Method for continuously producing carbon dioxide-capturing composite particles

Abstract

The present invention relates to a method for continuously producing carbon dioxide-capturing composite particles, the method, in a process for using seawater as usable water, i.e., in a process for turning seawater into usable water, fixing carbon dioxide through the mineralization of ions in the seawater which is supply water or discharge water in the process, thereby contributing to carbon neutrality.

Description

Continuous manufacturing method of carbon dioxide capture composite particles

[0001] The present invention relates to a continuous manufacturing method of carbon dioxide capture composite particles that contribute to carbon neutrality by fixing carbon dioxide through mineralization of ions in seawater, which is the feed water or discharge water of a process using seawater as water, i.e., a seawater water conversion process.

[0002] Modern society's consumption of petrochemicals leads to massive carbon emissions into the atmosphere, and the resulting carbon dioxide is contributing to a global climate crisis. To address this, efforts to reduce petrochemical production and consumption, along with advancements in technologies to effectively capture the carbon dioxide produced, are essential.

[0003] Conventionally, monoethanolamine (MEA) aqueous solutions are used for carbon dioxide adsorption, but this has the disadvantages of equipment corrosion, toxic vapor generation, and the need for high temperatures to reform the adsorbed carbon dioxide. Furthermore, attempts have been made to adsorb carbon dioxide gas using inorganic materials such as zeolites, adsorbents containing polyethyleneimine (PEI), porous carbon, and metal organic frameworks (MOFs). However, these are greatly affected by moisture and temperature in the air, and high pressure or high temperature is required for efficient adsorption. Among the existing known adsorbents, MOF / GO-U3 is known to have the highest carbon dioxide adsorption efficiency, at around 186 mg / g.

[0004] However, technology for adsorbing and removing carbon dioxide from water has not yet been developed. Furthermore, indiscriminately discharged industrial wastewater and concentrated seawater treatment wastewater contain high concentrations of carbonate ions and carbon dioxide, but there is no simple and effective method for removing them.

[0005] In order to achieve the above object, the present invention aims to provide a continuous manufacturing method of carbon dioxide capture composite particles that is safer and more convenient to use than a process using a conventionally known carbon dioxide absorbent, and can be performed continuously within a process.

[0006] In addition, the present invention aims to provide a continuous manufacturing method of carbon dioxide capture composite particles capable of continuously capturing and discharging carbon dioxide in particle form by simply adding a simple process without excessive cost burden in the existing seawater water purification process.

[0007] In order to achieve the above purpose, the inventors of the present invention have continuously conducted research to develop a method for continuously adsorbing and removing carbon dioxide in water using seawater, and as a result, they have discovered that when polyamidoamine particles of a specific structure are brought into contact with seawater for a specific residence time in a process using seawater as water, carbon dioxide and carbonate ions in seawater can be continuously removed without excessive cost increase even in a very simple manner, thereby completing the present invention.

[0008] The present invention provides a continuous manufacturing method of carbon dioxide capture composite particles, comprising a process using seawater as a feed water, and a step of contacting feed water or discharge water of the process with polyamidoamine particles.

[0009] In one embodiment, the step of contacting the feed water or the discharge water with the polyamidoamine particles may include (a) contacting the feed water or the discharge water with the polyamidoamine particles; and (b) forming calcium carbonate particles from calcium ions and carbonate ions in the feed water or the discharge water on the surface of the polyamidoamine particles.

[0010] In one embodiment, the feed water or the discharge water may include calcium ions and magnesium ions.

[0011] In one embodiment, the feed water or effluent may contain calcium ions at a concentration of 0.1 g / L or greater.

[0012] According to one embodiment, the polyamidoamine particles may be crosslinked particles prepared from a polyfunctional amine monomer having at least two amine groups and a polyfunctional acrylamide monomer having at least two acrylic groups.

[0013] According to one embodiment, the polyamidoamine particles may be prepared by reacting a polyfunctional amine monomer and a polyfunctional acrylamide monomer in a molar ratio of 1:0.8 to 2.5.

[0014] In one embodiment, the multifunctional amine monomer may contain two primary amine groups, and the multifunctional acrylamide monomer may contain two acrylic groups.

[0015] In one embodiment, the contact may be any one of the following methods:

[0016] (i) Filtration of feed water or effluent water in a column filled with polyamidoamine particles;

[0017] (ii) Dispersion of polyamidoamine particles in feed water or effluent;

[0018] (iii) Suspension of polyamidoamine particles on the surface of the supply water or effluent water;

[0019] In one embodiment, the column may be filled with polyamidoamine particles at a density of 1 to 50 g / ㎥ (L).

[0020] In one embodiment, the contact may satisfy a weight hourly space velocity (WHSV) in the range of 5 to 10,000 / hr depending on the amount of polyamidoamine particles.

[0021] In one embodiment, the polyamidoamine particles may have a particle size of 10 to 1000 μm.

[0022] According to one embodiment, in the step of contacting the supply water or the discharge water with the polyamidoamine particles, a step of injecting carbon dioxide into the supply water or the discharge water may be further performed.

[0023] According to one embodiment, a polyamidoamine-calcium carbonate composite particle may be formed by the process (b) above, in which calcium carbonate particles are formed on the surface of the polyamidoamine particles.

[0024] According to one embodiment, after step (b), a step of removing calcium carbonate from the surface using an ultrasonic grinder may be further performed.

[0025] According to one embodiment, the amount of carbon dioxide removed per 24 hours (M) for 100 g of polyamidoamine particles CO2-24h ) can be more than 1g / 24h.

[0026] In one embodiment, the process may include one or more selected from the group consisting of a seawater desalination process, an industrial cooling water process, an aquaculture process, and an agricultural irrigation process.

[0027] The present invention can provide an automobile reinforcing material including carbon dioxide capturing composite particles manufactured according to the continuous manufacturing method of carbon dioxide capturing composite particles described above.

[0028] The present invention can provide a construction cement including carbon dioxide capturing composite particles manufactured according to the continuous manufacturing method of carbon dioxide capturing composite particles described above.

[0029] The continuous manufacturing method for carbon dioxide capture composite particles according to one embodiment of the present invention has the advantage of being easily applicable to processes utilizing seawater, enabling the continuous reuse of carbonate ions and carbon dioxide within seawater. Utilizing the continuous manufacturing method for carbon dioxide capture composite particles allows for outstanding carbon dioxide reduction effects to be achieved with the addition of simple processes and equipment, without excessive cost burdens, compared to conventional seawater treatment processes.

[0030] Figure 1 is a schematic diagram roughly showing the process sequence of a continuous manufacturing method of carbon dioxide capture composite particles according to one embodiment.

[0031] Figure 2 is a schematic diagram schematically showing a process device of a continuous manufacturing method of carbon dioxide capture composite particles according to one embodiment.

[0032] Figure 3 is a schematic diagram of a reactor of a carbon dioxide capture composite particle according to one embodiment.

[0033] Figure 4 is an SEM analysis image of polyamidoamine particles manufactured in Manufacturing Example 1.

[0034] Figure 5 is an SEM analysis image of the surface of a carbon dioxide capture composite particle in which calcium carbonate minerals are formed on the surface of polyamidoamine particles manufactured in Manufacturing Examples 2 to 5.

[0035] Figure 6 is a TGA analysis graph of carbon dioxide capture composite particles obtained from the filter over time after the mineralization reaction was completed in Example 1.

[0036] Figure 7 is an XRD analysis graph of carbon dioxide capture composite particles obtained from the filter over time after the mineralization reaction was completed in Example 1.

[0037] The present invention will be described in more detail below. However, the following specific examples or examples are merely references for explaining the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

[0038] Additionally, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein is for the purpose of describing specific embodiments only and is not intended to be limiting.

[0039] Additionally, the singular forms used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly dictates otherwise.

[0040] In addition, units used in this specification without special mention are based on weight, and for example, units of % or ratio mean weight% or weight ratio, and weight% means the weight% that any one component of the entire composition occupies in the composition unless otherwise defined.

[0041] Additionally, the numerical ranges used herein include lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes. Unless otherwise specifically defined in the specification of the present invention, values ​​outside the numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0042] The term "includes" in this specification is an open-ended description equivalent to expressions such as "comprises," "contains," "has," or "characterizes," and does not exclude additional elements, materials, or processes not listed.

[0043] Additionally, the term "substantially" in this specification means that other elements, materials or processes not listed together with the specified elements, materials or processes may be present in an amount or degree that does not significantly affect at least one basic and novel technical idea of ​​the invention to an unacceptable degree.

[0044] In addition, the term water (available for use) in this specification means water for use in fire prevention, irrigation, industry, power generation, drinking, etc., and includes, but is not limited to, industrial water such as agricultural water, fishery water, and industrial water, environmental water, swimming water, and domestic water.

[0045] In addition, the term "process using seawater as water" in this specification means a comprehensive process using seawater (seawater) as water as defined above, and examples thereof include, but are not limited to, a seawater desalination process, an industrial cooling water process, an aquaculture process, or an agricultural irrigation process.

[0046] Hereinafter, one aspect of the continuous manufacturing method of the carbon dioxide capture composite particles of the present invention will be described in more detail.

[0047] The present invention provides a continuous manufacturing method of carbon dioxide capture composite particles, including a process using seawater as a feed water, and a step of contacting feed water or discharge water of the process with polyamidoamine particles (hereinafter referred to as a contact step).

[0048] In one embodiment, the process includes all processes for using seawater supplied from the ocean as industrial water, such as agricultural water, fishing water, and industrial water, environmental water, swimming water, and domestic water, and may include, for example, one or more selected from the group consisting of a seawater desalination process, an industrial cooling water process, an aquaculture process, and an agricultural irrigation process.

[0049] According to one embodiment, the seawater may be one or a mixture of two or more selected from the group consisting of normal seawater, seawater desalination concentrate, brine, bittern, etc. In order to replace the seawater for testing, artificial seawater, which is an aqueous solution in which calcium ions are dissolved, may be used, and specifically, the seawater may be Ca2+ Concentration of 0.04 g / L-water or more, CO3 2- The concentration may be greater than 0.02 g / L-water.

[0050] According to one embodiment, the continuous manufacturing method of the carbon dioxide capture composite particles may include a step of contacting the feed water of the process with the polyamidoamine particles. In this case, the contact step may be performed prior to the process, as in case ① of FIG. 1.

[0051] According to one embodiment, the continuous manufacturing method of the carbon dioxide capture composite particles may include a step of contacting the feed water of the process with the polyamidoamine particles. In this case, the contact step may be performed during the process, as in case ② of FIG. 1.

[0052] According to one embodiment, the continuous manufacturing method of the carbon dioxide capture composite particles may include a step of contacting the effluent of the process with the polyamidoamine particles. In this case, the contact step may be performed after the process, as in case ③ of FIG. 1.

[0053] According to another embodiment, the continuous manufacturing method of the carbon dioxide capture composite particles may include a step of contacting the feed water and the discharge water of the process with the polyamidoamine particles. In this case, the contact step may be performed both before and after the process, such as when performing both ① and ③ of FIG. 1.

[0054] At this time, the seawater injected from the ocean during the above process is defined as supply water, and the seawater or water discharged after the process is performed is defined as discharge water.

[0055] According to one embodiment, the feed water or the effluent may generally contain metal ions contained in seawater, and specifically may contain calcium ions and magnesium ions. The feed water or the effluent may contain calcium ions in a concentration of 0.1 g / L water or more, 0.1 to 10 g / L, or 0.2 to 5 g / L. If the feed water is general seawater, the calcium ion concentration is not high, but if the effluent is concentrated water, it may have a considerably high calcium ion concentration. In that case, it may have a calcium ion concentration of 0.5 g / L or more, but is not limited thereto.

[0056] In one embodiment, the feed water or effluent may contain carbonate ions formed by dissolving carbon dioxide in seawater. The feed water or effluent may have a carbonate ion concentration of, but is not limited to, 10 mg / L or more, 20 mg / L to 5 g / L, or 50 mg / L to 2 g / L.

[0057] In one embodiment, the polyamidoamine particles are cross-linked particles having a hyperbranched structure, and those containing amine and amide bonds (or peptide bonds) are more preferable for forming calcium carbonate. Hydrolysis of the amide can cause the polyamidoamine particles to decompose in water. Typically, the polyamidoamine particles can be easily hydrolyzed and decomposed within two weeks at 37°C in deionized water, and can be completely decomposed within three months. However, when the polyamidoamine particles are continuously contacted with seawater, the polyamidoamine particles are partially decomposed and swell, and calcium carbonate particles or calcite-type calcium carbonate particles are formed in the nano-sized pores formed on the surface of the swollen polyamidoamine particles, thereby allowing continuous growth of carbon dioxide capture composite particles. That is, as the polyamidoamine particles decompose, amine derivatives are generated on the surface, and as a result, under conditions where the pH is 8 or higher, the concentration of carbonate ions increases, creating an environment favorable for the formation of calcium carbonate. In addition, it is believed that the amine functional group of the decomposed polyamidoamine particles captures calcium ions, and the ammonium functional group captures carbonate ions, thereby locally increasing the concentration of mutual ions, resulting in the mineralization of calcium carbonate on the surface of the polyamidoamine particles. In addition, it is believed that calcium carbonate particles are formed and grow in the nano-sized pores formed on the surface of the polyamidoamine particles as they swell. Accordingly, it can provide the very surprising effect of producing a large amount of stable calcium carbonate particles in bulk seawater at room temperature and pressure.

[0058] According to one embodiment, when the polyamidoamine particles come into contact with seawater, the calcium carbonate particles, more specifically, calcite-type calcium carbonate particles, can be formed under conditions where the pH is 7 to 10, or 8 or higher, or 8 to 10, without adding a separate base, but the present invention is not limited thereto. In addition, the higher the concentration of the polyamidoamine particles in the seawater, the faster the growth rate of calcite, and the calcite can be formed better under conditions where the pH is 8 or higher. Therefore, if necessary, a step of adjusting the pH to 8 or higher by adding a basic substance may be further included, but the concentration of the polyamidoamine particles in the seawater can be adjusted without adding a separate basic substance.

[0059] According to one embodiment, the polyamidoamine particles may be crosslinked particles prepared from a polyfunctional amine monomer having at least two amine groups and a polyfunctional acrylamide monomer having at least two acrylic groups.

[0060] According to one embodiment, a method for producing the polyamidoamine particles may include the steps of: producing a polyamidoamine precursor aqueous solution from a polyfunctional amine monomer and a polyfunctional acrylamide monomer; and subjecting the polyamidoamine precursor aqueous solution to reverse-phase suspension polymerization to obtain cross-linked polyamidoamine particles.

[0061] The above-mentioned multifunctional amine monomer and multifunctional acrylamide monomer can produce a polyamidoamine precursor mixture by a Michael addition reaction in which the nitrogen atom of the amine reacts with the acryl group carbon of the acrylamide. In addition, the above-mentioned Michael addition reaction can also be used in a crosslinking reaction for producing hyperbranched polyamidoamine particles in a subsequent step, a reverse-phase suspension polymerization method.

[0062] In one embodiment, the polyamidoamine precursor aqueous solution is an intermediate for producing crosslinked hyperbranched polyamidoamine particles from the polyfunctional amine monomer and the polyfunctional acrylamide monomer, and is a mixture of oligomeric monomers. For example, the polyamidoamine precursor mixture may include an oligomer obtained by reacting one amine monomer and one acrylamide monomer, an oligomer obtained by reacting two amine monomers and one acrylamide monomer, an oligomer obtained by reacting one amine monomer and two acrylamide monomers, an oligomer obtained by reacting two amine monomers and two acrylamide monomers, an oligomer obtained by reacting three amine monomers and two acrylamide monomers, an oligomer obtained by reacting two amine monomers and three acrylamide monomers, etc.

[0063] According to one embodiment, in the case where an alkylenediamine (A) and a bisacrylamide monomer (B) are used as a compound of an amine compound and an acrylamide, when a polyamidoamine precursor mixture is prepared using each monomer, linear oligomer compounds such as AB, ABA, BAB, A-BA-B, BABA, ABABA, BABAB, ... can be obtained, and the polyamidoamine precursor mixture can mean a mixture thereof.

[0064] According to one embodiment, in the case of the alkylenediamine, one amine group can undergo a Michael addition reaction with the acrylamide twice, so that not only the linear oligomeric compound but also a branched oligomeric compound in which two acrylamides are bonded to one amine group can be obtained, and the polyamidoamine precursor mixture can also include such a case.

[0065] In one embodiment, the polyfunctional amine monomer may have at least two amine groups in one monomer. That is, it may be a diamine, triamine, or polyamine having two or more amine groups at the terminal of an alkylene group, and an amine group may be included in place of a hydrogen atom in the middle of the alkylene group, or an alkyl group including an amine group in place of a hydrogen atom in the middle of the alkylene group may be substituted. In the case of the diamine, a primary diamine may be capable of an additional cross-linking reaction because one amine group is capable of a Michael addition reaction with two acrylamides.

[0066] In one embodiment, the multifunctional amine monomer may be a C1-10 alkylenediamine, a C1-7 alkylenediamine, a C1-5 alkylenediamine, or a C3-5 alkylenediamine.

[0067] According to one embodiment, the multifunctional amine monomer may be ethylenediamine, 1,2-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, diethylenetriamine, triethylenetetraamine, tris(2-aminoethyl)amine, diaminocyclohexane, pentaethylenehexaamine, 2-aminoethylpiperazine, and the like, but is not limited thereto, and preferably, ethylenediamine, 1,4-butylenediamine, diethylenetriamine, and the like may be used.

[0068] In one embodiment, the multifunctional acrylamide monomer may have at least two, 2 to 5, 2 to 4, 2, or 3 acryl groups in one monomer, and the preferred number of acryl groups in the multifunctional acrylamide monomer may be 2 to 5, 2 to 4, 2, or 3.

[0069] In one embodiment, the multifunctional amine monomer may be a diamine having two primary amine groups in one monomer, and the multifunctional acrylamide monomer may include two acryl groups in one monomer.

[0070] In one embodiment, examples of the multifunctional acrylamide monomer include N,N'-methylenebisacrylamide, N,N'-(1,2-dihydroxyethylene)bisacrylamide, N,N'-ethylenebisacrylamide, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, and triethylene glycol diacrylate, but are not limited thereto, preferably N,N'-methylenebisacrylamide or N,N'-ethylenebisacrylamide can be used.

[0071] According to one embodiment, the step of preparing the polyamidoamine precursor mixture can be easily accomplished by selecting monomers that have differences in solubility in water when reacted in an aqueous solution state. That is, even if a monomer having a large difference in solubility in water is first dissolved in water to form an aqueous solution and then a monomer that is poorly soluble in water is added all at once, the water-insoluble monomer has low solubility in water, so that the effect is the same as if the water-insoluble monomer was gradually added to the aqueous solution in which the water-soluble monomer was dissolved.

[0072] In one embodiment, for example, when the polyamidoamine precursor mixture is prepared by a Michael addition reaction of ethylenediamine and N,N'-methylenebisacrylamide, the ethylenediamine is a B4 monomer that is highly soluble in water and can exist in a soluble state in an aqueous solution. However, N,N'-methylenebisacrylamide, which is an A2 monomer, is not soluble in water, so even if N,N'-methylenebisacrylamide is injected into the ethylenediamine aqueous solution at once, the N,N'-methylenebisacrylamide does not react with ethylenediamine all at once due to the difference in solubility in water, and in the initial state of the reaction, since an absolutely large number of ethylenediamines exist in the aqueous solution, the terminal of the polyamidoamine precursor mixture may mostly include an amine group.

[0073] As the reaction continues, methylene bisacrylamide gradually dissolves and Michael addition polymerization continues, continuously producing a hyperbranched polyamidoamine precursor mixture.

[0074] In one embodiment, in the preparation of the crosslinked hyperbranched polyamidoamine particles, the degree of crosslinking can be controlled by varying the molar ratio of each of the multifunctional monomers without using an additional crosslinking agent.

[0075] In one embodiment, the polyfunctional amine monomer and the polyfunctional acrylamide monomer may be mixed in a molar ratio of 1:0.5 to 5, 1:0.6 to 3.0, 1:0.8 to 2.5, 1:0.8 to 2.0, 1:0.8 to 1.5, or 1:0.9 to 1.2. When the molar ratio is satisfied, the amount of predominant calcium carbonate particles, the amount of carbon dioxide captured per g of polyamidoamine particles, and the amount of carbon dioxide removed per 24 hours for 100 g of polyamidoamine particles may be exhibited.

[0076] In one embodiment, the reverse phase suspension polymerization may be performed by dispersing the polyamidoamine precursor in an organic solvent having a volume of about 2 to 20 times that of the organic solvent, without or together with a stabilizer, and performing the reverse phase suspension polymerization at 30 to 80° C. In one embodiment, the reverse phase suspension polymerization may be performed by dispersing an aqueous solution of the polyamidoamine precursor mixture in a water-immiscible solvent, such as toluene or cyclohexane, using an appropriate stabilizer, and as the polymerization reaction progresses, crosslinking may occur, thereby producing hyperbranched polyamidoamine particles with controlled sizes.

[0077] According to one embodiment, the solvent used in the reverse phase suspension polymerization may be any one selected from among an alkane having 5 to 12 carbon atoms, a cycloalkane having 5 to 12 carbon atoms, and an aromatic hydrocarbon having 6 to 12 carbon atoms, and the stabilizer may be any one or a combination of two or more selected from among sorbitan esters of fatty acids including span 60 and span 80, 12-butinoyloxy-9-octadecenate, poly(hydroxy stearic acid)-copoly(ethylene oxide) block copolymers, and the like.

[0078] According to one embodiment, the reverse phase suspension polymerization may be carried out at 40 to 50° C. for 2 to 5 hours, but is not limited thereto.

[0079] According to one embodiment, the polyamidoamine particles may have a particle size (average particle diameter) of 1 μm to 2000 μm, 10 μm to 1000 μm, 10 μm to 500 μm, 20 μm to 200 μm, or 30 μm to 100 μm, but is not limited thereto, and the particle size may be easily adjusted to control carbon dioxide capture performance. In addition, the polyamidoamine particles may have a PDI of 2 or less, 1.5 or less, 1 to 1.2, or 1 to 1.1.

[0080] In one embodiment, the contacting step may include: (a) contacting the feed water or the discharge water with the polyamidoamine particles; and (b) forming calcium carbonate particles from calcium ions and carbonate ions in the feed water or the discharge water on the surface of the polyamidoamine particles.

[0081] According to one embodiment, in step (a), the contact may be any means that brings the supply water or the discharge water into contact with the polyamidoamine particles without significant limitation, and may be any one selected from the following methods.

[0082] (i) Filtration of feed water or effluent water in a column filled with polyamidoamine particles;

[0083] (ii) Dispersion of polyamidoamine particles in feed water or effluent;

[0084] (iii) Suspension of polyamidoamine particles on the surface of the supply water or effluent water;

[0085] The above method (i) is a method for manufacturing a column (or vessel such as a reactor or filter) filled with polyamidoamine particles and filtering the feed or discharge water by flowing it into the column, and may be a contact method suitable for performing a continuous process. Optionally, during the filtration method, a process for imparting fluidity to the feed or discharge water within the column, such as stirring or ultrasonic treatment, may be further performed.

[0086] According to one embodiment, the column may be filled with polyamidoamine particles at a density of 1 to 200 g / ㎥, 1 to 50 g / ㎥, or 3 to 30 g / ㎥, but is not limited thereto, and the packing density of the polyamidoamine particles can be easily controlled depending on the scale of the process or the size of the column.

[0087] In one embodiment, the contact may be such that, based on a 4L reactor, the feed water or the discharge water contacts a column in which the polyamidoamine particles have a density per unit volume of 2 to 20 g / ㎥, 3 to 15 g / ㎥, or 5 to 8 g / ㎥, at a flow rate of 0.1 to 200 L / h for a residence time (h) of 30 minutes or more, at a flow rate of 0.5 to 100 L / h for a residence time of 1 hour to 60 hours, or at a flow rate of 0.5 to 20 L / h for a residence time of 1 hour to 36 hours. Here, the residence time refers to the time taken from the time the feed water is introduced until it contacts the polyamidoamine particles and is discharged. When the above range is satisfied, the production efficiency of carbon dioxide capture composite particles or the carbon dioxide removal efficiency may be superior.

[0088] In one embodiment, the contact may satisfy a weight hourly space velocity (WHSV) range of 5 to 10,000 / hr, 5 to 1,000 / hr, 10 to 500 / hr, or 20 to 200 / hr depending on the amount of polyamidoamine particles (catalysts). In this case, the flow rate of seawater is calculated as 1 kg / hr = 1 L / hr.

[0089] WHSV = seawater flow rate (mass) (kg / hr) / catalyst mass (kg)

[0090] In one embodiment, the contact may satisfy a liquid hourly space velocity (LHSV) range of 0.01 to 100 / hr, 0.1 to 50 / hr, 0.1 to 10 / hr, or 0.2 to 5 / hr, depending on the reactor volume.

[0091] LHSV = seawater flow rate (㎥ / hr or L / hr) / reactor volume (㎥ or L)

[0092] The above method (i) is recommended for replacement if the surface of the polyamidoamine particles in the column is sufficiently covered with calcium carbonate, and the replacement cycle can be easily controlled depending on the type of process or the concentration of seawater.

[0093] Additionally, the above method (i) can further include a step of removing calcium carbonate from the surface by installing a separate ultrasonic grinder within the column. In this case, the lifespan of the polyamidoamine particles, which are the catalyst, is significantly improved, and the replacement cycle is extended, resulting in economic benefits.

[0094] The above method (ii) can be performed according to a conventional method for dispersing solid particles in a liquid, and may involve uniformly dispersing polyamidoamine particles in the feed or discharge water. After a certain period of time has elapsed after dispersion, the particles can be recovered. Optionally, a process for imparting flowability to the feed or discharge water, such as stirring or ultrasonic treatment, may be further performed during the dispersion process.

[0095] The above method (iii) can be used when the density of the polyamidoamine particles is lower than the density of the feed water or the discharge water, and is a method for floating the polyamidoamine particles on the surface of the feed water or the discharge water. A conventional floating method can be used, and the particles can be recovered after floating and a certain period of time has elapsed. Optionally, a process for imparting fluidity to the feed water or the discharge water, such as stirring or ultrasonic treatment, can be further performed during the floating method.

[0096] In one embodiment, during the step of contacting the feed water or the discharge water with the polyamidoamine particles, a step of injecting carbon dioxide into the feed water or the discharge water may be further performed. The carbon dioxide may be injected as a gas and may be ionized as carbonate in seawater to mineralize with calcium ions.

[0097] According to one embodiment, a polyamidoamine-calcium carbonate composite particle may be formed by the process (b) above, in which calcium carbonate particles are formed on the surface of the polyamidoamine particles.

[0098] Calcium carbonate has three major forms: calcite, aragonite, and vaterite. Among them, calcite-type calcium carbonate, with its trigonal crystal structure, is more thermally and chemically stable than other crystal forms. It is particularly advantageous industrially because it does not deform even in high-temperature environments. Its high purity and excellent optical properties make it a filler and coating agent for plastics, rubber, paints, and paper, and its outstanding light reflection and refractive properties make it a preferred choice for industries requiring durability and stability, such as the construction industry.

[0099] According to one embodiment, the calcium carbonate particles in the process (b) may be calcite-type calcium carbonate particles. The calcite-type calcium carbonate particles may be formed to account for 5% or more, or 5 to 100%, or 10% or more, or 10% to 90% of the surface of the polyamidoamine particles, and the degree of distribution of calcium carbonate particles on the surface of the polyamidoamine particles can be easily measured by using a conventional crystallography analysis method such as XRD (X-ray Diffraction), but is not limited thereto.

[0100] In one embodiment, a step of removing calcium carbonate from the surface using an ultrasonic grinder may be further performed after step (b). In this case, the lifespan of the polyamidoamine particles, which are the catalyst, is significantly improved, and the replacement cycle is extended, resulting in economic benefits.

[0101] According to one embodiment, the amount of calcium carbonate (M) produced per day (per 24 hours) for 100 g of polyamidoamine particles CaCO3-24h ) can be 1g / 24h or more, 1 to 2000g / 24h, 10 to 1000g / 24h, but can be easily adjusted according to process conditions.

[0102] According to one embodiment, the amount of carbon dioxide removed per 24 hours (M) for 100 g of polyamidoamine particles CO2-24h ) can be 1g / 24h or more, 1 to 500g / 24h, 10 to 200g / 24h, but can be easily adjusted according to process conditions.

[0103] In one embodiment, the process may include one or more selected from the group consisting of a seawater desalination process, an industrial cooling water process, an aquaculture process, and an agricultural irrigation process.

[0104] The present invention can provide carbon dioxide capture composite particles manufactured according to the continuous manufacturing method of carbon dioxide capture composite particles described above. The carbon dioxide capture composite particles are identical to the polyamidoamine-calcium carbonate composite particles described above, and the calcium carbonate particles are formed on the surface of the polyamidoamine particles, and the calcite-type calcium carbonate particles may grow by interfacing with each other on the surface of the polyamidoamine particles. In addition, when the composite particles come into contact with seawater again, their catalytic function can be regenerated and they can be reactivated.

[0105] The carbon dioxide capture composite particles described above can be used as a replacement for conventional calcium carbonate. Conventional calcium carbonate (CaCO3) is widely used in various industries, including construction materials, paper, plastics, food, pharmaceuticals, environmental protection, chemicals, and agriculture. In construction materials, it is used in cement, concrete, stone, and marble. In the paper industry, it is used as a filler and coating agent to improve the gloss and texture of paper. In the plastics and automotive materials industries, it is used as a filler.

[0106] The present invention can provide an automotive reinforcement material comprising the carbon dioxide capture composite particles described above. In compliance with existing legal regulations mandating the inclusion of recycled materials in automotive reinforcement materials, the high-strength composite particles described above can be filled into the automotive reinforcement material, achieving both environmental friendliness and economic efficiency.

[0107] The present invention can provide a construction cement comprising the carbon dioxide capture composite particles described above. Conventional construction cement has the side effect of weakening the strength of the cement when it comes into contact with seawater, but when construction is performed using a construction cement composition or construction cement comprising the carbon dioxide capture composite particles described above, even when it comes into contact with seawater, the particles are regenerated as a catalyst to form calcite-type calcium carbonate from carbonate ions or calcium ions in the seawater, thereby further improving the strength of the cement. In addition, since it is a recycled material, it has the advantage of being environmentally friendly and economical.

[0108] The present invention will be described in more detail based on the following examples and comparative examples. However, the following examples and comparative examples are merely illustrative examples for further explaining the present invention, and the present invention is not limited by the following examples and comparative examples.

[0109] <Physical property evaluation>

[0110] 1. Amount of carbon dioxide mineralization

[0111] In order to calculate the amount of calcium carbonate particles (CaCO3) formed on the surface of polyamidoamine particles of composite particles, TG (Thermogravimetric), DTG (Derivative Thermogravimetry), and DTA (Differential Thermal Analysis) were obtained using a thermogravimetric analyzer (TGA, Pyris 1, Perkin Elmer, USA), and the TG (Thermogravimetric) graph, which is a graph of weight change according to temperature, was analyzed to derive the ratio of polymer (polyamidoamine particles) and mineral (calcium carbonate).

[0112] The analysis conditions of the thermogravimetric analyzer were measured in the temperature range of 100 to 650℃, and after maintaining it at 100℃ for 10 minutes to remove moisture, it was heated to 650℃ at a heating rate of 10 celcius / min. In addition, oxygen was injected at a rate of 40 ml / min for oxidation. When the temperature was raised to 650℃, the organic polymer polyamidoamine particles were oxidized in the range of approximately 200 to 400℃, and inorganic substances such as calcium carbonate (CaCO3) formed on the surface of the polyamidoamine particles remained. From 600℃, calcium carbonate (CaCO3) was also separated into CaO and thermal decomposition began.

[0113] Accordingly, the polymer is thermally decomposed, but 550°C, which is before CaCO3 is thermally decomposed, was set as the standard, and the amount of calcium carbonate particles remaining at a temperature of 550°C and the amount of carbon dioxide removed per g of polyamidoamine particles used were obtained from the TGA graph, and specifically, the calculations were made using the following equations 1 and 2.

[0114] [Formula 1]

[0115] Amount of calcium carbonate particles = W1xMs

[0116] (In the above formula 1, W1 is the weight % value of the TGA peak of the residual calcium carbonate at 550 ℃, and Ms is the mass of the composite particles obtained after mineralization. At this time, the Ms is obtained as M0 / (1-W1), and the MO is the mass of the polyamidoamine particles introduced before mineralization.)

[0117] [Formula 2]

[0118] Amount of carbon dioxide per gram of polyamidoamine particles

[0119] = (Amount of calcium carbonate particles in the above formula 1 x ) / M0

[0120] (In the above equation 2, MO is the mass of polyamidoamine particles introduced before mineralization.)

[0121] In addition, the average carbon dioxide removal amount per hour was obtained using Equation 3 below, and the carbon dioxide removal rate per hour, which indicates the carbon dioxide removal speed, was obtained using Equation 4 below.

[0122] [Formula 3]

[0123] Total amount of carbon dioxide per gram of polyamidoamine particles / sum of residence time

[0124] [Formula 4]

[0125]

[0126] In the above equation 4, MCO2(t1) and MCO2(t2) are the amounts of carbon dioxide per g of polyamidoamine particles according to the above equation 2 at each residence time t1 and t2.

[0127]

[0128] 2. Amount of carbon dioxide mineralization in seawater

[0129] The concentrations of calcium cations and carbonate anions in seawater were measured using ICP-OES (inductively coupled plasma, Thermo Scientific, iCA P6300) and ion chromatography, and the amount of calcium carbonate particles (CaCO3) produced by polyamidoamine particles was calculated using Equation 5 below.

[0130] [Formula 5]

[0131] Amount of calcium carbonate particles (CaCO3) produced per 1 L of seawater (mg / L)

[0132] = Difference in calcium concentration (ppm) x

[0133] In the above equation 5, the difference in calcium concentration may be a value obtained by subtracting the calcium concentration in seawater before mineralization from the calcium concentration in seawater after mineralization, and to obtain the difference in calcium concentration over time, it may be a value obtained by subtracting the calcium concentration in seawater before mineralization for a certain period of time from the calcium concentration in seawater after mineralization for a certain period of time.

[0134]

[0135] [Manufacturing Example 1]

[0136] In a 1-neck round-neck flask, 0.6 g (10 mmol) of ethylene diamine (EDA) and 1.541 g (10 mmol) of N,N′-methylene bisacrylamide (MBA) were added in equal molar ratios, 4 mL of distilled water was added, and the mixture was stirred until a homogeneous mixture was formed.

[0137] After dissolving 0.02 g of span 60 (sorbitane monosterate) in 16 mL of toluene, it was added to a round-bottom flask with the prepared precursor aqueous solution, and reacted at 45°C for 3.5 hours while blowing nitrogen, then washed with methanol and filtered. The obtained particles were vacuum-dried at 60°C for 24 hours.

[0138] The cross-linked polyamidoamine particles of the above Manufacturing Example 1 had an average diameter of 51.49 μm and a PDI of 1.02 as measured by Mastersizer 2000. An image of the surface of the particles analyzed by SEM is shown in Fig. 4.

[0139] [Manufacturing Example 2]

[0140] In the above Manufacturing Example 1, polyamidoamine particles were manufactured in the same manner as in Manufacturing Example 1, except that 1,4-butanediamine (BDA), instead of EDA, was added in the same molar amount.

[0141] [Manufacturing Example 3]

[0142] In the above Manufacturing Example 1, polyamidoamine particles were manufactured in the same manner as in Manufacturing Example 1, except that hexamethylenediamine (HDA), instead of EDA, was added in the same molar amount.

[0143] [Manufacturing Example 4]

[0144] In the above Manufacturing Example 1, polyamidoamine particles were manufactured in the same manner as in Manufacturing Example 1, except that diethylenetriamine (DETA), instead of EDA, was added in the same molar amount.

[0145] [Manufacturing Example 5]

[0146] In the above Manufacturing Example 1, polyamidoamine particles were manufactured in the same manner as in Manufacturing Example 1, except that tris(2-aminoethyl)amine (TAEA), not EDA, was added in the same molar amount.

[0147] 100 mg of polyamidoamine particles according to Manufacturing Examples 1 to 5 were prepared at pH 8.10 to 8.50 and Ca 2+ The concentration is 450 mg / L, CO3 -The particle surface and seawater concentration changes were observed before and after being placed in 1000 mL of seawater with a concentration of 150 mg / L and left at room temperature of 20°C for 3 days.

[0148] The particle surface was analyzed using a scanning electron microscope (SEM), and the change in seawater concentration was measured using ICP-OES (inductively coupled plasma-optical spectroscopy) and ion chromatography. The measured SEM image is shown in Fig. 5, and the change in seawater concentration is recorded in Table 1 below. The amount (mg / L) of calcium carbonate particles (CaCO3) generated per 1 L of seawater calculated by [Equation 3] through the change in seawater concentration is also shown in Table 1 below.

[0149] Initial Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Calcium ion concentration 450 ppm 306 ppm 55 ppm 292 ppm 286 ppm 273 ppm Carbonate ion concentration 150 ppm Less than 5 ppm Less than 5 ppm Less than 5 ppm Less than 5 ppm Less than 5 ppm Amount of calcium carbonate particles (CaCO3) - 359.6 mg / L 986.4 mg / L 394.6 mg / L 409.6 mg / L 442.0 mg / L

[0150] As shown in Table 1 above, it was confirmed that the concentration of calcium ions and carbonate ions in seawater could be effectively reduced using the polyamidoamine particles according to Manufacturing Examples 1 to 5. In particular, it was confirmed that the polyamidoamine particles using butenediamine of Manufacturing Example 2 exhibited superior performance by showing a higher removal rate and amount of calcium carbonate particles than the other manufacturing examples.

[0151] 20 g of the polyamidoamine particles manufactured in the above manufacturing examples 1 to 5 were prepared by manufacturing them into the disclosed 80 mesh plate and filling them into a 2.6 L empty cylindrical filter in the center, and mounting the filter in a 4 L reactor as disclosed in Fig. 3.

[0152] [Example 1]

[0153] The pH of seawater is 8.10 to 8.50 and Na + 9300~9700(mg / L), Mg 2+ 1400-1450(mg / L), K + 360-410(mg / L), Ca 2+ 430-450(mg / L), Sr 2+ 9.0~10.50(mg / L), Rb 2+ 0.11~0.13(mg / L), Fe 0.06~0.20(mg / L), Li + 0.14~0.16(mg / L), Cl - 17300~17800(mg / L), SO4 2- 2260~2550(mg / L), CO3 - 130~150(mg / L), Br - 20~40(mg / L), F - Artificial seawater was prepared with a concentration of 0.8 to 1.1 (mg / L) for A and 4.0 to 6.0 (mg / L) for B.

[0154] A reactor equipped with a filter filled with the polyamidoamine particles manufactured in Manufacturing Example 1 was used, and the artificial seawater was provided as feed water and the pump was operated in a continuous system identical to the diagram disclosed in Fig. 1.

[0155] Specifically, 12 L of feed water was pumped from the feed tank at a flow rate of 1 L / h through the reactor and storage tank in that order, and was discharged as discharge water, and the reaction (mineralization) was performed under the conditions of a total operating time (retention time) of 8 hours and a mass space velocity (WHSV) of 50 / hr. The feed water continuously flows from the feed tank to the reactor, and when the reactor capacity is full, it moves from the reactor to the storage tank. Out of the total operating time of 8 hours, the polyamidoamine-calcium carbonate composite particles in which calcium carbonate was formed on the surface of the polyamidoamine particles in the filter at the 1st, 4th, and 8th hours were sampled, washed, and dried in an oven at 60°C for more than 12 hours before being analyzed.

[0156] At this time, the above reactor is an upflow reactor, in which the feed is injected from the bottom of the reactor, the reaction progresses while moving upward, and the material after the reaction is discharged through the upper outlet.

[0157] In addition, the above supply tank and storage tank have a capacity of 20L and a size of 200mmDia x 600mmL. The above reactor is equipped with a mineral collection tank connected by a separate connecting pipe, so that the produced calcium carbonate (CaCO3) can be stored. The mineral collection tank also has the same capacity and size as the supply tank.

[0158] The sampled polyamidoamine-calcium carbonate composite particles were analyzed by XRD and TGA, and the content ratio of calcite-type calcium carbonate in the calcium carbonate formed on the surface of the composite particles was calculated by calculating the area ratio of the peak (29.2° to 29.6°) corresponding to calcite-type calcium carbonate to the total peak area of ​​calcium carbonate in the XRD graph. It was confirmed that 11.97%, 11.94%, and 12.91% of calcite-type calcium carbonate were formed in the sample at 1 hour, 4 hours, and 8 hours, respectively. This indicates that the content of calcite-type calcium carbonate increases as the retention time increases.

[0159] [Example 2]

[0160] Example 1 was performed in the same manner as Example 1, except that a reactor equipped with an ultrasonic grinder inside was used as shown in Fig. 3. Specifically, the ultrasonic grinder was installed at the top of the reactor, close to the discharge portion, and operated continuously under the conditions of 45% amplitude, 20 minutes timer, 10 seconds pulse operation, and 5 seconds pause.

[0161] [Example 3]

[0162] The same procedure as Example 1 was followed, except that the supply water flow rate was 2 L / h and the total operating time (residence time) was 4 hours instead of 8 hours.

[0163] [Example 4]

[0164] In the above Example 1, the same procedure as Example 1 was carried out, except that the polyamidoamine particles manufactured in Manufacturing Example 2 were used instead of the polyamidoamine particles manufactured in Manufacturing Example 1.

[0165] Figure 6 shows a TGA analysis graph of carbon dioxide capture composite particles, which are polyamidoamine particles formed with calcium carbonate obtained from an hourly filter in Example 1. As shown in Figure 6, it was confirmed that the calcium carbonate content increased as the retention time elapsed.

[0166] Fig. 7 shows an XRD analysis graph of carbon dioxide capture composite particles, which are polyamidoamine particles formed of calcium carbonate obtained from an hourly filter in Example 1.

[0167] In Table 2 below, the amount of calcium carbonate particles calculated from Equations 1 and 2 above and the amount of carbon dioxide captured per g of polyamidoamine particles (M) are shown through TGA analysis graphs of carbon dioxide capture composite particles obtained from filters after the mineralization reaction was completed in Examples 1 to 4. CO2 ) was shown. In addition, the amount of carbon dioxide removed per 24 hours (M) for 100 g of polyamidoamine particles was calculated by Equation 6 below. CO2-24h ) was calculated and shown in Table 2 below.

[0168] [Formula 6]

[0169] M CO2-24h = [(M CO2 )x100] / stay time x 24hr

[0170] M CO2 M CO2-24hExample 10.1172g / g35.16gExample 20.1274g / g38.24gExample 30.1197g / g71.82gExample 40.1258g / g37.74g

[0171] As shown in Table 2 above, in the case of the continuous manufacturing method of carbon dioxide capture composite particles according to one embodiment, it was confirmed that carbon dioxide capture composite particles can be manufactured by continuously mineralizing carbon dioxide. In addition, when concentrated water with a calcium ion concentration of 786 mg / L rather than artificial seawater was used, the activity of the particles increased, increasing the calcium ion removal rate by more than three times, and it was confirmed that the amount of calcium carbonate produced and the amount of carbon dioxide removed also increased.

[0172] In particular, when controlling the flow rate or residence time, a higher flow rate showed superior results, and also, Example 4 using butenediamine showed better results than Example 1. In particular, Example 2 using a filter equipped with an ultrasonic grinder showed excellent carbon dioxide removal and life characteristics, and Example 3 showed the highest M CO2-24h Although the values ​​were shown, the replacement cycle was shorter than that of Example 2, and it was confirmed that the continuous manufacturing process of Example 2 showed the most superior work efficiency and economy.

[0173] As described above, the present invention has been described through specific matters and limited examples, but these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and those skilled in the art to which the present invention pertains can make various modifications and variations based on this description.

[0174] Therefore, the idea of ​​the present invention should not be limited to the described embodiments, and all things that are equivalent or equivalent to the following claims as well as the claims are considered to fall within the scope of the idea of ​​the present invention.

Claims

1. Includes a process that uses seawater as water, A continuous manufacturing method of carbon dioxide capture composite particles, comprising a step of contacting feed water or effluent water of the above process with polyamidoamine particles.

2. In paragraph 1, The step of contacting the above supply water or discharge water with the polyamidoamine particles is (a) contacting the feed water or the effluent with polyamidoamine particles; and (b) A continuous manufacturing method of carbon dioxide capturing composite particles, comprising a step of forming calcium carbonate particles from calcium ions and carbonate ions in the feed water or the discharge water on the surface of the polyamidoamine particles.

3. In paragraph 1, The above feed water or discharge water is a continuous manufacturing method of carbon dioxide capturing composite particles containing calcium ions and magnesium ions.

4. In paragraph 1, A continuous manufacturing method of carbon dioxide capturing composite particles, wherein the above feed water or discharge water contains calcium ions at a concentration of 0.1 g / L or more.

5. In paragraph 1, The above polyamidoamine particles are a continuous manufacturing method for carbon dioxide capturing composite particles which are crosslinked particles manufactured from a polyfunctional amine monomer having at least two amine groups and a polyfunctional acrylamide monomer having at least two acrylic groups.

6. In paragraph 5, A continuous manufacturing method for carbon dioxide capturing composite particles, wherein the above polyamidoamine particles are manufactured by reacting a polyfunctional amine monomer and a polyfunctional acrylamide monomer in a molar ratio of 1:0.8 to 2.

5.

7. In paragraph 6, A continuous manufacturing method of carbon dioxide capturing composite particles, wherein the above-mentioned multifunctional amine monomer contains two primary amine groups and the above-mentioned multifunctional acrylamide monomer contains two acrylic groups.

8. In paragraph 1, The above contact is a continuous manufacturing method of carbon dioxide capture composite particles selected from the following methods. (i) Filtration of feed water or effluent water in a column filled with polyamidoamine particles; (ii) Dispersion of polyamidoamine particles in feed water or effluent; (iii) Suspension of polyamidoamine particles on the surface of the supply water or effluent water; 9. In paragraph 8, The above column is a continuous manufacturing method of carbon dioxide capturing composite particles filled with polyamidoamine particles at a density of 1 to 50 g / ㎥.

10. In paragraph 8, The above contact is a continuous manufacturing method of carbon dioxide capturing composite particles, wherein the weight hourly space velocity (WHSV) ranges from 5 to 10,000 / hr depending on the amount of polyamidoamine particles.

11. In paragraph 1, The above polyamidoamine particles are a continuous manufacturing method for carbon dioxide capturing composite particles having a particle size of 10 to 1000 ㎛.

12. In paragraph 1, A continuous manufacturing method for carbon dioxide capture composite particles, wherein a step of injecting carbon dioxide into the feed water or the discharge water is further performed in the step of contacting the feed water or the discharge water with the polyamidoamine particles.

13. In paragraph 2, A continuous manufacturing method for carbon dioxide capturing composite particles, wherein polyamidoamine-calcium carbonate composite particles are formed by the above process (b) in which calcium carbonate particles are formed on the surface of polyamidoamine particles.

14. In paragraph 2, A continuous manufacturing method for carbon dioxide capturing composite particles, which further comprises performing a step of removing calcium carbonate on the surface using an ultrasonic grinder after the above step (b).

15. In paragraph 2, Amount of carbon dioxide removed per 24 hours for 100 g of polyamidoamine particles (M CO2-24h ) is a continuous manufacturing method of carbon dioxide capture composite particles having a yield of 1 g / 24 h or more.

16. In paragraph 1, The above process is a continuous manufacturing method of carbon dioxide capture composite particles comprising at least one selected from the group consisting of a seawater desalination process, an industrial cooling water process, an aquaculture process, and an agricultural irrigation process.

17. An automobile reinforcing material comprising carbon dioxide capture composite particles manufactured according to a continuous manufacturing method of carbon dioxide capture composite particles according to any one of claims 1 to 16.

18. Construction cement comprising carbon dioxide capture composite particles manufactured according to the continuous manufacturing method of carbon dioxide capture composite particles of any one of claims 1 to 16.

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