Method for manufacturing a dry carbon dioxide adsorption molded body
The independent molding and synthesis process for carbon dioxide adsorption molded bodies addresses high pressure loss and scalability issues, achieving enhanced adsorption efficiency and production capacity for small and medium-sized ships.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-11-21
- Publication Date
- 2026-04-15
AI Technical Summary
Existing methods for reducing greenhouse gases in small and medium-sized ships face challenges such as high pressure loss, energy inefficiency, and lack of scalable production due to the use of powdered carbon dioxide adsorbents and one-pot synthesis processes.
A method involving independent carrier molding and adsorbent synthesis, followed by impregnation and drying, to produce a dry carbon dioxide adsorption molded body suitable for one-pass systems in small and medium-sized vessels, using fumed silica as a carrier and amine compounds without silicates.
This method enables high adsorption rates with reduced pressure loss, facilitating large-scale production and improved carbon dioxide adsorption efficiency, exceeding conventional methods by 3-30%.
Smart Images
Figure 2026512333000001_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to a method for manufacturing a dry-type carbon dioxide adsorbing molding (METHOD FOR MANUFACTURING 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 that enables mass production, has a small pressure loss, and a high adsorption rate.
Background Art
[0002] With the advent of the carbon-neutral era and the recent tightening of regulations on ship exhaust gases, there is a growing need for technologies that can reduce greenhouse gases (especially CO2) in ship exhaust gases.
[0003] Exhaust gas reduction devices usually focus on reducing SOx, NOx or fine dust, and the only reduction devices for greenhouse gases are wet-type ones installed for large ships.
[0004] However, since the number of small and medium-sized ships is much larger along the coast, a greenhouse gas reduction system for small and medium-sized ship exhaust gases is needed to effectively prevent air pollution caused by small and medium-sized ship exhaust gases.
[0005] However, the greenhouse gas reduction system for exhaust gases has been intensively developed for large ships and the equipment itself is expensive. At the same time, the greenhouse gas reduction device for large ships may not be installed on small and medium-sized ships due to weight and volume problems.
[0006] As a result, there is no technology applicable to actual small and medium-sized ships for reducing greenhouse gases. Therefore, it is actually necessary to develop a small and lightweight adsorbent applicable to an adsorption system for greenhouse gas adsorption suitable for small and medium-sized ships.
[0007] On the other hand, conventionally, in the case of dry-type carbon dioxide adsorbents used for other applications, a method in which an adsorbent in powder form flows in a fluidized bed according to the flow and adsorbs carbon dioxide without a separate molding process is mainly used.
[0008] However, since exhaust gas reduction devices for small and medium-sized vessels must reduce carbon dioxide in a single pass, using powdered carbon dioxide adsorbents results in excessively large pressure losses and significant energy losses due to fluid flow, making it difficult to expect high adsorption rates.
[0009] Furthermore, one-pot synthesis is introduced as a conventional method for producing dry carbon dioxide adsorbents. One-pot synthesis refers to a method in which, when synthesizing the final compound through multiple reaction steps, the reactants are continuously added and reacted in a single reaction vessel without separately purifying intermediate products.
[0010] Therefore, in conventional one-pot synthesis, the carrier material and adsorbent material are placed in a single reaction vessel and reacted at once, followed by drying, pulverization, and molding processes to complete the final adsorbent molded body. However, each of these processes takes a considerable amount of time, making large-scale production practically difficult. [Overview of the Initiative] [Problems that the invention aims to solve]
[0011] The object of the embodiments of the present invention is to provide a method for manufacturing a dry carbon dioxide adsorption molded body that is applicable to greenhouse gas reduction devices for small and medium-sized vessels using a one-pass system, is capable of large-scale production, and has a high adsorption rate despite low pressure loss.
[0012] An object of the embodiments of the present invention is to provide a dry carbon dioxide adsorption molded body manufactured by the method described above.
[0013] The problems addressed by the embodiments of the present invention are not limited to those mentioned above, and other problems not mentioned should be clearly understood by those with ordinary skill in the art to which the present invention pertains from the following description. [Means for solving the problem]
[0014] A method for producing a dry carbon dioxide adsorbent molded article according to one embodiment of the present invention includes the steps of: extruding a mixture of a carrier raw material and a binder to obtain a carrier, and sintering the carrier at a predetermined temperature; synthesizing an adsorbent by mixing a solvent, an amine compound, and a structure directing agent in a reaction vessel; and physically impregnating the pores of the carrier with the adsorbent and then drying it.
[0015] The binder may be included in an amount of 50 to 70 parts by weight based on 100 parts by weight of the carrier material.
[0016] The aforementioned carrier material may be one or more 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 structures.
[0017] The binder may be methylcellulose.
[0018] The carrier can be sintered at 500 to 600 degrees Celsius.
[0019] The carrier may be polyhedron, polygonal prism, or cylindrical in shape.
[0020] The step of synthesizing the adsorbent can be carried out without silicates.
[0021] The adsorbent may consist of 25-35% by weight of the amine compound, 2-8% by weight of the structure-directing agent, and the remaining solvent.
[0022] The solvent may be one or more selected from the group consisting of water, methanol, ethanol, methyl chloride, carbon tetrachloride, and tetrahydrofuran.
[0023] The amine compound may be one or more selected from the group consisting of ethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, polyethyleneimine, and polypropyleneimine.
[0024] The amine compound may be polyethyleneimine partially substituted and modified with epoxybutane.
[0025] The structure-directing agent may be one or more selected from the group consisting of tetramethylammonium phosphate (TMAH2PO4), tetraethylammonium phosphate (TEAH2PO4), tetrapropylammonium phosphate (TPAH2PO4), and tetrabutylammonium phosphate (TBAH2PO4).
[0026] The dry carbon dioxide adsorbent molded body according to an embodiment of the present invention can be manufactured by the method described above.
[0027] The step of synthesizing the adsorbent may be a synthesis reaction without sodium silicate.
[0028] The adsorbent can consist of 29.1% by weight of the amine compound, 4.7% by weight of the structure-directing agent, and 66.2% by weight of the solvent.
[0029] The adsorbent molded body can be used in a greenhouse gas reduction device for medium and small ships that reduces carbon dioxide in a one-pass format.
[0030] Specific matters of other embodiments are included in the specific content and drawings.
Advantages of the Invention
[0031] As described above, the method for producing a dry carbon dioxide adsorption molded body according to the present invention and the dry carbon dioxide adsorption molded body produced thereby do not follow a one-pot synthesis that is carried out in a series of time-series processes. Instead, carrier molding and adsorbent synthesis are carried out independently and in parallel, and then the adsorbent is impregnated into the pores of the carrier to complete the adsorption molded body. This dramatically reduces the manufacturing time and enables large-scale production.
[0032] Fumed silica, commonly used as a carrier material, is excessively light and prone to scattering, making it extremely difficult to directly mold polyhedral, polygonal prism, or cylindrical carriers from the carrier material. This invention allows for the molding of high-strength carriers by extruding a mixture of carrier material and binder, followed by sintering at high temperatures (500-600 degrees Celsius, preferably 550 degrees Celsius). Furthermore, the superior performance of the carrier according to this invention was confirmed in terms of total pore volume and average adsorption efficiency over 5 minutes.
[0033] Furthermore, since the present invention allows for independent carrier molding and adsorbent synthesis, there is no need to add silicates (e.g., sodium silicate), which are additives that help bind the carrier raw materials, during adsorbent synthesis. Consequently, when the experimental group according to the present invention was compared with the control group (adsorbent with added sodium silicate), it was confirmed that the average carbon dioxide adsorption efficiency over 5 minutes increased by more than 3%, and the average maintenance time of 15% carbon dioxide adsorption efficiency increased by more than 30%. [Brief explanation of the drawing]
[0034] [Figure 1] This is a flowchart showing a method for manufacturing a dry carbon dioxide adsorption molded body according to one embodiment of the present invention. [Figure 2a] This graph shows the results of a nitrogen isothermal adsorption experiment using BET analysis. [Figure 2b] This graph shows the total pore volume and average adsorption efficiency over 5 minutes, measured by BET analysis. [Figure 3]This is a photograph and diagram showing a one-pass exhaust gas reduction device, which is a replica of a ship's exhaust gas reduction device installed to measure the adsorption efficiency of carbon dioxide. [Figure 4] This graph shows the carbon dioxide concentration measured using a single-pass reduction device. [Figure 5] This graph shows the carbon dioxide adsorption efficiency measured using a one-pass reduction device. [Figure 6] This graph shows the carbon dioxide adsorption efficiency measured using a one-pass reduction device. [Figure 7] This graph shows the carbon dioxide adsorption efficiency measured using a single-pass reduction device in a carbon dioxide atmosphere. [Modes for carrying out the invention]
[0035] The advantages and features of the present invention, and methods for achieving them, will become apparent with reference to the embodiments described below in detail with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but can be embodied in a variety of different forms, and these embodiments are merely provided to complete the disclosure of the present invention and to fully inform those who are ordinary skill in the art to which the invention pertains of the invention of the scope of the invention, and the present invention is defined solely by the scope of the claims. Throughout the specification, the same reference numerals refer to the same components.
[0036] The method for manufacturing a dry carbon dioxide adsorption molded article according to one embodiment of the present invention will be described in detail below with reference to the attached drawings. Figure 1 is a flowchart showing the method for manufacturing a dry carbon dioxide adsorption molded article according to one embodiment of the present invention.
[0037] In one embodiment of the present invention, a method for manufacturing a dry carbon dioxide adsorption molded body involves independently and in parallel carrying out carrier molding (S10) and adsorbent synthesis (S15) for large-scale production. That is, while the carrier is being molded, the adsorbent is synthesized using a separate reaction vessel. The following describes each process in detail.
[0038] A carrier is obtained by extruding a mixture of carrier raw materials and a binder, and the carrier is sintered at a predetermined temperature (S10).
[0039] The carrier material can consist of one or more 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 structures. Preferably, the carrier material can consist of fumed silica. Fumed silica is a synthetic silica produced by a dry process, is a high-purity substance of 99.9% or more, and can be produced by gas-phase thermal decomposition of a silane chloride compound.
[0040] The binder is an organic binder that binds the carrier raw materials and may consist of methylcellulose. The binder may be included in an amount of 50 to 70 parts by weight based on 100 parts by weight of the carrier raw materials. The binder may be included in an amount of 60 parts by weight based on 100 parts by weight of the carrier raw materials.
[0041] The extruded carrier is sintered in an atmospheric environment at 500-600 degrees Celsius, preferably 550 degrees Celsius, for 2-5 hours. The sintering temperature may affect the pore volume of the carrier, the presence or absence of binder residue, etc.
[0042] If the sintering temperature is lower than 500 degrees Celsius, the binder remains in the porous support, reducing the carbon dioxide adsorption efficiency. If the sintering temperature is higher than 600 degrees Celsius, the binder is removed by the high heat, but the pore volume in the support decreases, further reducing the carbon dioxide adsorption efficiency.
[0043] The extruded carrier can be polyhedral, polygonal prism, or cylindrical in shape. The carrier can be extruded in pellet or honeycomb form.
[0044] Separately from carrier molding, the adsorbent is synthesized by mixing a solvent, an amine compound, and a structure-directing agent in a reaction vessel (S15). In this embodiment, the adsorbent can be synthesized at room temperature for 1 to 2 hours.
[0045] The solvent can consist of one or more selected from the group comprising water, methanol, ethanol, methyl chloride, carbon tetrachloride, and tetrahydrofuran. For example, the solvent can be water.
[0046] The amine compound may consist of one or more compounds selected from the group consisting of ethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, polyethyleneimine, and polypropyleneimine. Preferably, the amine compound may consist of polyethyleneimine. More preferably, the amine compound may be polyethyleneimine modified by partial substitution with epoxybutane (EB-PEI).
[0047] A structure-directing agent is a compound that forms the backbone of a support and acts as a template for forming a specific structure. The structure-directing agent can consist of one or more compounds 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 can consist of tetraethylammonium phosphate.
[0048] In this embodiment, since carrier molding (S10) and adsorbent synthesis (S15) are performed independently, it is not necessary to add an additive that helps bind the carrier raw materials during the adsorbent synthesis step.
[0049] Specifically, the synthesis reaction can be carried out without the additive silicate during the synthesis of the adsorbent. Preferably, the synthesis reaction can be carried out without the additive sodium silicate during the synthesis of the adsorbent.
[0050] The adsorbent may consist of 25-35% by weight of the amine compound, 2-8% by weight of the structure-directing agent, and the remaining solvent. Preferably, the adsorbent may consist of 29.1% by weight of the amine compound, 4.7% by weight of the structure-directing agent, and 66.2% by weight of the solvent.
[0051] Using the carrier and adsorbent obtained independently in this way, the adsorbent is physically impregnated into the pores of the carrier and then dried (S20). In this embodiment, the carrier is placed in the adsorbent in the reaction vessel and impregnated for a predetermined time, then the carrier is separated and dried at room temperature in an atmospheric environment for a predetermined time to remove the solvent and complete the final adsorbent molded body. The adsorbent molded body of this embodiment can be used in greenhouse gas reduction devices for small and medium-sized vessels that reduce carbon dioxide in a single pass.
[0052] The following describes the performance measurement results of dry carbon dioxide adsorption molded bodies according to sintering temperature, with reference to Figures 2a to 5. Figure 2a is a graph showing the results of a nitrogen isothermal adsorption experiment by BET analysis. Figure 2b is a graph showing the total pore volume and the average adsorption efficiency over 5 minutes measured by BET analysis. Figure 3 is a photograph and configuration diagram showing a one-pass reduction device, which is a replica of a ship's exhaust gas reduction device installed to measure the carbon dioxide adsorption efficiency. Figure 4 is a graph showing the carbon dioxide concentration measured using the one-pass reduction device. Figure 5 is a graph showing the carbon dioxide adsorption efficiency measured using the one-pass reduction device.
[0053] In this experiment, a carrier was produced by mixing 100 parts by weight of fumed silica and 60 parts by weight of methylcellulose, extruding the mixture, and then sintering it at various sintering temperatures (450°C, 550°C, 650°C, and 750°C) under an atmospheric environment. An adsorbent was synthesized at room temperature by mixing 29.1% by weight of partially substituted and modified polyethyleneimine (EB-PEI) with epoxybutane, 4.7% by weight of tetraethylammonium phosphate (TEAH2PO4), 11.1% by weight of water, and 55.1% by weight of ethanol (C2H6O) in a reaction vessel. The adsorbent was then impregnated into the pores of the carrier, and the final adsorbent molded body was completed by drying it at room temperature under an atmospheric environment.
[0054] [Table 1] As shown in Figures 2a-2b and Table 1, when the sintering temperature is 550 degrees, the nitrogen gas absorption volume per unit mass of the adsorbent molded body is (V ads It was confirmed that the pore volume was significantly larger at this temperature compared to other sintering temperatures. Furthermore, at a sintering temperature of 550 degrees Celsius, the total pore volume was 0.98 cm³. 3 The concentration was measured at / g, and the average adsorption efficiency for 5 minutes was measured at 22.64%, which was found to be significantly higher compared to other sintering temperatures.
[0055] The one-pass reduction device shown in Figure 3 operates as follows: Carbon dioxide and nitrogen supplied through two MFCs are heated to the actual exhaust gas temperature range using a preheater before being supplied to the reactor. The concentration of carbon dioxide is measured before and after the adsorption molded body located inside the reactor. Adsorption and desorption are controlled using a bypass channel connected in parallel to the reactor and two valves V1 and V2 located on either side of it.
[0056] Figures 4 and 5 show that the adsorption capacity was measured by placing the adsorbent molded body in the one-pass reduction apparatus shown in Figure 3 and maintaining a temperature of 60 degrees Celsius 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 apparatus, 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" refer to the adsorbent molded bodies sintered at 450°C, 550°C, 650°C, and 750°C, respectively. As shown in Figures 4 and 5 and Table 1, when the sintering temperature was 550°C, the amount of carbon dioxide adsorbed after 5 minutes was measured to be 0.436 mmol / g, which was found to be significantly higher than at other sintering temperatures.
[0057] The silicate removal effect during the synthesis of the adsorbent will be explained below with reference to Figures 6 and 7. Figure 6 is a graph showing the carbon dioxide adsorption efficiency measured using a one-pass reduction device. Figure 7 is a graph showing the carbon dioxide adsorption efficiency measured using a one-pass reduction device in a carbon dioxide atmosphere. In this embodiment, the carbon dioxide adsorption efficiency can be used with substantially the same meaning as the carbon dioxide removal efficiency of the one-pass reduction device.
[0058] In this experiment, a carrier was produced by mixing 100 parts by weight of fumed silica and 60 parts by weight of methylcellulose, extruding the mixture, and then sintering it at 550 degrees Celsius under an atmospheric environment. An adsorbent was synthesized at room temperature by mixing 29.1% by weight of partially substituted polyethyleneimine (EB-PEI) with epoxybutane, 4.7% by weight of tetraethylammonium phosphate (TEAH2PO4), 11.1% by weight of water, and 55.1% by weight of ethanol (C2H6O) in a reaction vessel. The adsorbent was then impregnated into the pores of the carrier, and the final adsorbent molded body of 320 g was obtained by drying it at room temperature under an atmospheric environment.
[0059] In the comparative example, when synthesizing the adsorbent, sodium silicate was added to a mixture of EB-PEI, tetraethylammonium phosphate, water, and ethanol (each component having the same weight ratio as in the experimental example) to synthesize the adsorbent. After impregnating the same carrier as in the experimental example with the adsorbent, it was dried at room temperature under an atmospheric environment to obtain a final adsorbent molded body of 320 g. The sodium silicate was included at 10 parts by weight based on 100 parts by weight of fumed silica.
[0060] Figures 6 and 7 show that the adsorption capacity was measured by placing the adsorption molded body in the one-pass reduction device shown in Figure 3 and maintaining it at 60 degrees Celsius 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 adsorption molded body in the one-pass reduction device, and "Downstream" indicates the concentration of carbon dioxide after passing through the adsorption molded body. "Comparative Example" and "Experimental Example" show the respective carbon dioxide adsorption efficiencies. Under conditions of a 5% carbon dioxide atmosphere similar to ship exhaust gas, the experimental example (18.04%) showed an improvement of more than 2.5% compared to the comparative example (15.53%) in terms of the average carbon dioxide absorption efficiency over 5 minutes, and the experimental example (139s) showed an improvement of more than 30% compared to the comparative example (107s) in terms of the maintenance time for 15% carbon dioxide absorption efficiency.
[0061] While embodiments of the present invention have been described above with reference to the attached drawings, those with ordinary skill in the art to which the present invention pertains should understand that the present invention can be implemented in other specific forms without altering its technical idea or essential features. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting.
Claims
1. In a method for manufacturing a dry carbon dioxide adsorption molded body that can be produced in large quantities, A step in which a carrier obtained by extruding a mixture of carrier raw materials and binder is sintered at a predetermined temperature; The steps include: and; and; A method for producing a dry carbon dioxide adsorbent molded article, comprising the step of physically impregnating the pores of the carrier with the adsorbent and then drying it.
2. The method for producing a dry carbon dioxide adsorbent molded article according to claim 1, characterized in that the binder is included in an amount of 50 to 70 parts by weight based on 100 parts by weight of the carrier raw material.
3. The method for producing a dry carbon dioxide adsorbent molded article according to claim 1, characterized in that the carrier material is one or more 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 structures.
4. The method for producing a dry carbon dioxide adsorbent molded article according to claim 1, characterized in that the binder is methylcellulose.
5. A method for producing a dry carbon dioxide adsorption molded article according to claim 1, characterized in that the carrier is sintered at 500 to 600 degrees Celsius.
6. The method for producing a dry carbon dioxide adsorption molded article according to claim 1, characterized in that the carrier is polyhedral, polygonal prism, or cylindrical in shape.
7. The method for producing a dry carbon dioxide adsorbent molded article according to claim 1, characterized in that the step of synthesizing the adsorbent is carried out without silicate.
8. The method for producing a dry carbon dioxide adsorbent molded article according to claim 1, characterized in that the adsorbent comprises 25 to 35% by weight of the amine compound, 2 to 8% by weight of the structure directing agent, and the remaining solvent.
9. The method for producing a dry carbon dioxide adsorbent molded article according to claim 1, characterized in that the solvent is one or more selected from the group consisting of water, methanol, ethanol, methyl chloride, carbon tetrachloride, and tetrahydrofuran.
10. The method for producing a dry carbon dioxide adsorbent molded article according to claim 1, characterized in that the amine compound is one or more selected from the group consisting of ethylenediamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, polyethyleneimine, and polypropyleneimine.
11. The method for producing a dry carbon dioxide adsorbent molded article according to claim 1, characterized in that the amine compound is polyethyleneimine modified by partial substitution with epoxybutane.
12. The aforementioned structure directing agent 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 A method for producing a dry carbon dioxide adsorbent molded article according to claim 1, characterized in that it is one or more selected from the group consisting of ).
13. A dry carbon dioxide adsorption molded body manufactured by the method described in any one of claims 1 to 12.