Method for producing alkaline earth metal carbonate

Abstract

This method for producing an alkaline earth metal carbonate comprises: a step (I) for preparing a slurry containing a salt of a first organic amine and an acid forming a water-soluble salt with an alkaline earth metal, an alkaline earth metal-containing substance and water; a step (II) for subjecting the slurry prepared in the step (I) to solid-liquid separation to obtain a liquid component; a step (III) for bringing the liquid component obtained in the step (II) into contact with carbon dioxide to precipitate an alkaline earth metal carbonate; and a step (IV) for separating the alkaline earth metal carbonate precipitated in the step (III) from the liquid component. In the step (III), the liquid component obtained in the step (II) is brought into contact with carbon dioxide in the presence of a second organic amine.

Description

Method for producing alkaline earth metal carbonate

[0001] The present invention relates to a method for producing alkaline earth metal carbonates.

[0002] With the growing concern about global warming in recent years, there is a need to reduce carbon dioxide emissions into the atmosphere. Studies are being conducted to reduce the amount of carbon dioxide emitted into the atmosphere by capturing and fixing the carbon dioxide generated at various facilities such as power plants, incinerators, and cement plants.

[0003] For example, Patent Document 1 discloses a concrete sludge treatment device, which discloses that calcium carbonate can be produced by eluting calcium from concrete sludge into water as calcium hydroxide and supplying carbon dioxide to the water into which the calcium has eluted. However, in the production of calcium carbonate using the device disclosed in Patent Document 1, concrete sludge is dispersed in water, but the calcium oxide contained in the concrete sludge and the calcium hydroxide produced by its hydration only dissolve in an amount of about 0.17 g per 100 mL of water at 25°C. Therefore, the method disclosed in Patent Document 1 is inefficient, and there are limitations on the amount of calcium carbonate that can be produced, such as requiring larger facilities to increase the production amount.

[0004] Patent Document 2 also discloses a method for immobilizing carbon dioxide using a salt of a weak base and a strong acid. In this method, an alkaline earth metal-containing material, such as converter slag, is contacted with an aqueous solution obtained from a salt of a weak base and a strong acid. The alkaline earth metal, such as calcium, is first converted into a salt with the strong acid, thereby increasing its solubility in water. This increases the amount of alkaline earth metal carbonate produced when the water containing the dissolved alkaline earth metal is contacted with a gas containing carbon dioxide. However, Patent Document 2 only discloses an example in which ammonium chloride is used as the salt of a weak base and a strong acid, requiring the use of an excess amount of ammonium chloride relative to the converter slag. Furthermore, the ammonium chloride produced after the carbon dioxide fixation reaction is reused in the alkaline earth metal dissolution reaction to immobilize carbon dioxide. However, the amount of calcium carbonate obtained in the second reaction is significantly lower than that in the first reaction, suggesting that ammonium chloride or the produced ammonia is lost somewhere in the reaction system.

[0005] Patent Document 3 discloses a method for producing alkaline earth metal carbonates by contacting an extractable material containing alkaline earth metals with a substoichiometric amount of an amine-containing leaching agent to produce solvated alkaline earth metals, and then contacting the resulting alkaline earth metals with carbon dioxide. This method uses a salt of a basic compound, such as ammonia or an organic amine, and an acidic compound as the amine-based leaching agent. The method also discloses a method for recovering calcium from low-grade lime using monoethanolamine hydrochloride as the organic amine leaching agent and carbon dioxide, but does not provide any examples using calcium-rich waste such as concrete sludge. The inventors' investigations revealed that when alkaline earth metal carbonates were produced using concrete sludge as calcium-rich waste, the reaction did not proceed sufficiently.

[0006] JP 2009-136770 A JP 2005-097072 A JP 2017-513806 A

[0007] SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a method for producing alkaline earth metal carbonates that allows for mass synthesis and improves the efficiency of producing high-purity alkaline earth metal carbonates.

[0008] As a result of intensive research into solving the above-mentioned problems, the inventors have found that a high-purity alkaline earth metal carbonate can be produced in a higher yield by extracting the alkaline earth metal as a water-soluble salt from a slurry containing an alkaline earth metal-containing substance, water, and a salt of an acid that forms a water-soluble salt with the alkaline earth metal with a first organic amine, filtering the extracted salt, and then contacting the filtrate with carbon dioxide in the presence of a second organic amine to precipitate the alkaline earth metal carbonate, thereby completing the present invention.

[0009] That is, the present invention provides a method for producing an alkaline earth metal carbonate, comprising: step (I) of preparing a slurry containing an alkaline earth metal-containing substance, a salt of an acid that forms a water-soluble salt with an alkaline earth metal and a first organic amine; step (II) of obtaining a liquid component by solid-liquid separation of the slurry prepared in step (I); step (III) of contacting the liquid component obtained in step (II) with carbon dioxide to precipitate an alkaline earth metal carbonate; and step (IV) of separating the alkaline earth metal carbonate precipitated in step (III) from the liquid component, wherein the method for producing an alkaline earth metal carbonate comprises contacting the liquid component obtained in step (II) with carbon dioxide in the presence of a second organic amine in step (III).

[0010] The acid that forms a water-soluble salt with an alkaline earth metal is preferably an acid that forms a salt having a solubility in water at 20°C of 10 g or more / 100 g, and more preferably at least one acid selected from hydrochloric acid, hydrobromic acid, hydroiodic acid, nitrous acid, nitric acid, formic acid, acetic acid, and propionic acid. Also, the alkaline earth metal-containing substance is preferably alkaline earth metal-containing waste.

[0011] In step (III), the contact is preferably carried out by blowing carbon dioxide into the liquid. The first organic amine is preferably an alkylamine, and the alkylamine is preferably a cyclic amine or a polyamine. The second organic amine is preferably an alkylamine, and the alkylamine is preferably a cyclic amine or a polyamine.

[0012] Furthermore, step (I) may be a step of preparing a slurry using the liquid component separated in step (IV). The present inventors have found that in this case, the yield of alkaline earth metal carbonate may decrease, and that this decrease is due to the reaction of a portion of the acid that forms a water-soluble salt with the alkaline earth metal constituting the first amine salt with the alkaline earth metal-containing substance and / or unreacted residue in step (I), resulting in separation as unreacted residue in step (II). The present inventors have also found that the decrease in the yield of alkaline earth metal carbonate can be avoided by adding, in any of steps (I) to (III), a salt of the alkaline earth metal and an acid that forms a water-soluble salt with the alkaline earth metal, or an acid that forms a water-soluble salt with the alkaline earth metal. Therefore, it is preferable to add, in any of steps (I) to (III), a salt of the alkaline earth metal and an acid that forms a water-soluble salt with the alkaline earth metal, or an acid that forms a water-soluble salt with the alkaline earth metal. The salt of an alkaline earth metal and an acid that forms a water-soluble salt with the alkaline earth metal is more preferably at least one of chloride, bromide, iodide, nitrite, nitrate, formate, acetate, and propionate of the alkaline earth metal, and more preferably at least one of hydrochloric acid, hydrobromic acid, hydroiodic acid, nitrous acid, nitric acid, formic acid, acetic acid, and propionic acid.

[0013] The second invention of the present invention is a method for producing alkaline earth metal carbonate, which comprises contacting an aqueous solution of a water-soluble alkaline earth metal salt containing an organic amine with carbon dioxide to produce an alkaline earth metal carbonate, wherein the aqueous solution contains an organic amine in an amount exceeding the stoichiometric amount relative to the water-soluble alkaline earth metal salt.

[0014] According to the method of the present invention, high-purity alkaline earth metal carbonates can be produced with improved yields.

[0015] Furthermore, the method of the present invention makes it possible to produce high-purity alkaline earth metal carbonates while reducing energy costs and carbon dioxide emissions.

[0016] The method for producing an alkaline earth metal carbonate of the present invention includes: step (I) of preparing a slurry containing a salt of an acid that forms a water-soluble salt with an alkaline earth metal and a first organic amine (hereinafter sometimes abbreviated as first amine salt), an alkaline earth metal-containing substance, and water; step (II) of performing solid-liquid separation of the slurry prepared in step (I) to obtain a liquid component; step (III) of contacting the liquid component obtained in step (II) with carbon dioxide to precipitate an alkaline earth metal carbonate; and step (IV) of separating the alkaline earth metal carbonate precipitated in step (III) from the liquid component, wherein step (III) is characterized in that the liquid component obtained in step (II) is contacted with carbon dioxide in the presence of a second organic amine.

[0017] The alkaline earth metal in the alkaline earth metal-containing substance is generally present as a hydroxide or oxide and does not have high solubility in water. Therefore, production of calcium carbonate using eluted calcium hydroxide as in Patent Document 1 is inefficient, and the production amount is limited relative to the size of the production equipment.

[0018] The alkaline earth metal in an alkaline earth metal-containing substance generally exists as a hydroxide or oxide and is not highly soluble in water, so that in order to solve this problem, Patent Documents 2 and 3 use a salt of a weak base such as ammonium chloride and a strong acid, or an organic amine leaching agent such as monoethanolamine hydrochloride, to increase the solubility of the alkaline earth metal and thereby increase the productivity of alkaline earth metal carbonate. However, by using the production method of the present invention, productivity can be further increased.

[0019] The mechanism by which the effects of the present invention are produced is thought to be as follows.

[0020] As mentioned above, alkaline earth metals in alkaline earth metal-containing materials exist as hydroxides or oxides. These are converted into alkaline earth metal hydroxides (AE(OH)) in water. ２ In step (I), a slurry containing an acid (HX) that forms a water-soluble salt with an alkaline earth metal and a first organic amine (R ３-N; R is a hydrogen atom or any organic residue, at least one of which is an organic residue) ３ The first amine salt contains a water-soluble alkaline earth metal salt (AEX). This first amine salt is acidic in water. Therefore, in step (I), a neutralization reaction occurs between the alkaline earth metal hydroxide and the first amine salt, resulting in the formation of a water-soluble alkaline earth metal salt (AEX). ２ ) and a first organic amine is produced (Equation 1).

[0021] AE (OH) ２ +2R ３ -N・HX → AEX ２ +2R ３ -N+2H ２ O (Formula 1)

[0022] Subsequently, in step (II), solid-liquid separation is performed to separate the reaction solution from the unreacted residue of the alkaline earth metal-containing substance (hereinafter also referred to as the unreacted residue). The reaction solution contains the water-soluble alkaline earth metal salt and the first organic amine.

[0023] Furthermore, in step (III), the first organic amine is contacted with carbon dioxide to form a carbonate salt of the first organic amine ((R ３ -NH ＋ ) ２ CO ３ ２－ ) is generated (Equation 2).

[0024] 2nd Round ３ -N+CO ２ +H ２ O → (R ３ -NH ＋ ) ２ CO ３ ２－ (Formula 2)

[0025] In addition, the water-soluble alkaline earth metal salt present in the system is acidic, while the carbonate of the first organic amine produced is basic. Therefore, a neutralization reaction occurs, and the alkaline earth metal carbonate (AECO ３ ) is produced and the first amine salt is simultaneously regenerated (Equation 3).

[0026] AEX ２ + (R ３ -NH ＋ )２ CO ３ ２－ →AECO ３ +2R ３ -N.HX (Equation 3) In step (III), two reactions occur: carbonation of the organic amine and neutralization of the resulting carbonate of the organic amine. Therefore, this step is considered to be the rate-determining step in the present invention. Therefore, under the conditions of step (III), the presence of a second organic amine in addition to the first organic amine as organic amines and the infusion of carbon dioxide into the reaction solution can shift the equilibrium of the reaction in equation 2 to the right, allowing the reaction to be completed quickly.

[0027] Finally, the alkaline earth metal carbonate produced in step (IV) is separated from the reaction liquid by solid-liquid separation to recover the alkaline earth metal carbonate. In addition, the liquid component obtained by solid-liquid separation contains the first amine salt regenerated in step (III), and therefore, the liquid component can be reused in step (I).

[0028] In step (I), the acid that forms a water-soluble salt with the alkaline earth metal that constitutes the first amine salt reacts with the alkaline earth metal hydroxide to form a water-soluble alkaline earth metal salt, but a portion of this salt may react with the alkaline earth metal-containing substance and / or unreacted residue and be separated as an unreacted residue in step (II). As a result, the amount of the first amine salt in the liquid component obtained in step (IV) decreases. Therefore, when the liquid component obtained in step (IV) is reused in step (I), the amount of the first amine salt decreases compared to the amount initially used in step (I). In this case, as the liquid component is reused, the first amine salt becomes insufficient relative to the alkaline earth metal hydroxide, leading to a decrease in the yield of the alkaline earth metal carbonate.

[0029] Therefore, when reusing the liquid component separated in step (IV) in step (I), a salt of an alkaline earth metal and an acid that forms a water-soluble salt with an alkaline earth metal, or an acid that forms a water-soluble salt with an alkaline earth metal, can be added in any of steps (I) to (III), thereby making it possible to avoid a decrease in the yield of alkaline earth metal carbonate during reuse.

[0030] The components of the present invention will be described in detail below.

[0031] (Salt of a first organic amine and an acid that forms a water-soluble salt with an alkaline earth metal (first amine salt)) The salt of a first organic amine and an acid that forms a water-soluble salt with an alkaline earth metal used in the present invention is a salt formed between a first organic amine and an acid that forms a water-soluble salt with an alkaline earth metal, and as described above, has the function of neutralizing with an alkaline earth metal oxide or hydroxide in the alkaline earth metal-containing substance to produce a water-soluble salt of the alkaline earth metal.

[0032] Examples of acids that form water-soluble salts with alkaline earth metals include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, hypochlorous acid, chloric acid, perchloric acid, hypobromous acid, bromic acid, perbromic acid, hypoiodous acid, iodic acid, periodic acid, nitrous acid, nitric acid, and formic acid, and organic acids such as citric acid, malic acid, acetic acid, thioacetic acid, propionic acid, and lactic acid. These acids may be used alone or in combination of two or more.

[0033] The acid that forms a water-soluble salt with an alkaline earth metal is preferably an acid that forms a salt having a solubility in water at 20°C of 10 g or more / 100 g, and more preferably hydrochloric acid, hydrobromic acid, hydroiodic acid, nitrous acid, nitric acid, formic acid, acetic acid, or propionic acid.

[0034] As the first organic amine, any commonly known organic amine can be used without limitation, but from the viewpoint of water solubility, it is preferable to use an alkylamine. Here, alkylamine refers to an amine in which the amino group is substituted with an alkyl group, and does not include aromatic amines or aromatic heterocyclic amines. Furthermore, the alkyl group of the alkylamine may be linear, branched, or cyclic. Alternatively, a polyamine having two or more amino groups per molecule may be used. Furthermore, a functional group such as a hydroxyl group may be present on the alkyl group to impart water solubility. Additionally, primary amines, secondary amines, and tertiary amines exist depending on the number of substituents, but are not particularly limited thereto.

[0035] As the first organic amine, it is preferable to use an alkylamine, and among these alkylamines, it is preferable to use a cyclic amine or a polyamine from the viewpoint of reactivity.

[0036] Examples of alkylamines include methylamine, ethylamine, propylamine, dipropylamine, butylamine, diaminopropane, triethylamine, dimethylamine, trimethylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, pyrrolidine, piperidine, piperazine, hexamethyleneimine, ethylenediamine, diethylenetriamine, triethylenetetramine, N,N'-bis(3-aminopropyl)ethylenediamine, spermine, spermidine, putrescine, cadaverine, hexamethylenediamine, tetraethylmethylenediamine, and polyethyleneamine. Among the above, from the viewpoint of the carbonation reaction of the first organic amine in step (III), primary amines and secondary amines are preferred, and cyclic amines such as morpholine, pyrrolidine, piperidine, piperazine and hexamethyleneimine or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, N,N'-bis(3-aminopropyl)ethylenediamine, spermine, spermidine, putrescine, cadaverine, hexamethylenediamine, tetraethylmethylenediamine and polyethyleneamine are more preferred, and pyrrolidine, piperidine and piperazine are particularly preferred as cyclic amines, and diethylenetriamine, triethylenetetramine, N,N'-bis(3-aminopropyl)ethylenediamine, putrescine, cadaverine, spermine and spermidine are particularly preferred as polyamines.

[0037] The salt of the first organic amine and an acid that forms a water-soluble salt with an alkaline earth metal is not particularly limited as long as it is a salt of the first amine and an acid that forms a water-soluble salt with an alkaline earth metal as described above, and examples thereof include monoethanolamine, diethanolamine, triethanolamine, morpholine, pyrrolidine, piperidine, piperazine, hexamethyleneimine, ethylenediamine, diethylenetriamine, triethylenetetramine, N,N'-bis(3-aminopropyl)ethylenediamine, methylamine, ethylamine, propylamine, dipropylamine, butylamine, diaminopropane, triethylamine, dimethylamine, and trimethylamine. , spermine, spermidine, putrescine, cadaverine, hexamethylenediamine, tetraethylmethylenediamine, polyethyleneamine, and hydrochloric acid, hydrobromic acid, hydroiodic acid, nitrous acid, nitric acid, formic acid, acetic acid, and propionic acid are preferred, and among these, from the viewpoint of reactivity, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitrous acid, nitric acid, formic acid, acetic acid, and propionic acid of pyrrolidine, piperidine, piperazine, diethylenetriamine, triethylenetetramine, N,N'-bis(3-aminopropyl)ethylenediamine, putrescine, cadaverine, spermine, and spermidine are more preferred, and from the viewpoint of ease of availability, hydrochlorides of pyrrolidine, piperidine, piperazine, diethylenetriamine, triethylenetetramine, N,N'-bis(3-aminopropyl)ethylenediamine, putrescine, cadaverine, spermine, and spermidine are particularly preferred.

[0038] (Alkaline earth metal-containing material) The alkaline earth metal-containing material used in the present invention is not particularly limited as long as it contains an alkaline earth metal, and examples thereof include alkaline earth metal oxides, hydroxides, natural minerals, and by-products and waste materials discharged during manufacturing processes. The alkaline earth metal may be contained in the form of an oxide, hydroxide, complex with silica, aluminum, or the like. Furthermore, as the alkaline earth metal, calcium, which is present in large quantities in terms of the amount of carbon dioxide fixed, is preferred, and among these, calcium oxide, calcium hydroxide, calcium (alumino) silicate, and the like are preferred. As the alkaline earth metal-containing material, it is more preferred to use waste materials that are currently landfilled due to their low usefulness.

[0039] Examples of waste materials containing calcium as an alkaline earth metal include coal ash, biomass ash, incineration ash, paper sludge ash, concrete sludge, crushed concrete, crushed cement, steel slag, soda-lime glass, and potassium-lime glass.

[0040] (Second organic amine) The second organic amine used in the present invention may be any of the organic amines exemplified as the first organic amine that forms the first amine salt. The second organic amine may be the same as or different from the first organic amine.

[0041] (Carbon dioxide) The carbon dioxide used in the present invention is preferably a gas. It may be 100% pure carbon dioxide gas, or may be carbon dioxide contained in air, the exhaled breath of living organisms, exhaust gases generated when burning waste materials such as food waste, wood chips, waste plastics, and organic sludge, or exhaust gases generated from thermal power plants, steel plants, cement plants, and the like. The carbon dioxide content cannot be generalized, and the carbon dioxide-containing gas to which the present invention is applied is not particularly limited as long as it contains carbon dioxide gas. From the viewpoint of reaction efficiency, the carbon dioxide content is preferably 1% or more, more preferably 5% or more, and most preferably 10% or more. Carbon dioxide-containing exhaust gases emitted from various manufacturing facilities are also included.

[0042] The steps (I) to (IV) of the present invention will be described in detail below.

[0043] [Step (I)] Step (I) is a step of preparing a slurry containing a first amine salt, an alkaline earth metal-containing substance, and water. In this step, an alkaline earth metal oxide or hydroxide in the alkaline earth metal-containing substance is neutralized with the first amine salt to produce a water-soluble alkaline earth metal salt and a first organic amine. Here, the water-soluble alkaline earth metal salt produced is a salt of the alkaline earth metal contained in the alkaline earth metal-containing substance and an acid that forms a water-soluble salt with the alkaline earth metal that constitutes the first amine salt.

[0044] The slurry containing the first amine salt, the alkaline earth metal-containing substance, and water may be prepared by adding and mixing the first amine salt, the alkaline earth metal-containing substance, and water in any order. The first amine salt may be formed by adding and mixing a first organic amine and an acid (a salt-forming component). The prepared slurry contains the water-soluble alkaline earth metal salt, the first organic amine, unreacted first amine salt, and unreacted residue.

[0045] Although the slurry concentration is not particularly limited, the mixing ratio of the alkaline earth metal-containing material to water (alkaline earth metal-containing material:water) is preferably in the range of 1:1.0 to 50.0 by mass, more preferably 1:2.0 to 30.0, and even more preferably 1:3.0 to 20.0 by mass. This range allows the alkaline earth metal-containing material and the first amine salt to react sufficiently.

[0046] The addition ratio of the alkaline earth metal-containing material to the first amine salt may be appropriately determined depending on the amount of alkaline earth metal contained in the alkaline earth metal-containing material. For example, when using a calcium-rich calcium-containing material such as concrete sludge, the first amine salt is preferably in the range of 5 to 500 mol%, more preferably 10 to 400 mol%, and even more preferably 20 to 300 mol%, relative to 100 mol% of calcium contained in the calcium-containing material. By setting the ratio in such a range, the alkaline earth metal-containing material and the first amine salt can be reacted well.

[0047] The temperature during the preparation of the slurry is not particularly limited, and the slurry may be prepared at room temperature or by heating.

[0048] The time for preparing the slurry is not particularly limited, but from the viewpoint of reaction efficiency, it is preferably from 1 minute to 24 hours, more preferably from 2 minutes to 6 hours, and most preferably from 5 minutes to 1 hour.

[0049] The preparation of the slurry is preferably carried out with stirring, and any stirring method can be used as long as it can uniformly mix the slurry to be treated, and a general stirrer can be used.

[0050] Furthermore, in order to make the second organic amine present in step (III), a second organic amine may be added to the slurry in step (I). The addition of the second organic amine may be carried out at any time during step (I). From the viewpoint of reaction efficiency, the amount of the second organic amine added is preferably such that the total amount of amino groups in the second organic amine is 10 to 2000%, more preferably 30 to 1500%, and most preferably 50 to 500%, relative to 100% of the total amount of amino groups in the first organic amine salt.

[0051] [Step (II)] Step (II) is a step of obtaining a liquid component by solid-liquid separation of the slurry prepared in step (I). The liquid component contains a water-soluble alkaline earth metal salt and a first organic amine dissolved in water. If a second organic amine is added in step (I), the liquid component also contains the second organic amine. Unreacted residue is separated as a solid component.

[0052] The method for solid-liquid separation of the slurry prepared in step (I) can be any known method such as filtration, centrifugation, sedimentation, etc., without limitation. From the viewpoint of obtaining a liquid component with few impurities, solid-liquid separation by filtration is preferred.

[0053] Any filtration method can be used, including, for example, methods using a filter press, a belt filter, a drum filter, etc. The filtration temperature can also be set to any temperature, since the dissolution amount of the water-soluble alkaline earth metal salt is sufficiently high even at room temperature. The liquid used for washing can be industrial water, tap water, distilled water, ion-exchanged water, etc., and is preferably used in an amount equal to or greater than the amount of alkaline earth metal-containing waste, and more preferably equal to or greater than two times the amount. For the reasons mentioned above, the temperature of the washing water can also be set to any temperature.

[0054] [Step (III)] Step (III) is a step in which the liquid component obtained in step (II) is contacted with carbon dioxide to precipitate an alkaline earth metal carbonate. In this step, the liquid component obtained in step (II) is contacted with carbon dioxide in the presence of a second organic amine. The presence of the second organic amine when the liquid component obtained in step (II) is contacted with carbon dioxide promotes the carbonation of the organic amine of formula 2 as described above, and as a result, the production of an alkaline earth metal carbonate can also be promoted.

[0055] The liquid component obtained in step (II) in the presence of the second organic amine contains a water-soluble alkaline earth metal salt and organic amines (first organic amine and second organic amine). At this time, the liquid component contains the first organic amine so that there are two amino groups derived from the first organic amine per molecule of the alkaline earth metal, as shown in the reaction (Equation 1) in step (I), and also contains the second organic amine. Therefore, the amount of organic amine, which is the total of the first organic amine and the second organic amine, exceeds the stoichiometric amount relative to the water-soluble alkaline earth metal in the carbonation reaction of the organic amine in step (III) (Equation 2).

[0056] That is, the total number of amino groups in the organic amines derived from the first organic amine and the second organic amine before contact with carbon dioxide is more than two per molecule of the water-soluble alkaline earth metal.

[0057] The second organic amine may be added to the slurry in step (I) as described above, or may be added to the liquid component obtained in step (II) in this step. Furthermore, the second organic amine may be added in this step at any time before contact with carbon dioxide. The amount of the second organic amine added is the same as when added in step (I).

[0058] In this step, the contact with carbon dioxide can be carried out by bringing the carbon dioxide into contact at the liquid surface or by blowing the carbon dioxide directly into the liquid. From the viewpoint of reaction efficiency, however, it is preferable to blow the carbon dioxide directly into the obtained liquid component.

[0059] The temperature at which carbon dioxide is brought into contact is not particularly limited, and the contact may be carried out at room temperature or by heating using an apparatus.

[0060] The time for contacting with carbon dioxide varies depending on the carbon dioxide concentration in the carbon dioxide-containing gas and is not particularly limited, but from the viewpoint of carbonation reaction efficiency, it is preferably from 1 minute to 24 hours, more preferably from 2 minutes to 6 hours, and most preferably from 5 minutes to 2 hours.

[0061] In this step, it is preferable to carry out the step with stirring from the viewpoint of uniformly dispersing carbon dioxide in the liquid component. Since the liquid component becomes a slurry due to the precipitation of alkaline earth metal carbonate, any stirring method can be used as long as it can uniformly mix the slurry, and a general stirrer can be used.

[0062] [Step (IV)] Step (IV) is a step of separating the alkaline earth metal carbonate precipitated in step (III) from the liquid component.

[0063] The alkaline earth metal carbonate can be separated from the liquid component by any known method, such as filtration, centrifugation, sedimentation, etc., without limitation. From the viewpoint of obtaining a liquid component with few impurities, solid-liquid separation by filtration is preferred.

[0064] The filtration method can be the same as that described in step (II). The filtration temperature can be any temperature because alkaline earth metal carbonates have low solubility in water regardless of the temperature. The liquid used for washing can be industrial water, tap water, distilled water, ion-exchanged water, or the like, and is preferably used in an amount equal to or greater than the amount of alkaline earth metal-containing waste, and more preferably equal to or greater than the amount of alkaline earth metal-containing waste. For the reasons mentioned above, the temperature of the washing water can also be any temperature.

[0065] In addition, since the liquid component separated from the alkaline earth metal carbonate in step (IV) contains the regenerated first amine salt in a dissolved state, the liquid component separated in this step can be returned to step (I) and reused as at least a part of the first amine salt and water used in step (I).Furthermore, since the second organic amine is also contained, by returning the liquid component to step (I), it can be reused as at least a part of the first amine salt and water, and also as at least a part of the second organic amine to be present in step (III).

[0066] [Reuse of Liquid Component] As described above, the liquid component obtained in step (IV) can be reused by returning it to step (I). The amount to be reused may be a portion or the entire amount, but from the viewpoint of cost, it is preferable to reuse the entire amount. When the entire amount of the liquid component obtained in step (IV) is to be reused, the liquid component obtained in step (IV) may be mixed with an alkaline earth metal-containing substance to prepare a slurry containing a salt of an acid that forms a water-soluble salt with the alkaline earth metal and a first organic amine, the alkaline earth metal-containing substance, and water.

[0067] In addition, an acid that forms a water-soluble salt with an alkaline earth metal may be adsorbed as an anion in the unreacted residue obtained in step (II). If an acid that forms a water-soluble salt with an alkaline earth metal is adsorbed in the unreacted residue, the amount of water-soluble alkaline earth metal eluted from the alkaline earth metal-containing substance will decrease when the liquid component obtained in step (IV) is reused. Therefore, when the entire amount of the liquid component obtained in step (IV) is utilized, it is preferable to add a salt of an alkaline earth metal and an acid that forms a water-soluble salt with an alkaline earth metal to the liquid component.

[0068] The amount of the salt of an alkaline earth metal with an acid that forms a water-soluble salt with an alkaline earth metal, or the amount of the acid that forms a water-soluble salt with an alkaline earth metal, added should be approximately the same as the amount of the acid that forms a water-soluble salt with an alkaline earth metal adsorbed in the unreacted residue, and although the amount cannot be generalized, it is preferably 0.01 to 5.0 mol %, more preferably 0.05 to 2.5 mol %, and even more preferably 0.1 to 2.0 mol %, relative to 100 mol % of the acid that forms a water-soluble salt with an alkaline earth metal contained in the first amine salt. By adding such an amount, alkaline earth metal carbonate can be obtained in good yield even when the liquid components are reused.

[0069] Examples and comparative examples are shown below, but the technical scope of the present invention is not limited to these.

[0070] Example 1 First, the carbonation reaction in step (III) was evaluated. Assuming a liquid component resulting from a reaction between a calcium-containing substance as the alkaline earth metal-containing substance and a hydrochloride salt of a first organic amine as the first amine salt, a carbonation reaction was carried out using calcium chloride as the water-soluble alkaline earth metal salt to be produced and predetermined amounts of the first organic amine and the second organic amine as the organic amines.

[0071] 20 mmol and 10 mmol of 2-ethanolamine, respectively, were weighed into a beaker as the first organic amine produced in step (I) and the second organic amine present in step (III), totaling 30 mmol (1.85 g). Subsequently, a solution was prepared using 50 mL of water, and 10 mmol (1.10 g) of calcium chloride, which is assumed to be produced when calcium hydroxide in the alkaline earth metal-containing material reacts with the first organic amine hydrochloride in step (I), was added and completely dissolved. 100% carbon dioxide gas was blown into the resulting solution at 0.1 L / min with stirring for 30 minutes, and then the reaction was carried out with stirring for another 30 minutes. Thereafter, the reaction solution was subjected to solid-liquid separation by filtration, and the solids were washed with 20 mL of water. The resulting white solid was dried at 105°C for 3 hours and then analyzed using an X-ray diffractometer (Burker, D8 ADVANCE) with a measurement range of 2θ 5-65°, a step width of 0.02°, and a scan speed of 0.25° / min. The solid was found to be calcium carbonate composed of calcite, aragonite, and vaterite. Furthermore, composition analysis was performed using a fluorescent X-ray analyzer (Rigaku, ZSX Primus IV) and the fundamental parameter method, revealing a purity of 98%. The resulting calcium carbonate was weighed to be 7.8 mmol (0.78 g, yield 78%).

[0072] Comparative Example 1 The same operation as in Example 1 was carried out except that 20 mmol (1.24 g) of 2-ethanolamine was used as the first organic amine. After completion of the reaction, 4.0 mmol (0.4 g, yield 40%) of calcium carbonate was obtained.

[0073] From the above results, it was found that the carbonation reaction is significantly accelerated by the presence of the second organic amine in step (III) in addition to the first organic amine produced in step (I).

[0074] Comparative Examples 2 and 3 Comparative Example 2 is an example in which ammonia was used as a substitute compound for the first and second organic amines, but calcium carbonate was only obtained in a low yield. Comparative Example 3 is an example in which no organic amine was used, but the production of calcium carbonate was not confirmed.

[0075] Examples 2 to 14 Calcium carbonate was synthesized in the same manner as in Example 1, except that the type and amount of amine and the water-soluble calcium salt were changed as shown in Table 1.

[0076] In Examples 2 to 10, various types and amounts of the first organic amine and the second organic amine were used in combination with calcium chloride. In all cases, it was found that the carbonation reaction proceeded quickly and in high yield.

[0077] Furthermore, in Examples 11 to 14, the water-soluble calcium salt was changed, but calcium carbonate could be synthesized in good yield. The above results suggest that the carbonation reaction proceeds through the reaction of various water-soluble alkaline earth metal salts with organic amines. Therefore, the acid for the organic amine in step (I) may be any acid that forms a water-soluble salt with an alkaline earth metal.

[0078]

[0079] From the above results, it was found that the yield of calcium carbonate could be significantly increased by adding a second organic amine in step (III).

[0080] Example 15 A study was carried out on reacting an alkaline earth metal salt-containing substance with a first amine salt to produce carbonation.

[0081] Calcium hydroxide was used as the alkaline earth metal-containing substance, and a stoichiometric amount of a first amine salt was used relative to the amount of calcium hydroxide used. 10 mmol (1.77 g) of piperazine dihydrochloride monohydrate as the first amine salt and 10 mmol (0.88 g) of piperazine as the second organic amine were weighed into a beaker and completely dissolved in 50 mL of water. 10 mmol (0.74 g) of calcium hydroxide was added to the solution as the alkaline earth metal-containing substance. After stirring for 10 minutes at room temperature, filtration was performed, and the solid unreacted residue was washed with 20 mL of water. The unreacted residue was dried at 105 ° C for 3 hours and used to calculate the amount of calcium hydroxide eluted from the alkaline earth metal-containing substance.

[0082] The resulting filtrate was reacted by blowing in 100% carbon dioxide gas at 0.1 L / min while stirring for 30 minutes. The reaction was then continued for another 30 minutes with stirring. After 30 minutes of stirring, the reaction solution was subjected to solid-liquid separation by filtration, and the solid was washed with 20 mL of water. After washing, the solid was dried at 105°C for 3 hours and analyzed in the same manner as in Example 1. The results are shown in Table 2.

[0083] Almost all of the calcium hydroxide was dissolved by piperazine dihydrochloride and converted to calcium chloride. The dissolved calcium was then carbonated to obtain 9.30 mmol (0.93 g) of calcium carbonate with a purity of 97%, with a yield of 96% based on the amount of calcium hydroxide eluted from the alkaline earth metal-containing material (9.31 mmol (0.69 g)).

[0084] The amount of calcium hydroxide eluted from the alkaline earth metal-containing substance was calculated as the amount of calcium hydroxide eluted from the alkaline earth metal-containing substance, which was obtained by subtracting the amount of unreacted residue dried at 105°C for 3 hours from the amount of alkaline earth metal-containing substance used.

[0085] Comparative Example 4 The same procedure as in Example 15 was carried out, except that the second organic amine was not used. The results are shown in Table 2. 5.10 mmol (0.51 g) of calcium carbonate was obtained in a yield of 55% based on the amount of calcium hydroxide eluted from the alkaline earth metal-containing substance, 9.31 mmol (0.69 g).

[0086] Comparative Example 5 The same procedure as in Example 15 was carried out, except that 20 mmol (3.54 g) of piperazine dihydrochloride monohydrate was used as the first amine salt and no second organic amine was used. The results are shown in Table 2. 2.40 mmol (0.24 g) of calcium carbonate was obtained in a yield of 25% based on the amount of calcium hydroxide eluted from the alkaline earth metal-containing substance, 9.45 mmol (0.70 g).

[0087] In Example 15, a stoichiometric amount of the first amine salt relative to calcium hydroxide was used, but the yield of calcium carbonate obtained was significantly increased compared to Comparative Example 4, in which no second organic amine was used, although the amount of calcium hydroxide eluted was the same. This shows that the presence of a second organic amine in step (III) makes it possible to obtain alkaline earth metal carbonate with good efficiency.

[0088] Comparative Example 5 is an example in which the first amine salt was used in an amount twice the stoichiometric amount relative to the amount of calcium hydroxide used, and no second organic amine was used. All of the calcium hydroxide was converted to calcium chloride and eluted, but the yield of calcium carbonate was even lower than in Comparative Example 4. It can be seen that even when the first amine salt is present in excess instead of the second organic amine, alkaline earth metal carbonate cannot be obtained with high efficiency.

[0089] From these facts, it can be seen that the presence of a second amine in step (III) is essential for the reaction to proceed efficiently.

[0090] Example 16: 10 mmol (1.77 g) of piperazine dihydrochloride monohydrate as the first amine salt and 10 mmol (0.88 g) of piperazine as the second organic amine were weighed into a beaker and completely dissolved in 50 mL of water. 5 g of powdered concrete sludge dried at 105°C for 24 hours as the alkaline earth metal-containing substance was added to the solution. After stirring at room temperature for 10 minutes, the solution was filtered, and the solid unreacted residue was washed with 20 mL of water. The unreacted residue was dried at 105°C for 3 hours and used to calculate the amount of calcium hydroxide eluted from the alkaline earth metal-containing substance.

[0091] The reaction was carried out by blowing 100% carbon dioxide gas into the obtained filtrate at 0.1 L / min while stirring for 30 minutes. The reaction was then carried out with stirring for another 30 minutes. After 30 minutes of stirring, the reaction solution was subjected to solid-liquid separation by filtration, and the solid was washed with 20 mL of water. After washing, the solid was dried at 105°C for 3 hours and analyzed in the same manner as in Example 1. The results are shown in Table 2. 9.35 mmol (0.93 g) of calcium carbonate with a purity of 97% was obtained in a yield of 99% based on the amount of calcium hydroxide eluted from the alkaline earth metal-containing material, 9.45 mmol (0.70 g).

[0092] Comparative Example 6 The same procedure as in Example 15 was carried out, except that the second organic amine was not used. After completion of the reaction, 0.50 g (5.00 mmol) of calcium carbonate was obtained in a yield of 53% based on the calcium hydroxide eluted from the alkaline earth metal-containing substance.

[0093] Although the amounts of calcium hydroxide eluted from the concrete sludge in step (I) were the same, there was a large difference in the amount of calcium carbonate finally obtained. From the above results, it can be seen that the presence of the second organic amine in step (III) enabled good reactivity and reaction efficiency to be achieved.

[0094] Examples 17 to 21 In Examples 17 to 21, the same procedure as in Example 16 was carried out, except that the alkaline earth metal-containing substance, the first amine salt, and the second organic amine were changed as shown in Table 2. The results are shown in Table 2. In all of Examples 17 to 21, the yield based on the calcium hydroxide eluted from the alkaline earth metal-containing substance was good, and the presence of the second amine allowed the reaction to proceed well.

[0095]

[0096] [Example 22] 10 mmol (1.77 g) of piperazine dihydrochloride monohydrate as a first amine salt and 10 mmol (0.88 g) of piperazine as a second organic amine were weighed into a beaker and completely dissolved in 50 mL of water. 5 g of concrete sludge as an alkaline earth metal-containing substance was then added to the solution. After stirring at room temperature for 5 minutes, the solution was filtered, and the unreacted solid residue was washed away with 20 mL of water to obtain a filtrate.

[0097] The resulting filtrate was reacted by blowing in 100% carbon dioxide gas at 0.1 L / min while stirring for 30 minutes. The reaction was then continued with stirring at 100°C for 3 hours. Approximately 30 mL of water was evaporated during this process. After stirring for 3 hours, the reaction solution was subjected to solid-liquid separation by filtration, and the solid was washed with 10 mL of water. The filtrate and washings were collected as liquid components. After washing, the solid was dried at 105°C for 3 hours. The resulting white solid was then dried at 105°C for 3 hours and analyzed using an X-ray diffractometer (Burker, D8 ADVANCE) with a measurement range of 2θ 5-65 deg, a step width of 0.02 deg, and a scan speed of 0.25 deg / min. The solid was found to be calcium carbonate composed of calcite, aragonite, and vaterite. Furthermore, a composition analysis was performed using a fluorescent X-ray analyzer (Rigaku Corporation, ZSX Primus IV) and the fundamental parameter method, which revealed a purity of 98%. The obtained calcium carbonate was weighed to be 9.35 mmol (0.935 g). Furthermore, the recovered 4.34 g of concrete sludge contained approximately 0.28 wt% (0.34 mmol) of chlorine atoms, suggesting that chlorine was adsorbed into the concrete sludge.

[0098] In addition, 5 g of concrete sludge was added again to the liquid component obtained after solid-liquid separation of the reaction liquid, and the following series of operations was performed a total of four times. - After stirring for 5 minutes at room temperature, filtering was performed, and the unreacted residue (solid content) was washed with 20 mL of water to obtain a filtrate. - 100% carbon dioxide gas was blown into the obtained filtrate at 0.1 L / min while stirring for 30 minutes, and then the mixture was stirred at 100°C for 3 hours to allow the reaction to proceed. - After stirring for 3 hours, the reaction liquid was subjected to solid-liquid separation by filtration, and the solid content was washed with 10 mL of water.

[0099] The results are shown in Table 3, and it was observed that the yield of calcium carbonate gradually decreased with repeated use of the liquid components.

[0100] [Example 23] Calcium carbonate was obtained by repeating the procedure of Example 22, except that concrete sludge was added again to the liquid component obtained after solid-liquid separation of the reaction liquid, and 0.17 mmol (19 mg) of anhydrous calcium chloride was added to the resulting slurry. The results are shown in Table 3.

[0101] Example 24 The same procedure as in Example 23 was carried out, except that 0.34 mmol (1.4 mL) of a 0.25 M aqueous hydrochloric acid solution was added instead of anhydrous calcium chloride. The results are shown in Table 3.

[0102] The results of Examples 23 and 24 show that when a salt of an alkaline earth metal and an acid that forms a water-soluble salt with an alkaline earth metal, or an acid that forms a water-soluble salt with an alkaline earth metal, was added to the liquid component, the rate of decrease in calcium carbonate when the liquid component was repeatedly reused ((mass of calcium carbonate product in the previous repetition−mass of calcium carbonate product in the current repetition) / mass of calcium carbonate product in the previous repetition×100) could be suppressed compared to Example 22 in which no addition was made.

[0103]

Claims

1. A method for producing alkaline earth metal carbonate, comprising: step (I) of preparing a slurry containing an alkaline earth metal-containing substance, a salt of an acid that forms a water-soluble salt with an alkaline earth metal and a first organic amine; step (II) of performing solid-liquid separation of the slurry prepared in step (I) to obtain a liquid component; step (III) of contacting the liquid component obtained in step (II) with carbon dioxide to precipitate an alkaline earth metal carbonate; and step (IV) of separating the alkaline earth metal carbonate precipitated in step (III) from the liquid component, wherein in step (III), the liquid component obtained in step (II) is contacted with carbon dioxide in the presence of a second organic amine.

2. The method for producing alkaline earth metal carbonates according to claim 1, wherein the acid which forms a water-soluble salt with an alkaline earth metal is an acid which forms a salt having a solubility in water at 20°C of 10 g or more / 100 g.

3. The method for producing alkaline earth metal carbonates according to claim 2, wherein the acid which forms a water-soluble salt with the alkaline earth metal is at least one acid selected from the group consisting of hydrochloric acid, hydrobromic acid, hydroiodic acid, nitrous acid, nitric acid, formic acid, acetic acid and propionic acid.

4. The method for producing alkaline earth metal carbonate according to claim 1, wherein the alkaline earth metal-containing material is an alkaline earth metal-containing waste.

5. The method for producing alkaline earth metal carbonate according to claim 1, wherein in step (III), carbon dioxide is contacted by blowing it into the liquid.

6. The method for producing alkaline earth metal carbonate according to claim 1, wherein the first organic amine is an alkylamine.

7. The method for producing alkaline earth metal carbonates according to claim 6, wherein the alkylamine is a cyclic amine or a polyamine.

8. The method for producing alkaline earth metal carbonate according to claim 1, wherein the second organic amine is an alkylamine.

9. The method for producing alkaline earth metal carbonate according to claim 8, wherein the alkylamine is a cyclic amine or a polyamine.

10. A method for producing alkaline earth metal carbonate according to claim 1, characterized in that step (I) is a step of preparing a slurry using the liquid component separated in step (IV).

11. The method for producing alkaline earth metal carbonate according to claim 10, wherein a salt of an alkaline earth metal and an acid that forms a water-soluble salt with an alkaline earth metal, or an acid that forms a water-soluble salt with an alkaline earth metal, is added in any one of steps (I) to (III).

12. The method for producing alkaline earth metal carbonate according to claim 11, wherein the salt of an alkaline earth metal with an acid that forms a water-soluble salt with the alkaline earth metal is at least one of the chloride, bromide, iodide, nitrite, nitrate, formate, acetate, and propionate of the alkaline earth metal.

13. The method for producing alkaline earth metal carbonate according to claim 11, wherein the acid that forms a water-soluble salt with the alkaline earth metal is at least one of hydrochloric acid, hydrobromic acid, hydroiodic acid, nitrous acid, nitric acid, formic acid, acetic acid, and propionic acid.

14. A method for producing alkaline earth metal carbonate, comprising contacting an aqueous solution of a water-soluble alkaline earth metal salt containing an organic amine with carbon dioxide to produce alkaline earth metal carbonate, wherein the aqueous solution contains an organic amine in an amount exceeding the stoichiometric amount relative to the water-soluble alkaline earth metal salt.

Images