Method for manufacturing dry-type carbon dioxide adsorbing molding

Abstract

Provided is a method for manufacturing a dry-type carbon dioxide adsorbing molding which is applicable to a one pass-type greenhouse gas reduction device for small and medium-sized vessels, can be mass produced, and has a high adsorption efficiency while exhibiting low pressure loss. The method for manufacturing a dry-type carbon dioxide adsorbing molding may include: a step for sintering, at a predetermined temperature, a support prepared by extruding a mixture of a support raw material and a binder; a step for synthesizing an adsorbent by mixing a solvent, an amine compound, and a structure directing agent in a reaction vessel; and a step for physically impregnating pores of the support with the adsorbent and then drying.

Description

Method for manufacturing a dry carbon dioxide adsorbent molded body

[0001] The present invention relates to a method for manufacturing a dry type carbon dioxide adsorbing molding, and more particularly, to a method for manufacturing a dry type carbon dioxide adsorbing molding for small and medium-sized ships, which can be manufactured in large quantities, has a small pressure loss, and a high adsorption rate.

[0002] As we enter the era of carbon neutrality and regulations on ship exhaust gas have become more stringent, the need for technologies that can reduce greenhouse gases (especially CO2) in ship exhaust gas is increasing.

[0003] Exhaust gas reduction devices are generally focused on reducing SOx, NOx, or fine dust, and reduction devices that reduce greenhouse gases are only installed as wet types for large ships.

[0004] However, since the number of small and medium-sized vessels is much greater in coastal areas, a greenhouse gas reduction system for small and medium-sized vessel exhaust gases is needed to effectively prevent air pollution caused by small and medium-sized vessel exhaust gases.

[0005] However, greenhouse gas reduction systems for exhaust gases have been developed intensively for large ships, so the equipment itself is expensive. In addition, greenhouse gas reduction devices for large ships may not be able to be installed on small and medium-sized ships due to weight and volume issues.

[0006] Accordingly, there is currently no greenhouse gas reduction technology applicable to small and medium-sized vessels. Consequently, there is a pressing need to develop compact, lightweight adsorbents suitable for greenhouse gas absorption systems for small and medium-sized vessels.

[0007] Meanwhile, in the case of dry carbon dioxide adsorbents used for other purposes, a method is mainly used in which the adsorbent in powder form flows along the fluid bed and adsorbs carbon dioxide without a separate molding process.

[0008] However, since exhaust gas reduction devices for small and medium-sized ships must reduce carbon dioxide in a one-pass format, it is difficult to expect a high adsorption rate when using powder-type carbon dioxide adsorbents because the pressure loss is too large and the energy loss for the flow is large.

[0009] Additionally, one-pot synthesis has been introduced as a method for manufacturing conventional dry carbon dioxide adsorbents. One-pot synthesis refers to a method in which reactants are continuously added to a single reaction vessel to synthesize the final compound through multiple reaction steps, without separately purifying the intermediate products.

[0010] Therefore, according to the conventional one-pot synthesis, the support raw material and the adsorbent raw material are placed in one reaction vessel at the same time to react, and then the final adsorbent molded body is completed through the drying, crushing, and molding processes. However, each process takes a lot of time, making large-scale production realistically difficult.

[0011] Embodiments of the present invention are intended to provide a method for manufacturing a dry carbon dioxide adsorbent molded body that is applicable to a greenhouse gas reduction device for a small and medium-sized ship to which a one-pass format is applied, can be manufactured in large quantities, has a small pressure loss, and has a high adsorption rate.

[0012] Embodiments of the present invention aim to provide a dry carbon dioxide adsorbent molded body manufactured by the above method.

[0013] The tasks according to the embodiments of the present invention are not limited to the tasks mentioned above, and other tasks not mentioned can be clearly understood by a person having ordinary skill in the technical field to which the present invention belongs from the description below.

[0014] A method for manufacturing a dry carbon dioxide adsorbent molded body according to one embodiment of the present invention comprises the steps of extruding a mixture of a support raw material and a binder, sintering the prepared support at a predetermined temperature; mixing a solvent, an amine compound, and a structure-inducing agent in a reaction vessel to synthesize an adsorbent; and physically impregnating the adsorbent into the pores of the support and then drying it.

[0015] The above binder may be included in an amount of 50 to 70 parts by weight based on 100 parts by weight of the above support raw material.

[0016] The above support raw material may be at least one selected from the group consisting of bentonite, attapulgite, kaolinite, montmorillonite, ball clay, fuller's earth, hectorite, palygorskite, saponite, sepiolite, halloysite, silica, calcium sulfate, zeolite, synthetic zeolite, alumina, fumed silica, activated carbon, and metal-organic framework.

[0017] The above binder may be methyl cellulose.

[0018] The above support can be sintered at 500 to 600 degrees.

[0019] The above support may be in the shape of a polyhedron, a polygonal column or a cylinder.

[0020] The step of synthesizing the above adsorbent may be carried out without silicate.

[0021] The above adsorbent may be composed of 25 to 35 wt% of the above amine compound, 2 to 8 wt% of the above structure-inducing agent, and the remainder of the above solvent.

[0022] The solvent may be at least one selected from the group consisting of water, methanol, ethanol, methyl chloride, carbon tetrachloride, and tetrahydrofuran.

[0023] The above amine compound may be at least one selected from the group consisting of ethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexaamine, hexaethyleneheptamine, polyethyleneimine, and polypropyleneimine.

[0024] The above amine compound may be a polyethyleneimine modified by partial substitution with epoxybutane.

[0025] The above structural inducer may be at least one selected from the group consisting of tetramethylammonium phosphate (TMAH2PO4), tetraethylammonium phosphate (TEAH2PO4), tetrapropylammonium phosphate (TPAH2PO4), and tetrabutylammonium phosphate (TBAH2PO4).

[0026] A dry carbon dioxide adsorbent molded body according to one embodiment of the present invention can be manufactured according to the method mentioned above.

[0027] The step of synthesizing the above adsorbent may be a synthesis reaction without sodium silicate.

[0028] The above adsorbent may be composed of 29.1 wt% of the above amine compound, 4.7 wt% of the above structure-inducing agent, and 66.2 wt% of the above solvent.

[0029] The above adsorbent molded body can be used in a greenhouse gas reduction device for small and medium-sized ships that reduces carbon dioxide in a one-pass format.

[0030] Specific details of other embodiments are included in the specific contents and drawings.

[0031] As described above, according to the method for manufacturing a dry carbon dioxide adsorbent molded body according to the present invention and the dry carbon dioxide adsorbent molded body manufactured thereby, the adsorbent molded body is completed by independently performing support molding and adsorbent synthesis in parallel and then impregnating the adsorbent into the pores of the support, rather than following a one-pot synthesis that proceeds in a series of time-series processes, thereby drastically shortening the manufacturing time and enabling large-scale manufacturing.

[0032] Fumed silica, which is generally used as a support raw material, is very light and tends to scatter, making it very difficult to directly form a polyhedral, polygonal columnar, or cylindrical support from the support raw material. The present invention can form a high-strength support by extruding a mixture of the support raw material and a binder and then sintering it at a high temperature (500 to 600 degrees, preferably 550 degrees). Furthermore, the excellent performance of the support of the present invention was confirmed in terms of total pore volume and average adsorption efficiency for 5 minutes.

[0033] In addition, since the present invention independently performs support molding and adsorbent synthesis, there is no need to add silicate (e.g., sodium silicate), which is an additive that helps bind the support raw materials during adsorbent synthesis. Accordingly, when comparing the experimental group according to the present invention with the control group (sodium silicate added to the adsorbent), it was confirmed that the average carbon dioxide adsorption efficiency for 5 minutes increased by more than 3%, and the average retention time for 15% carbon dioxide adsorption efficiency increased by more than 30%.

[0034] Figure 1 is a flowchart showing a method for manufacturing a dry carbon dioxide adsorbent molded body according to one embodiment of the present invention.

[0035] Figure 2a is a graph showing the results of a nitrogen isothermal adsorption experiment according to BET analysis.

[0036] Figure 2b is a graph measuring the total pore volume and the average adsorption efficiency for 5 minutes according to BET analysis.

[0037] Figure 3 is a photograph and schematic diagram showing a one-pass reduction device that simulates a ship exhaust gas reduction device designed to measure carbon dioxide adsorption efficiency.

[0038] Figure 4 is a graph showing the carbon dioxide concentration measured using a one-pass reduction device.

[0039] Figure 5 is a graph measuring carbon dioxide adsorption efficiency using a one-pass reduction device.

[0040] Figure 6 is a graph measuring carbon dioxide adsorption efficiency using a one-pass reduction device.

[0041] Figure 7 is a graph measuring carbon dioxide adsorption efficiency according to carbon dioxide atmosphere using a one-pass reduction device.

[0042] The advantages and features of the present invention, and the methods for achieving them, will become clearer with reference to the embodiments described in detail below together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms. These embodiments are provided only to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention, and the present invention is defined only by the scope of the claims. Like reference numerals designate like elements throughout the specification.

[0043] Hereinafter, a method for manufacturing a dry carbon dioxide adsorbent molded body according to an embodiment of the present invention will be described in detail with reference to the attached drawings. Figure 1 is a flowchart illustrating a method for manufacturing a dry carbon dioxide adsorbent molded body according to an embodiment of the present invention.

[0044] A method for manufacturing a dry carbon dioxide adsorbent molded body according to one embodiment of the present invention independently performs support molding (S10) and adsorbent synthesis (S15) in parallel for large-scale production. That is, while the support is being molded, the adsorbent is synthesized using a separate container. Each process is described in detail below.

[0045] A support is prepared by extruding a mixture of support raw materials and a binder, and the support is sintered at a predetermined temperature (S10).

[0046] The support raw material may be composed of at least one selected from the group consisting of bentonite, attapulgite, kaolinite, montmorillonite, ball clay, fuller's earth, hectorite, palygorskite, saponite, sepiolite, halloysite, silica, calcium sulfate, zeolite, synthetic zeolite, alumina, fumed silica, activated carbon, and metal-organic frameworks. Preferably, the support raw material may be composed of fumed silica. Fumed silica is a synthetic silica manufactured by a dry method and has a high purity of 99.9% or more, and can be manufactured by gas phase pyrolysis of a chlorosilane compound.

[0047] The binder is an organic binder that binds the support raw material and may be composed of methyl cellulose. The binder may be included in an amount of 50 to 70 parts by weight based on 100 parts by weight of the support raw material. The binder may be included in an amount of 60 parts by weight based on 100 parts by weight of the support raw material.

[0048] The extruded support is sintered in an air atmosphere at 500 to 600 degrees, preferably 550 degrees, for 2 to 5 hours. The sintering temperature can affect the pore volume of the support, whether binder remains, etc.

[0049] If the sintering temperature is lower than 500 degrees, the binder remains within the porous support, reducing the carbon dioxide adsorption efficiency. If the sintering temperature is higher than 600 degrees, the binder is removed by high heat, but the pore volume within the support is reduced, reducing the carbon dioxide adsorption efficiency.

[0050] The extruded support may be formed in the shape of a polyhedron, polygonal column, or cylinder. The support may be extruded in the form of a pellet or honeycomb.

[0051] Separately from the support molding, an adsorbent is synthesized by mixing a solvent, an amine compound, and a structural inducer in a reaction vessel (S15). In this example, the adsorbent can be synthesized at room temperature for 1 to 2 hours.

[0052] The solvent may be comprised of one or more selected from the group consisting of water, methanol, ethanol, methyl chloride, carbon tetrachloride, and tetrahydrofuran. For example, the solvent may be comprised of water.

[0053] The amine compound may be composed of at least one selected from the group consisting of ethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexaamine, hexaethyleneheptamine, polyethyleneimine, and polypropyleneimine. Preferably, the amine compound may be composed of polyethyleneimine. More preferably, the amine compound may be modified polyethyleneimine (EB-PEI) partially substituted with epoxybutane.

[0054] A structure-directing agent is a compound that forms the skeleton of a support and acts as a template for forming a specific structure. The structure-directing agent may be comprised of one or more selected from the group consisting of tetramethylammonium phosphate (TMAH2PO4), tetraethylammonium phosphate (TEAH2PO4), tetrapropylammonium phosphate (TPAH2PO4), and tetrabutylammonium phosphate (TBAH2PO4). For example, the structure-directing agent may be comprised of tetraethylammonium phosphate.

[0055] In this embodiment, since the support molding (S10) and the adsorbent synthesis (S15) are performed independently, the step of synthesizing the adsorbent may not include adding an additive that helps bind the support raw materials.

[0056] Specifically, the synthesis reaction can be performed without the additive silicate during the synthesis of the adsorbent. Preferably, the synthesis reaction can be performed without the additive sodium silicate during the synthesis of the adsorbent.

[0057] The adsorbent may be composed of 25 to 35 wt% of an amine compound, 2 to 8 wt% of a structure-directing agent, and the remainder of the solvent. Preferably, the adsorbent may be composed of 29.1 wt% of an amine compound, 4.7 wt% of a structure-directing agent, and 66.2 wt% of a solvent.

[0058] Using the independently prepared support and adsorbent, the adsorbent is physically impregnated into the pores of the support and then dried (S20). In this embodiment, the support is placed in the adsorbent in the reaction vessel and impregnated for a predetermined period of time. After that, the support is separated and dried in an air atmosphere at room temperature for a predetermined period of time to remove the solvent, thereby completing the final adsorbent molded body. The adsorbent molded body of this embodiment can be used in a greenhouse gas reduction device for small and medium-sized ships that reduces carbon dioxide in a one-pass manner.

[0059] Hereinafter, with reference to FIGS. 2a to 5, the performance measurement results of dry carbon dioxide adsorption molded bodies according to sintering temperature will be examined. FIG. 2a is a graph showing the results of a nitrogen isothermal adsorption experiment according to BET analysis. FIG. 2b is a graph measuring the total pore volume and the average adsorption efficiency for 5 minutes according to BET analysis. FIG. 3 is a photograph and diagram showing a one-pass reduction device simulating a ship exhaust gas reduction device prepared to measure carbon dioxide adsorption efficiency. FIG. 4 is a graph measuring carbon dioxide concentration using a one-pass reduction device. FIG. 5 is a graph measuring carbon dioxide adsorption efficiency using a one-pass reduction device.

[0060] In this experimental example, 100 parts by weight of fumed silica and 60 parts by weight of methyl cellulose were mixed, extruded, and sintered at various sintering temperatures (450 degrees, 550 degrees, 650 degrees, and 750 degrees) in an air atmosphere to produce a support. In addition, in a reaction vessel, 29.1 wt% of polyethyleneimine (EB-PEI) partially substituted with epoxybutane, 4.7 wt% of tetraethylammonium phosphate (TEAH2PO4), 11.1 wt% of water, and 55.1 wt% of ethanol (C2H6O) were mixed to synthesize an adsorbent at room temperature. Subsequently, the adsorbent was impregnated into the pores of the support, and then dried at room temperature in an air atmosphere to complete the final adsorbent molded body.

[0061] Sintering temperature (℃) 450 550 650 750 BET surface area, S BET (m 2 / g)120.9431.624.86.1Total pore volume, V total (cm 3 / g)0.260.980.0520.017Average adsorption efficiency for 5 min (%)6.8522.646.194.77CO2adsorbed for 5 min (mmol / g)-0.436-0.084

[0062] As shown in Figures 2a to 2b and Table 1, when the sintering temperature is 550 degrees, the nitrogen gas absorption volume (V) per unit mass of the adsorbent molded body ads ) was confirmed to be significantly larger than other sintering temperatures. In addition, when the sintering temperature was 550 degrees, the total pore volume was 0.98 cm 3 / g and the average adsorption efficiency for 5 min was measured to be 22.64%, which was confirmed to be significantly greater than other sintering temperatures.

[0063] The one-pass reduction device of Fig. 3 operates as follows. Carbon dioxide and nitrogen supplied through two MFCs are heated to the temperature range of the actual exhaust gas using a preheater and then supplied into the reactor. The carbon dioxide concentration is measured before and after the adsorbent molding located within the reactor. In addition, adsorption and desorption are controlled using a bypass path connected in parallel to the reactor and two valves (V1, V2) located on either side of it.

[0064] In FIGS. 4 and 5, the adsorption capacity was measured by placing the adsorbent molded body in the one-pass reduction device of FIG. 3 and maintaining it at 60 degrees for 5 minutes while flowing 5% CO2 and 95% N2 at 50 LPM (liter / min). "Upstream" indicates the concentration of carbon dioxide before passing through the adsorbent molded body in the one-pass reduction device, and "Downstream" indicates the concentration of carbon dioxide after passing through the adsorbent molded body. "Drying at 450°C," "drying at 550°C," "drying at 650°C," and "drying at 750°C" indicate adsorbent molded bodies sintered at 450°C, 550°C, 650°C, and 750°C, respectively. As shown in FIGS. 4 to 5 and Table 1, when the sintering temperature was 550 degrees, the carbon dioxide adsorbed for 5 minutes was measured to be 0.436 mmol / g, which was confirmed to be significantly greater than that at other sintering temperatures.

[0065] Hereinafter, the silicate removal effect during adsorbent synthesis will be examined with reference to FIGS. 6 and 7. FIG. 6 is a graph measuring carbon dioxide adsorption efficiency using a one-pass reduction device. FIG. 7 is a graph measuring carbon dioxide adsorption efficiency according to a carbon dioxide atmosphere using a one-pass reduction device. In this embodiment, carbon dioxide adsorption efficiency can be used with substantially the same meaning as carbon dioxide removal efficiency of a one-pass reduction device.

[0066] In this experimental example, 100 parts by weight of fumed silica and 60 parts by weight of methyl cellulose were mixed, extruded, and sintered at 550 degrees in an air atmosphere to produce a support. In addition, 29.1 wt% of polyethyleneimine (EB-PEI) partially substituted with epoxybutane, 4.7 wt% of tetraethylammonium phosphate (TEAH2PO4), 11.1 wt% of water, and 55.1 wt% of ethanol (C2H6O) were mixed in a reaction vessel to synthesize an adsorbent at room temperature. Then, the adsorbent was impregnated into the pores of the support, and then dried at room temperature in an air atmosphere to produce a final adsorbent molded body weighing 320 g.

[0067] In the case of a comparative example, an adsorbent was synthesized by adding sodium silicate to a mixture of EB-PEI, tetraethylammonium phosphate, water, and ethanol (each component having the same weight ratio as in the experimental example), and the adsorbent was impregnated into the same support as in the experimental example, and then dried at room temperature in an air atmosphere to obtain a final adsorbent molded body weighing 320 g. Sodium silicate is included in an amount of 10 parts by weight based on 100 parts by weight of fumed silica.

[0068] In Figs. 6 and 7, the adsorption capacity was measured by placing the adsorbent molded body in the one-pass reduction device of Fig. 3 and maintaining it at 60 degrees for 5 minutes while flowing 5% CO2 and 95% N2 at 50 LPM (liter / min). "Upstream" represents the concentration of carbon dioxide before passing through the adsorbent molded body in the one-pass reduction device, "Downstream" represents the concentration of carbon dioxide after passing through the adsorbent molded body, and "Comparative Example" and "Experimental Example" represent the respective carbon dioxide adsorption efficiencies. Under 5% carbon dioxide atmospheric conditions similar to ship exhaust gas, the experimental example (18.04%) showed an average carbon dioxide absorption efficiency for 5 minutes that was improved by more than 2.5% compared to the comparative example (15.53%), and the experimental example (139 s) showed an improvement of more than 30% compared to the comparative example (107 s) in the 15% carbon dioxide absorption efficiency maintenance time.

[0069] Although the embodiments of the present invention have been described with reference to the attached drawings, those skilled in the art will appreciate that the present invention can be implemented in other specific forms without altering the technical concept or essential features thereof. Therefore, the embodiments described above should be understood to be illustrative in all respects and not restrictive.

Claims

1. A method for manufacturing a dry carbon dioxide adsorption molded body capable of mass production, A step of extruding a mixture of support raw materials and a binder and sintering the prepared support at a predetermined temperature; A step of synthesizing an adsorbent by mixing a solvent, an amine compound, and a structure-inducing agent in a reaction vessel; and A method for producing a dry carbon dioxide adsorbent molded body, comprising the step of physically impregnating the adsorbent into the pores of the support and then drying it.

2. In paragraph 1, A method for producing a dry carbon dioxide adsorption molded body, characterized in that the binder is contained in an amount of 50 to 70 parts by weight based on 100 parts by weight of the support raw material.

3. In paragraph 1, A method for producing a dry carbon dioxide adsorbent molded body, characterized in that the support raw material is at least one selected from the group consisting of bentonite, attapulgite, kaolinite, montmorillonite, ball clay, fuller's earth, hectorite, palygorskite, saponite, sepiolite, halloysite, silica, calcium sulfate, zeolite, synthetic zeolite, alumina, fumed silica, activated carbon, and metal organic framework.

4. In paragraph 1, A method for producing a dry carbon dioxide adsorbent molded body, characterized in that the binder is methyl cellulose.

5. In paragraph 1, A method for producing a dry carbon dioxide adsorbent molded body, characterized by sintering the support at 500 to 600 degrees.

6. In paragraph 1, A method for producing a dry carbon dioxide adsorbent molded body, characterized in that the support has a polyhedral, polygonal columnar or cylindrical shape.

7. In paragraph 1, A method for producing a dry carbon dioxide adsorbent molded body, characterized in that the step of synthesizing the above adsorbent is carried out without silicate.

8. In paragraph 1, A method for producing a dry carbon dioxide adsorbent molded body, characterized in that the adsorbent comprises 25 to 35 wt% of the amine compound, 2 to 8 wt% of the structural inducer, and the remainder of the solvent.

9. In paragraph 1, A method for producing a dry carbon dioxide adsorbent molded body, characterized in that the solvent is at least one selected from the group consisting of water, methanol, ethanol, methyl chloride, carbon tetrachloride, and tetrahydrofuran.

10. In paragraph 1, A method for producing a dry carbon dioxide adsorbent molded body, characterized in that the amine compound is at least one selected from the group consisting of ethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, polyethyleneimine, and polypropyleneimine.

11. In paragraph 1, A method for producing a dry carbon dioxide adsorbent molded body, characterized in that the above amine compound is a polyethyleneimine modified by partial substitution with epoxybutane.

12. In paragraph 1, The above structural inducer is tetramethylammonium phosphate (TMAH). 2 PO 4 ), tetraethylammonium phosphate (TEAH 2 PO 4 ), tetrapropylammonium phosphate (TPAH) 2 PO 4 ) and tetrabutylammonium phosphate (TBAH) 2 PO 4 ) is characterized by at least one selected from the group consisting of.

13. A dry carbon dioxide adsorbent molded body manufactured according to any one of claims 1 to 12.

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