesite, by precipitating magnesium carbonate form a bicarbonate solution comprising a sodium or potassium bicarbonate electrolyte.
Accordingly the present invention provides a process for preparing a magnesite-enriched magnesium carbonate precipitate, comprising the steps of:
(a) providing an aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate;
(b) heating the aqueous solution to a temperature of at least 120°C under a carbon dioxide-comprising atmosphere having a carbon dioxide partial pressure of at least 0.2 bar to obtain a magnesite-enriched magnesium carbonate precipitate.
It is an advantage of the present invention that a magnesium carbonate precipitate is obtained, which is enriched in magnesite. As a result less water is incorporated in the magnesium carbonate precipitate and therefore the weight of the precipitate is reduced per unit volume and more carbon dioxide may sequestrated per magnesium ion. In the process according to the invention a magnesite-enriched magnesium carbonate precipitate is prepared. Reference herein to a magnesite-enriched magnesium carbonate precipitate is to a magnesium
carbonate precipitate comprising above 30 mol% of magnesite, preferably at least 60% of magnesite, more preferably at least 80% of magnesite based on the total number of moles of magnesite, hydromagnesite and nesquehonite in the magnesium carbonate precipitate.
The aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate may comprise any concentration of dissolved magnesium carbonate, it will be appreciated that it cannot comprise more dissolved magnesium carbonate than the solubility of magnesium bicarbonate in the aqueous solution at a given temperature and pressure. In order to allow precipitation of magnesium carbonate in step (b) the concentration at any temperature below 1200C should be higher than the solubility of magnesium bicarbonate in the aqueous solution on or above 1200C.
The aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate preferably comprises at least one electrolyte that is dissolved sodium bicarbonate. The aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate preferably comprises in the range of from 0.01 to 1 mol/1, more preferably 0.05 to 0.5 mol/1 of sodium bicarbonate and/or potassium bicarbonate. The latter range of sodium bicarbonate and/or potassium bicarbonate is particularly preferred as it requires much less sodium bicarbonate and/or potassium bicarbonate to be provided to the aqueous solution. As a result less electrolyte needs to
be provided, recovered and/or recycled while the solubility of magnesium bicarbonate is maximised.
In step (b) of the process according to the invention, the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate (also referred to as aqueous solution) is heated to induce bicarbonate decomposition. The dissociation products are precipitated magnesium carbonate, carbon dioxide and water. The sodium and/or potassium cations remain predominately dissolved as dissolved sodium and/or potassium bicarbonate salts due to the higher solubility of these salts compared to magnesium bicarbonate. Preferably, no other sodium or potassium salts are added to the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate (also referred to as aqueous solution) is heated to induce bicarbonate decomposition. The aqueous bicarbonate solution is heated to a temperature in the range of from 1200C or higher, preferably of from 120 to 1800C, even more preferably 125 to 160°C, still more preferably of from 140 to 1600C. The aqueous solution is heated in step (b) under a carbon dioxide-comprising atmosphere having a carbon dioxide partial pressure of at least 0.2 bara. Preferably, the aqueous solution is heated in step (b) under a carbon dioxide-comprising atmosphere having a carbon dioxide partial pressure of in the range of from 0.2 to 75 bara, more preferably 1 to 50 bara, even more preferably 1.1 to 40 bara. The carbon dioxide-comprising atmosphere may comprise any concentration of carbon dioxide, as long as the concentration is sufficient to
provide the required carbon dioxide partial pressure as described herein above at the chosen overall pressure of the carbon dioxide-comprising atmosphere. Preferably, the carbon dioxide-comprising atmosphere is an essentially pure carbon dioxide atmosphere, not taking steam into account. Preferably, the overall pressure of the carbon dioxide-comprising atmosphere is at least 1.0 bara, preferably at least 1.1 bara more preferably in the range of from 1.1 to 200 bara. In the process according to the invention a magnesite-enriched magnesium carbonate precipitate is obtained. However, magnesium carbonate precipitate may also comprise hydromagnesite and/or nesquehonite . In particular when low electrolyte concentration are used, i.e. 0.05 to 0.5 mol/1 of sodium bicarbonate and/or potassium bicarbonate the initial precipitate obtained in step (b) may comprise significant amounts of hydromagnesite. However, it was found that when following step (b) , the aqueous solution is maintained at the temperature and pressure conditions of step (b) for a time period of in the range of from 1 minute to 20 hours, preferably of from 1 hour to 10 hours, more preferably 3 to 7 hours, at least part of the hydromagnesite in the magnesium carbonate precipitate is converted to magnesite. Therefore, when performing the process according to the invention using low electrolyte concentration it is preferable to maintain, following step (b) , the aqueous solution at the temperature and pressure conditions of step (b) for a time period of in the range of from 1 minute to 20 hours, preferably of from 30 minutes to 10 hours, more preferably 1 to 7 hours .
Preferably, the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate provided in step (a) is obtained by a process which includes at least contacting an aqueous slurry of magnesium silicate mineral with carbon dioxide to convert the magnesium silicate mineral into an aqueous solution comprising dissolved magnesium bicarbonate . Suitable silicate minerals may have different structures. For instance, silicates may be composed of orthosilicate monomers, i.e. the orthosilicate ion SiOz[^" which has a tetrahedral structure. Orthosilicate monomers form oligomers by means of 0-Si-O bonds at the polygon corners. The Qs notation refers to the connectivity of the silicon atoms. The value of superscript s defines the number of nearest neighbour silicon atoms to a given Si. Orthosilicates, also referred to as nesosilicates, are silicates which are composed of distinct orthosilicate tetrathedra that are not bonded to each other by means of
0-Si-O bonds (QO structure) . Other structures include chain silicates, also referred to as inosilicates, which might be single chain (Siθ32~ as unit structure, i.e. a (Q^)n structure) or double chain silicates ( (Q3Q2)Π structure) . Also known are sheet silicate hydroxides, also referred to as phyllosilicates, which have a sheet structure (Q^)n.
It is known that orthosilicates or chain silicates can be relatively easy reacted with carbon dioxide to form carbonates and can thus suitably be used for carbon dioxide sequestration. Examples of magnesium orthosilicates suitable for mineral carbonation include
olivine, in particular forsterite. Examples of suitable chain silicates are minerals of the pyroxene group, in particular wollastonite .
The more abundantly available magnesium silicate hydroxide minerals, for example serpentine, are sheet silicates and are more difficult to convert into carbonates, i.e. the reaction times for carbonation are much longer. Such sheet silicate hydroxides need to undergo a heat treatment or activation at elevated temperatures prior to the reaction with carbon dioxide.
Above a certain temperature, the serpentine mineral is at least partly converted into its corresponding ortho- or chain silicate mineral, silica and water. Additionally, the activation of silicate hydroxide minerals may include a conversion of part of the silicate hydroxide minerals into an amorphous sheet silicate hydroxide mineral derived compound.
In the process according to the invention the carbon dioxide, which is contacted with the aqueous slurry is preferably provided as a carbon dioxide-comprising gas. The carbon dioxide-comprising stream may be contacted with an aqueous slurry comprising magnesium silicate mineral, preferably magnesium silicate mineral particles. Preferably, the carbon dioxide partial pressure in the carbon dioxide-comprising gas that is contacted with the aqueous slurry is at least 0.01 bar, more preferably the carbon dioxide partial pressure is in the range of from 0.01 bar to 0.5, even more preferably 0.1 bar to 0.2 bar at Standard Temperature and Pressure conditions of 00C and 1 bar. Such carbon dioxide partial pressures allow for the direct capture of carbon dioxide from dilute carbon dioxide-comprising gases, without the need
for a pre-treatment of the dilute gas in order to increase the carbon dioxide partial pressure.
When the carbon dioxide-comprising gas stream is contacted with the aqueous slurry comprising magnesium silicate mineral particles, magnesium ions are leached from the mineral and an aqueous solution comprising dissolved magnesium bicarbonate is formed.
Reference herein to leaching is to a conversion of the silicate mineral wherein at least part of the magnesium of calcium is removed from the mineral and dissolved in the aqueous medium as magnesium or calcium cations. Reference herein to the extent of leaching is to the mole% of magnesium and/or calcium leached from the mineral, based on the total number of moles of magnesium and/or calcium present in the original mineral.
The carbon dioxide-comprising gas stream is contacted with the aqueous slurry comprising magnesium silicate mineral particles under low temperature and low carbon dioxide partial pressure conditions. Preferably, the carbon dioxide-comprising gas stream is contacted with the aqueous slurry comprising magnesium or calcium- comprising silicate particles at a temperature in the range of from 1 to 1000C, more preferably 10 to 600C, even more preferably 15 to 500C and at a carbon dioxide partial pressure in the range of from 0.01 to 35 bara, more preferably 0.05 to 25 bara, even more preferably 0.1 to 10 bara. By maintaining low temperature and carbon dioxide partial pressure conditions during the leaching step, i.e. step (a), the solubility of the bicarbonate is maximised, and thus as a consequence so is the extent of leaching which may be achieved. Due to the low carbon dioxide partial pressure requirements there is no need to pressurise the carbon dioxide-comprising gas prior to
contacting it with the aqueous slurry. It will be appreciated that in case the temperature of the carbon dioxide-comprising gas is to high it can advantageously be cooled by heat-exchange with another process stream. In case magnesium silicate mineral particles are use they preferably have an average particle size in the range of from 0.1 μm to 5 cm, more preferably 0.5 to 500 μm. Reference herein to average diameter is to the volume medium diameter D(v,0.5), meaning that 50 volume% of the particles have an equivalent spherical diameter that is smaller than the average diameter and 50 volume% of the particles have an equivalent spherical diameter that is greater than the average diameter. The equivalent spherical diameter is the diameter calculated from volume determinations, e.g. by laser diffraction measurements. In order to reach optimal leaching of the magnesium and/or calcium cations from the mineral particles it is preferred that the mineral particles have an average particle size of 50 μm or less, more preferably 15 μm or less.
The at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate may be added to the aqueous slurry before or during contacting with the carbon dioxide-comprising gas or preferably is added to the aqueous solution comprising dissolved magnesium bicarbonate .
The at least one electrolyte may be provided as a solid sodium bicarbonate and/or potassium bicarbonate, which is to be dissolved, or in the form of an aqueous solution of the sodium bicarbonate and/or potassium bicarbonate .
Preferably, the aqueous solution comprising dissolved magnesium bicarbonate and at least one
electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate provided in step (a) is in the form of an aqueous slurry comprising the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate and additionally magnesium silicate mineral. This aqueous slurry may be directly obtained from the process for obtaining the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate provided in step (a) . During the dissociation of the bicarbonate carbon dioxide is formed. Due to the presence of the carbon dioxide atmosphere, the concentration of dissolved carbon dioxide in the aqueous solution remains high allowing additional leaching of magnesium or calcium from the magnesium silicate mineral during the dissociation of the bicarbonate and precipitation of the magnesium carbonate, thus a further increase the extent of leaching may be achieved.
Any magnesium silicate mineral may be used to obtain the the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate provided in step (a) . The magnesium silicate mineral may for example be a mixed silicate-oxide compound and/or a mixed silicate-oxide-hydroxide compound. The magnesium and/or calcium-comprising silicate mineral may be in its hydrated form. Reference herein to magnesium silicate is to silicates comprising magnesium. Part of the magnesium may be replaced by other metals, for example iron, aluminium or manganese.
Examples of suitable magnesium silicate minerals are natural occurring magnesium silicate minerals, e.g. olivine or serpentine, and industrial waste streams such as steel slag, paper bottom ash, or coal fly ash. Preferably, the magnesium silicate mineral is an olivine or serpentine, albeit after activation.
Serpentine is most preferred due to its natural abundance. Serpentine is a general name applied to several members of a polymorphic group of minerals having comparable molecular formulae, i.e. (Mg, Fe) 3Si2θ5 (OH) 4 or
Mg3Si2U5 (OH) 4, but different morphologic structures.
Serpentine with a high magnesium content, i.e. serpentine that has no Fe or deviates little from the composition Mg3Si2θ5 (OH) 4, is preferred since a possible resulting mineral after activation is has a chemical composition resembling an olivine, which has the composition Mg2Siθ4 and can sequester more carbon dioxide than olivine with a substantial amount of magnesium replaced by iron.
Olivine is a general name applied to several members of a polymorphic group of minerals having comparable molecular formulae, i.e. Mg2Siθ4 or (Mg, Fe) 2Siθ4, depending on the iron content.
As mentioned herein above sheet silicate minerals such as serpentine require a heat treatment or activation prior to being contacted with the carbon dioxide- comprising gas. Activation of serpentine minerals for mineralisation purposes has been described in for instance EP1951424. In EP1951424, the activation is performed by contacting the mineral with hot synthesis gas. However, it will be appreciated that also other hot gasses may be used such as for instance hot flue gas.
Preferably, such an activation is performed in a fluidized bed reactor, in particular in a fluidized bed
reactor, wherein a combustible fuel is provided together with a molecular oxygen-comprising gas, for instance natural gas and air, and the combustible gas is combusted inside the fluidized bed. This allows for a better control of the temperature in the fluidized bed and may result in an improved activated mineral quality, i.e. a high possible extent of leaching.
The carbon dioxide-comprising gas may be pure carbon dioxide or a mixture of carbon dioxide with one or more other gases. Preferably, the carbon dioxide is a dilute carbon dioxide-comprising gas. It is an advantage of the present invention that such dilute carbon dioxide- comprising gases may be used without the need to for pre- treatment, i.e. pre-concentrating (for instance by an amine absorption process) , pre-pressurising or preheating. Examples of suitable dilute carbon dioxide- comprising gases include flue gas, synthesis gas or the effluent of a water-gas-shift process. Reference herein to synthesis gas is to a gas comprising at least hydrogen, carbon monoxide and optionally carbon dioxide. The carbon monoxide content of synthesis gas may be reduced by a water-gas-shift process wherein carbon monoxide is converted with water to hydrogen and carbon dioxide . In another aspect the invention provides the use of a sodium bicarbonate and or potassium bicarbonate electrolyte to precipitate magnesite-enriched magnesium carbonate from an aqueous solution of magnesium bicarbonate . The invention is illustrated by the following non- limiting examples.
Example 1
An aqueous solution comprising dissolved magnesium bicarbonate and optionally dissolved sodium bicarbonate was prepared by contacting an aqueous slurry of activated serpentine (approximately 75 to 80 dehydroxylated) with carbon dioxide. The obtained aqueous slurry comprising dissolved magnesium bicarbonate was used to prepare a magnesium carbonate precipitate. The magnesium carbonate precipitate was formed by heating the aqueous solution under a carbon dioxide-comprising atmosphere. The precipitate was analysed after 3 hours. The composition of the magnesium carbonate precipitate was analysed using X-ray diffraction (XRD) . The obtained results are shown in Table 1. The use of temperatures below 1200C results in a predominately hydromagnesite precipitate. In addition it is shown that also at low electrolyte concentrations a magnesite-enriched magnesium carbonate precipitate can be obtained.
Table 1
* not according to the invention.
** mol% based on the total solids content including unreacted activated serpentine.
Example 2
An aqueous solution comprising dissolved magnesium bicarbonate and dissolved sodium bicarbonate was prepared by contacting an aqueous slurry of activated serpentine (approximately 75 to 80 dehydroxylated) with carbon dioxide. Sodium bicarbonate was added to the aqueous slurry to provide a sodium bicarbonate concentration of 0.1 mol/1 (based on the liquid content) . The obtained aqueous slurry comprising dissolved magnesium bicarbonate was used to prepare a magnesium carbonate precipitate.
The magnesium carbonate precipitate was formed by heating the aqueous solution under a carbon dioxide-comprising atmosphere (total pressure 5.6 bara, carbon dioxide partial pressure 2 bara) . The aqueous slurry together with the obtained precipitate were maintained at the elevated temperature under the carbon dioxide atmosphere for 5 hours. The composition of the magnesium carbonate precipitate was analysed using thermographimetric analysis (TGA combined with mass spectrometry (MS) . From the measured ratio of carbon dioxide and water, the composition of the precipitate was determined. The composition of composition of the precipitate was followed in time. The composition of the precipitate is shown in table 2. It will be clear that maintaining the aqueous solution under the conditions according to the invention for an extended time results in an increased magnesite content of the magnesium carbonate precipitate.
Table 2
Example 3
A model experiment was done by preparing an aqueous magnesium carbonate solution by contacting an aqueous brucite (MgOH2) solution with an carbon dioxide atmosphere. Sodium bicarbonate was added to the aqueous solution to provide a sodium bicarbonate concentration of 0.1 mol/1. The aqueous solution was heated to 1400C and magnesium carbonate precipitation commenced. The aqueous solution together with the obtained precipitate were maintained at the elevated temperature under carbon dioxide for 7 hours. The composition of the magnesium carbonate precipitate was analysed as described under example 2. At the start of the experiment the precipitate contained seven times more hydromagnesite than magnesite. After 7 hours no hydromagnesite could be detected in the precipitate only magnesite was found.
Claims
1. Process for preparing a magnesite-enriched magnesium carbonate precipitate, comprising the steps of:
(a) providing an aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate;
(b) heating the aqueous solution to a temperature of at least 1200C under a carbon dioxide-comprising atmosphere having a carbon dioxide partial pressure of at least 0.2 bara to obtain a magnesite-enriched magnesium carbonate precipitate
2. A process according to claim 1, wherein the aqueous solution comprises in the range of from 0.01 to 0.5 mol/1 sodium bicarbonate and/or potassium bicarbonate.
3. Process according to claim 1 and 2, wherein the aqueous solution is heated to a temperature in the range of from 120 to 1800C, preferably 125 to 160°C.
4. Process according to any one of the preceding claims, wherein the carbon dioxide partial pressure is in the range of from 0.2 to 200 bara, preferably 1 to 100 bara .
5. Process according to any one of the preceding claims, wherein following step (b) the aqueous solution is maintained at the temperature and pressure conditions of step (b) for a time period of in the range of from 1 minute to 20 hours, preferably of from 1 hour to 10 hours, more preferably 3 to 7 hours.
6. Process according to any one of the preceding claims, wherein the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate provided in step (a) is obtained by a process which includes contacting an aqueous slurry of magnesium silicate mineral with carbon dioxide to convert the magnesium silicate mineral into an aqueous solution comprising dissolved magnesium bicarbonate.
7. Process according to claim 6, wherein the at least one electrolyte is added to the aqueous solution comprising dissolved magnesium bicarbonate.
8. Process according to claim 6 or 7, wherein the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate provided in step (a) is in the form of an aqueous slurry comprising the aqueous solution comprising dissolved magnesium bicarbonate and at least one electrolyte selected from dissolved sodium bicarbonate and potassium bicarbonate and additionally magnesium silicate mineral.
9. Process according to any one of claims 6 to 8, wherein the magnesium silicate mineral is olivine or activated serpentine.
10. Use of a sodium bicarbonate and or potassium bicarbonate electrolyte to precipitate magnesite-enriched magnesium carbonate from an aqueous solution of magnesium bicarbonate .
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| EP09153985 | 2009-02-27 | ||
| EP09153985.8 | 2009-02-27 |
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Cited By (2)
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| CN104030326A (en) * | 2014-05-15 | 2014-09-10 | 宁波职业技术学院 | Method for preparing magnesium carbonate by using magnesium chloride hexammoniate |
| RU2681622C1 (en) * | 2018-06-06 | 2019-03-11 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" | Method of obtaining aqueous magnesium bicarbonate |
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| CN104030326B (en) * | 2014-05-15 | 2016-06-01 | 宁波职业技术学院 | A kind of method utilizing magnesium chloride hex-ammoniate to prepare magnesiumcarbonate |
| RU2681622C1 (en) * | 2018-06-06 | 2019-03-11 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" | Method of obtaining aqueous magnesium bicarbonate |
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