Adsorbent composition and method for producing the same

Abstract

To provide an adsorbent composition and a method for producing the same, capable of enhancing adsorption efficiency and / or capable of avoiding the adsorbent composition losing its effect.SOLUTION: An adsorbent composition comprises 100 pts.wt. of first particles and 3 to 450 pts.wt. of second particles. The first particles are base particles having an amino group and have a first heat release value. The second particles are base particles having an amino group and an epoxy group and have a second heat release value. The first heat release value is more than 90 J / g and 130 J / g or less. The second heat release value is 35 J / g or more and 90 J / g or less.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to an adsorbent composition and a method for manufacturing the same, and more particularly, to an adsorbent composition containing particles having different heat dissipation amounts and a method for manufacturing the same.

Background Art

[0002] Adsorbents are often used to adsorb and desorb gases such as carbon dioxide as a filling material for reactors such as fixed-bed reactors (also referred to as packed reactors). However, during adsorption and desorption, local areas in the reactor become high-temperature, and the adsorbent deteriorates, which may cause problems such as a decrease in adsorption efficiency and loss of the effect of the adsorbent composition. In addition, when a dispersion material is added as part of the filling material, stratification may occur during adsorption and desorption of the material due to the difference in density, which may lead to a decrease in adsorption efficiency. Furthermore, since the dispersion material occupies the volume inside the reactor, the total filling amount of the adsorbent decreases, which also leads to the problem of reducing the total adsorption amount of the system.

Summary of the Invention

Problems to be Solved by the Invention

[0003] Therefore, although existing adsorbent compositions and methods for manufacturing the same have met each requirement of their intended uses one by one, they do not perfectly meet all requirements in every aspect. Thus, there are still some problems that must be overcome regarding adsorbent compositions and methods for manufacturing the same.

Means for Solving the Problems

[0004] The adsorbent composition of the present disclosure may include adsorbent particles with different heat release amounts, which can enhance the adsorption efficiency and / or avoid the loss of the effect of the adsorbent composition. The adsorption efficiency may include the balance adsorption amount, the working adsorption amount, the balance adsorption recovery, the working adsorption recovery, and the like.

[0005] In some embodiments, an adsorbent composition is provided. The adsorbent composition includes 100 parts by weight of first particles and 3 to 450 parts by weight of second particles. The first particles are base particles having an amino group and having a first heat release amount. The second particles are base particles having an amino group and an epoxy group and having a second heat release amount. The first heat release amount is greater than 90 J / g and less than or equal to 130 J / g, and the second heat release amount is greater than or equal to 35 J / g and less than or equal to 90 J / g.

[0006] In some embodiments, a method for manufacturing an adsorbent composition is provided. The manufacturing method includes the step of preparing first particles, where the first particles are base particles having an amino group and having a first heat release amount. The first heat release amount is greater than 90 J / g and less than or equal to 130 J / g. Prepare second particles, where the second particles are base particles having an amino group and an epoxy group and having a second heat release amount. The second heat release amount is greater than or equal to 35 J / g and less than or equal to 90 J / g. Mix the first particles and the second particles to obtain an adsorbent composition. The first particles are 100 parts by weight, and the second particles are 3 to 450 parts by weight.

[0007] The adsorbent composition of the present disclosure can be used in a plurality of types of adsorption devices. In order to make the members and advantages of the present disclosure clearer and easier to understand, various embodiments will be given below and described in detail in correspondence with the accompanying drawings.

[0008] When read in conjunction with the drawings, the present disclosure can be more fully understood from the following detailed description. It should be noted that in accordance with industry standard practices, the components are not drawn to scale. In fact, for clarity, the dimensions of each component can be arbitrarily enlarged or reduced.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0010] Hereinafter, the adsorbent composition and its manufacturing method according to each embodiment in the present disclosure will be described in detail. In the following description, it should be understood that a plurality of different embodiments are presented as different aspects of some embodiments of the present disclosure. The specific components and arrangement methods described below are merely for concisely and clearly explaining some embodiments of the present disclosure. Of course, these are merely examples and not limitations to the present disclosure. Also, in different embodiments, the same or corresponding reference numerals may be used for similar and / or corresponding components to clearly explain the present disclosure. However, the use of these same or corresponding reference numerals is merely for concisely and clearly explaining some embodiments of the present disclosure and does not represent any correlation between the different embodiments and / or structures mentioned.

[0011] In the specification and claims, ordinal numbers such as "first", "second", etc. are used to modify components, and do not themselves imply or represent that there is a previous ordinal number for that (or those) component, nor do they represent the order of one component and another component or the order in a manufacturing method. It should be understood that these ordinal numbers are used only to clearly distinguish a component with a given name from another component with the same name. There may be cases where the same term is not used in the claims and the specification. For example, the first component in the specification may be the second component in the claims.

[0012] In this text, terms such as "approximate", "about", and "substantially" usually represent being within 10%, or 5%, or 3%, or 2%, or 1%, or 0.5% of a given value or range. Even when this given number is an approximate number, that is, when there is no specific description of "approximate", "about", or "substantially", the meaning of "approximate", "about", or "substantially" may be included. The expression "the range is between a first numerical value and a second numerical value" or "the first numerical value ~ the second numerical value" represents that the range includes the first numerical value, the second numerical value, and other numerical values therebetween. Further, there is a certain error between any two numerical values used for comparison. When it is said that a first numerical value is equal to a second numerical value, it means that there may be an error of about 10%, or within 5%, or within 3%, or within 2%, or within 1%, or within 0.5% between the first numerical value and the second numerical value. The expression "the value of the ratio of a first numerical value to a second numerical value" represents the value of the ratio (first numerical value / second numerical value) when the first numerical value is the numerator and the second numerical value is the denominator. The expression "the ratio of a first numerical value to a second numerical value" represents the ratio of the first numerical value: the second numerical value.

[0013] In the following description and claims, terms such as "comprising", "containing", "having", etc. are open-ended terms and thus must be construed to mean "including but not limited to". Therefore, when the terms "comprising", "containing" and / or "having" are used in the description of the present disclosure, it indicates the presence of the corresponding member, region, step, operation and / or element, but does not exclude the presence of one or more corresponding members, regions, steps, operations and / or elements.

[0014] It should be understood that the embodiments listed below can be combined with each other by replacing, rearranging, and combining the members in a plurality of different embodiments to form other embodiments, as long as they do not depart from the spirit of the present disclosure. Among the embodiments, the members can be arbitrarily combined and used as long as they do not violate or conflict with the spirit of the invention.

[0015] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art. It should be understood that, unless specifically defined in the embodiments of the present disclosure, these terms, such as those defined in a commonly used dictionary, should be construed to have a meaning consistent with the relevant art and the background or context of the present disclosure, and should not be construed in an idealized or overly formal manner.

[0016] In the following description, the "heat release amount" of the adsorbent particles is the heat release amount (joules (J)) in a gas environment of 10 volume percent (vol%) of carbon dioxide (90 vol% inert gas) per gram (g) of the adsorbent particles. Therefore, the unit of the heat release amount of the adsorbent particles can be J / g, and the numerical value is the pure numerical value of the heat released. Specifically, when it is described in the following description that the "heat release amount of the adsorbent particles is (A J / g)", it means that each gram of the adsorbent particles releases an absolute value of A joules of heat to the gas environment. Furthermore, depending on the composition of the gas environment, the heat release amount of the adsorbent particles can be changed. For example, when the same adsorbent particles are placed in different gas environments, the heat release amount of the adsorbent particles changes. The heat release amount of the adsorbent particles can be measured by a thermogravimetric analysis (TGA) and a differential scanning calorimetry (DSC).

[0017] In the following description, the "average heat release amount" of the adsorbent composition is obtained by calculating based on the weight ratio of different particles in the adsorbent composition. For example, the average heat release amount can be the sum of the product of the weight part (a dimensionless) of the first particle and the heat release amount (A J / g) of the first particle and the product of the weight part (b dimensionless) of the second particle and the heat release amount (B J / g) divided by the total weight part of the first particle and the second particle ((a×A + b×B) / (a + b)). For example, the average heat release amount can be the sum of the product of the weight percentage (a wt%) of the first particle in the adsorbent composition and the heat release amount (A J / g) of the first particle and the product of the weight percentage (b wt%) of the second particle in the adsorbent composition and the heat release amount (B J / g) (a wt%×A + b wt%×B).

[0018] Please refer to FIG. 1. A flowchart of a method for manufacturing an adsorbent composition according to some embodiments of the present disclosure is shown.

[0019] In step S1, prepare the first particles. In some embodiments, the first particles are base particles having an amino group, and the first particles have a first heat dissipation amount. In some embodiments, the first heat dissipation amount may be greater than 90 J / g and not more than 130 J / g. For example, the first heat dissipation amount may be 90.1 J / g, 100 J / g, 110 J / g, 111 J / g, 112 J / g, 112.9 J / g, 113 J / g, 114 J / g, 115 J / g, 119.6 J / g, 120 J / g, 130 J / g, or any value between these numerical values or a range of numerical values consisting of any numerical values, but the present disclosure is not limited thereto. For example, the first heat dissipation amount may be 90.1 J / g to 130 J / g, 100 J / g to 119.6 J / g, or 110 J / g to 115 J / g, but the present disclosure is not limited thereto.

[0020] In some embodiments, the step of preparing the first particles may include step a of mixing a base particle and a metal chelating agent to obtain a first powder, step b of mixing a material containing an amino group and the first powder to obtain a second powder, and step c of mixing the second powder and an adhesive to obtain the first particles. It may include.

[0021] In some embodiments, the base particle may include silicon dioxide, aluminum oxide, titanium oxide, calcium silicate, carbon nanotube, activated carbon, acetate fiber, their analogs or combinations thereof, but the present disclosure is not limited thereto. In some embodiments, the base particle may be a porous or non-porous powder material. In some embodiments, the particle size of the base particle may be from 1 μm to 500 μm. For example, the particle size of the base particle may be 1 μm, 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, or any value between these numbers or a range of values consisting of any of these numbers, but the present disclosure is not limited thereto.

[0022] In some embodiments, the metal chelating agent is used to chelate the metal element in the base particle, and it is possible to avoid the metal ions in the base particle from becoming impurities and causing disturbances. In some embodiments, the metal chelating agent may be an inorganic metal chelating agent, an organic metal chelating agent or a combination thereof. In some embodiments, the inorganic metal chelating agent may include sodium phosphate.

[0023] In some embodiments, the amine group material may include a compound or polymer having a primary amine group (-NH2), a secondary amine group (-NHR), or a tertiary amine group (-NR2). In some embodiments, the molecular weight of the amine group material may be 500 or more and less than 10,000. For example, the molecular weight of the amine group material may be 500 to 9999, 3000 to 9999, 5000 to 8000, 600 to 3000, or 800 to 1200, but the present disclosure is not limited thereto. In some embodiments, the amine group material may include linear polyethyleneimine (PEI), branched polyethyleneimine, or a combination thereof, but the present disclosure is not limited thereto.

[0024] In some embodiments, in the first particles, the value of the ratio of the weight of the amine group material to the weight of the base particles may be 0.5 to 0.75. For example, in the first particles, the value of the ratio of the weight of the amine group material to the weight of the base particles may be 0.5, 0.55, 0.6, 0.64, 0.65, 0.7, 0.75, or any numerical value between these numerical values or any range of numerical values consisting of these numerical values, but the present disclosure is not limited thereto. For example, in the first particles, the value of the ratio of the weight of the amine group material to the weight of the base particles may be 0.55 to 0.7 or 0.6 to 0.65, but the present disclosure is not limited thereto.

[0025] In some embodiments, the adhesive may include nitrile butadiene rubber latex, chloroprene rubber, styrene-butadiene rubber, analogs thereof, or combinations thereof, but the present disclosure is not limited thereto. In some embodiments, the weight of the adhesive is 0.5% to 30% of the total weight of the first particles. For example, the weight of the adhesive is 0.5%, 1%, 4%, 4.1%, 5%, 10%, 20%, 30% of the total weight of the first particles, or any numerical value or range of numerical values between these values, but the present disclosure is not limited thereto.

[0026] In step S2, second particles are prepared. In some embodiments, the second particles are base particles having an amino group and an epoxy group, and the second particles have a second heat dissipation amount. In some embodiments, the second heat dissipation amount may be 35 J / g or more and 90 J / g or less. For example, the second heat dissipation amount is 35 J / g, 40 J / g, 45 J / g, 45.1 J / g, 46 J / g, 50 J / g, 55 J / g, 60 J / g, 63 J / g, 63.3 J / g, 64 J / g, 65 J / g, 69 J / g, 69.2 J / g, 70 J / g, 75 J / g, 76 J / g, 76.3 J / g, 77 J / g, 80 J / g, 85 J / g, 90 J / g, or any numerical value or range of numerical values between these values, but the present disclosure is not limited thereto. For example, the second heat dissipation amount may be 35 J / g to 90 J / g, 40 J / g to 85 J / g, or 45 J / g to 80 J / g, but the present disclosure is not limited thereto.

[0027] In some embodiments, the second particle may include a third particle and a fourth particle. The third particle may have a third heat dissipation amount, and the fourth particle may have a fourth heat dissipation amount different from the third heat dissipation amount. In some embodiments, the third heat dissipation amount may be greater than 65 J / g and less than or equal to 90 J / g. For example, the third heat dissipation amount may be 66 J / g, 69 J / g, 69.2 J / g, 70 J / g, 75 J / g, 76 J / g, 76.3 J / g, 77 J / g, 80 J / g, 85 J / g, 90 J / g, or any numerical value between these numerical values or a numerical range consisting of any numerical values, but the present disclosure is not limited thereto. For example, the third heat dissipation amount may be 66 J / g to 90 J / g, 66 J / g to 80 J / g, or 69 J / g to 77 J / g, but the present disclosure is not limited thereto. In some embodiments, the fourth heat dissipation amount may be 35 J / g or more and less than 65 J / g. For example, the fourth heat dissipation amount may be 35 J / g, 40 J / g, 45 J / g, 45.1 J / g, 46 J / g, 50 J / g, 55 J / g, 60 J / g, 63 J / g, 63.3 J / g, 64.9 J / g, or any numerical value between these numerical values or a numerical range consisting of any numerical values, but the present disclosure is not limited thereto. For example, the fourth heat dissipation amount may be 35 J / g to 64.9 J / g, 40 J / g to 64 J / g, or 45 J / g to 64 J / g, but the present disclosure is not limited thereto.

[0028] In some embodiments, the step of preparing the second particle may include step d of mixing a material containing an amino group and an epoxide to obtain a solution, step e of mixing the solution and the first powder to obtain a third powder, and step f of mixing the third powder and an adhesive to obtain the second particle.

[0029] ​In some embodiments, the epoxide may include ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-epoxypentane, 1,2-epoxyhexane, their analogs, or combinations thereof, but the present disclosure is not limited thereto. In some embodiments, the value of the ratio of the weight of the epoxide to the weight of the material containing an amino group may be greater than 0. In some embodiments, the value of the ratio of the weight of the epoxide to the weight of the material containing an amino group is 0.01 to 0.8. For example, the value of the ratio of the weight of the epoxide to the weight of the material containing an amino group may be 0.01, 0.1, 0.2, 0.3, 0.4, 0.5, 0.58, 0.588, 0.59, 0.594, 0.6, 0.7, 0.8, or any numerical value between these numerical values or any range of numerical values consisting of any of these numerical values, but the present disclosure is not limited thereto.

[0030] In some embodiments, the third particles and the fourth particles can be obtained by preparing the value of the ratio of the weight of the epoxide to the weight of the material containing an amino group. For example, in the third particles, the value of the ratio of the weight of the epoxide to the weight of the material containing an amino group may be 0.4 to 0.7, 0.5 to 0.6, or 0.594, but the present disclosure is not limited thereto. For example, in the fourth particles, the value of the ratio of the weight of the epoxide to the weight of the material containing an amino group may be 0.4 to 0.7, 0.5 to 0.6, or 0.594, but the present disclosure is not limited thereto.

[0031] In some embodiments, the value of the ratio of the weight of the material containing an amino group to the weight of the base particles in the second particles may be from 0.2 to 0.65. For example, in the second particles, the value of the ratio of the weight of the material containing an amino group to the weight of the base particles may be 0.2, 0.25, 0.3, 0.31, 0.32, 0.33, 0.35, 0.4, 0.45, 0.5, 0.51, 0.52, 0.55, 0.6, 0.64, 0.65, or any value between these numbers or any range of values consisting of any of these values, but the present disclosure is not limited thereto. For example, in the second particles, the value of the ratio of the weight of the material containing an amino group to the weight of the base particles may be from 0.2 to 0.55, or from 0.25 to 0.53, but the present disclosure is not limited thereto.

[0032] In some embodiments, the third particles and the fourth particles can be obtained by adjusting the value of the ratio of the weight of the material containing an amino group to the weight of the base particles. For example, in the third particles, the value of the ratio of the weight of the material containing an amino group to the weight of the base particles may be from 0.45 to 0.65 or from 0.5 to 0.55, but the present disclosure is not limited thereto. For example, in the fourth particles, the value of the ratio of the weight of the material containing an amino group to the weight of the base particles may be from 0.2 to 0.45, from 0.25 to 0.4, or from 0.3 to 0.35, but the present disclosure is not limited thereto.

[0033] In step S3, the first particles and the second particles are mixed to obtain an adsorbent composition. In some embodiments, the first particles may be 100 parts by weight, and the second particles may be 3 to 450 parts by weight. For example, the parts by weight of the second particles may be 3, 4, 4.16, 5, 10, 13.63, 50, 100, 108.37, 125, 132.65, 150, 175, 200, 225, 250, 257.14, 275, 300, 325, 334.7, 350, 375, 400, 425, 450, or any numerical value between these values or any range of numerical values consisting of any numerical values, but the present disclosure is not limited thereto. If the parts by weight of the second particles are less than 3, the adsorbent composition may deteriorate due to heat destruction during adsorption and desorption. If the parts by weight of the second particles are greater than 450, the adsorption amount of the adsorbent composition may be excessively low.

[0034] In some embodiments, the weight of the first particles is 20% to 90% of the total weight of the adsorbent composition, and the weight of the second particles is 10% to 80% of the total weight of the adsorbent composition. For example, the weight of the first particles may be 20%, 23%, 28%, 30%, 40%, 48%, 50%, 60%, 70%, 80%, 88%, 90% of the total weight of the adsorbent composition, or any numerical value between these values or any range of numerical values consisting of any numerical values, but the present disclosure is not limited thereto. If the weight of the first particles occupies more than 80% of the total weight of the adsorbent composition, the adsorbent composition may deteriorate due to heat destruction during adsorption and desorption. If the weight of the first particles occupies less than 20% of the total weight of the adsorbent composition, the adsorption amount of the adsorbent composition may be excessively low. In some embodiments, the ratio of the weight of the first particles to the weight of the second particles is 20 to 90:10 to 80. For example, the ratio of the weight of the first particles to the weight of the second particles may be 20 to 50:50 to 80.

[0035] In some embodiments, the second particles may contain from 0 to 330 parts by weight of the third particles and from 0 to 150 parts by weight of the fourth particles, and the third particles and the fourth particles may not be 0 parts by weight at the same time. In other words, the second particles may contain at least the third particles or the fourth particles. For example, the parts by weight of the third particles may be 0, 2, 2.08, 2.27, 4.65, 5, 10, 11.36, 20, 50, 100, 104.2, 125, 150, 175, 200, 225, 250, 275, 300, 325, 326, 330, or any numerical value between these numerical values or a range of numerical values consisting of any numerical value, but the present disclosure is not limited thereto. For example, the parts by weight of the fourth particles may be 0, 2, 2.08, 2.27, 4.17, 5, 7.14, 8.7, 10, 11.36, 25, 50, 75, 80, 100, 125, 128, 150, or any numerical value between these numerical values or a range of numerical values consisting of any numerical value, but the present disclosure is not limited thereto. If the parts by weight of the third particles are greater than 330, or the parts by weight of the fourth particles are greater than 150, the adsorption amount of the adsorbent composition may be excessively low.

[0036] In some embodiments, the average heat release amount of the adsorbent composition may be 65 J / g or more and 120 J / g or less. For example, the average heat release amount of the adsorbent composition may be 65 J / g to 119.9 J / g, 70 J / g to 115 J / g, 75 J / g to 110 J / g, or 80 J / g to 105 J / g, but the present disclosure is not limited thereto. If the average heat release amount of the adsorbent composition is greater than 120 J / g, the adsorbent composition may deteriorate due to heat destruction during adsorption and desorption. If the average heat release amount of the adsorbent composition is less than 65 J / g, the adsorption amount of the adsorbent composition may be excessively low.

[0037] In some embodiments, the first particle may contain an amino group, and the second particle may contain an amino group and an epoxy group. In some embodiments, the content of the amino group in the first particle may be greater than the content of the amino group in the second particle, and thus the adsorption amount of carbon dioxide by the first particle may be higher than the adsorption amount of carbon dioxide by the second particle. In some embodiments, the third particle and the fourth particle may each contain an amino group and an epoxy group, and the content of the amino group in the third particle may be greater than the content of the amino group in the fourth particle.

[0038] The more amino groups there are in the adsorption particles, the more easily carbon dioxide can be adsorbed (collected), and the adsorption amount of carbon dioxide increases. Since the epoxy group causes a cross-linking reaction with the amino group, the content of the amino group capable of adsorbing carbon dioxide decreases. Therefore, the more epoxy groups there are in the adsorption particles, the more difficult it is for the adsorption particles to adsorb carbon dioxide, and the adsorption amount of carbon dioxide decreases. Therefore, the higher the adsorption amount of carbon dioxide, the more likely the exothermic reaction occurs, and the temperature in the reactor rises at least locally, deteriorating the adsorption particles. For example, if it can be observed that the appearance of the adsorption particles changes from white to yellow, it indicates the deterioration of the adsorption particles.

[0039] In some embodiments, the density of the first particle and the second particle is 0.3 g / cm 3 ~0.8 g / cm 3 and may be. For example, the density of the first particle and the second particle is 0.3 g / cm 3 、0.4 g / cm 3 、0.5 g / cm 3 、0.58 g / cm 3 、0.6 g / cm 3 、0.63 g / cm 3 、0.65 g / cm 3 、0.67 g / cm 3 、0.7 g / cm 3 、0.72 g / cm 3 、0.8 g / cm 3or any numerical value or range of numerical values between these numerical values, although the present disclosure is not limited thereto. In some embodiments, the density of the first particle is 0.58 g / cm 3 ~0.65 g / cm 3 and the density of the second particle may be 0.6 g / cm 3 ~0.72 g / cm 3 In some embodiments, the density of the third particle is 0.67 g / cm 3 ~0.72 g / cm 3 and the density of the fourth particle may be 0.6 g / cm 3 ~0.63 g / cm 3

[0040] In some embodiments, the adsorbent composition of the present disclosure can be used to adsorb and desorb gases. For example, the gas may be carbon dioxide or other suitable gases, although the present disclosure is not limited thereto. In some embodiments, the adsorbent composition of the present disclosure can be used as a filling material for a reactor. For example, the reactor may be a fixed-bed reactor or other suitable reactor, although the present disclosure is not limited thereto.

[0041] In the following description, an example of a method for manufacturing an adsorbent composition will be given and described.

[0042] In some embodiments, the base particles in step a are silicon dioxide powder with an average particle size of 35 μm, and the metal chelating agent is a phosphate. Specifically, the moisture in the silicon dioxide powder was removed at a temperature of 100°C. The phosphate was dissolved in water, mixed and stirred with the silicon dioxide powder from which the moisture had been removed, and then the moisture was removed at a temperature of 100°C using a vacuum oven to obtain the first powder.

[0043] ​In some embodiments, the material containing an amino group in step b is polyethyleneimine (molecular weight: 1200). Specifically, polyethyleneimine was added to a solvent (such as alcohol) to obtain a polyethyleneimine solution. After mixing and stirring the polyethyleneimine solution and the first powder, it was dried to obtain a second powder. Drying was carried out at a temperature of 40°C to 50°C under negative pressure.

[0044] In some embodiments, the adhesive in step c is chloroprene rubber (including a polymer of about 50 wt% of 2,3-dichloro-1,3-butadiene and 2-chloro-1,3-butadiene (1,3-butadiene, 2,3-dichloro-, polymer with 2-chloro-1,3-butadiene), or including a polymer of about 45 wt% of 2-methyl-2-propenoic acid and 2-chloro-1,3-butadiene (2-propenoic acid, 2-methyl-, polymer with 2-chloro-1,3-butadiene)). Specifically, after wetting the second powder with deionized water, the adhesive was added and mixed and stirred, and then water was removed at a temperature of 105°C under vacuum to obtain the first particles. In some embodiments, granulation can be further carried out with a syringe or a granulator. In some other embodiments, the granulation step can be omitted.

[0045] In some embodiments, the epoxide in step d is butylene oxide. Specifically, butylene oxide was dropped into the polyethyleneimine solution and uniformly stirred at room temperature (such as 25°C) to allow the cross-linking reaction to proceed, and a transparent and clear solution was obtained.

[0046] In some embodiments, in step e, after mixing and stirring the transparent and clear liquid and the first powder, a milky white liquid containing a white suspension was obtained. The milky white liquid was dried to obtain a third powder. The milky white liquid can be dried at a temperature of 40°C to 50°C under negative pressure.

[0047] In some embodiments, during step f, after wetting the third powder with deionized water, adding an adhesive and mixing and stirring, and then removing moisture at a temperature of 105°C under vacuum, the second particles were obtained. In some embodiments, a granulation step can be further performed, or the granulation step can be omitted.

[0048] Therefore, the present disclosure can adjust the heat release amount when the adsorption particles adsorb and / or desorb carbon dioxide by adjusting the ratio of polyethyleneimine (providing amino groups) to butylene oxide (providing epoxy groups) (amino group-epoxy group modification amount), and the ratio of polyethyleneimine to silicon dioxide powder (coating amount of amino groups on the surface of the silicon dioxide powder). Therefore, adsorption particles with similar densities but different heat release amounts can be obtained.

[0049] In some embodiments, examples are provided in which the adsorbent composition includes first particles and second particles, and the second particles include third particles and fourth particles.

[0050] First particles: After heating and drying 50 g of porous silicon powder at 100°C to remove moisture, it was mixed and stirred with 260 g of a 0.79 wt.% sodium phosphate aqueous solution for 2 hours, and then vacuum dried at 100°C again to remove moisture, obtaining a white powder. 94 g of a 34 wt.% polyethyleneimine aqueous solution was prepared, mixed and stirred with the white powder for 2 hours, and the solution was removed under negative pressure at 40°C, obtaining an amino group-modified white powder. 5 g of the amino group-modified white powder was taken, wetted with deionized water, and then 0.65 g of an adhesive was further added and mixed and stirred. Then, moisture was removed by heating and drying under vacuum at 105°C, obtaining white first particles with a high heat release amount and a high carbon dioxide adsorption amount. The value of the ratio of the weight of the amino group-containing material to the weight of the base particles is about 0.64.

[0051] Third particle: After heating and drying 50 g of porous silicon powder at 100 °C to remove moisture, it was mixed and stirred with 260 g of a 0.79 wt.% sodium phosphate aqueous solution for 2 hours, and then vacuum dried at 100 °C again to remove moisture, obtaining a white powder. 94 g of a 34 wt.% polyethyleneimine aqueous solution was prepared, 19 g of butylene oxide was added dropwise, and the mixture was mixed and stirred at 25 °C for 20 hours. Then, it was further mixed and stirred with the white powder for 2 hours, and the solution was removed under negative pressure at 40 °C to obtain an amino group-epoxy group modified white powder. 5 g of the amino group-epoxy group modified white powder was taken, moistened with deionized water, and then 0.65 g of an adhesive was further added and mixed and stirred. Subsequently, moisture was removed by vacuum drying at 105 °C and heat dried to obtain white third particles with a medium heat release amount and a medium carbon dioxide adsorption amount. The value of the ratio of the weight of the amino group-containing material to the weight of the base particles is about 0.64. The value of the ratio of the weight of the epoxide to the weight of the amino group-containing material is about 0.594.

[0052] Fourth particle: After heating and drying 50 g of porous silicon powder at 100 °C to remove moisture, it was mixed and stirred with 260 g of a 0.79 wt.% sodium phosphate aqueous solution for 2 hours, and then vacuum dried at 100 °C again to remove moisture, obtaining a white powder. 47 g of a 34 wt.% polyethyleneimine aqueous solution was prepared, 9.5 g of butylene oxide was added dropwise, and the mixture was mixed and stirred at 25 °C for 20 hours. Then, it was further mixed and stirred with the white powder for 2 hours, and the solution was removed under negative pressure at 40 °C to obtain an amino group-epoxy group modified white powder. 5 g of the amino group-epoxy group modified white powder was taken, moistened with deionized water, and then 0.65 g of an adhesive was further added and mixed and stirred. Subsequently, moisture was removed by vacuum drying at 105 °C and heat dried to obtain white fourth particles with a low heat release amount and a low carbon dioxide adsorption amount. The value of the ratio of the weight of the amino group-containing material to the weight of the base particles is about 0.32. Therefore, the coating amount of amino groups on the surface of the fourth particles can be smaller than the coating amount of amino groups on the surface of the third particles. The value of the ratio of the weight of the epoxide to the weight of the amino group-containing material is about 0.594. Therefore, the amino group-epoxy group modification amount of the third particles may be similar to the amino group-epoxy group modification amount of the fourth particles.

[0053] Refer to FIG. 2. It shows a Fourier transform infrared spectroscopy (FTIR) analysis diagram according to some embodiments of the present disclosure. The adsorbed particles were placed in an oven at 105° C. to remove moisture, pulverized, and then analyzed by FTIR. The test wavelength was 4000 cm -1 ~400 cm -1 as shown. As shown in FIG. 2, the first particles, the third particles, and the fourth particles have a peak indicating -NH2 (primary amine) at 1564 cm -1 ~1587 cm -1 and a peak indicating -NHR (secondary amine) at 3275 cm -1 . As shown in FIG. 2, the content of primary amine in the first particles is greater than that in the third particles and the fourth particles, and the content of primary amine in the third particles is greater than that in the fourth particles. As shown in FIG. 2, the content of secondary amine in the first particles is greater than that in the third particles and the fourth particles, and the content of secondary amine in the third particles is greater than that in the fourth particles.

[0054] In some embodiments, the thermal performance of the adsorbed particles was analyzed by a thermogravimetric analyzer (TGA) and a differential scanning calorimeter (DSC) in a gas environment of 10% CO2. Also, the particle density could be calculated by measuring the volume of the particles and weighing them with a balance. The results are as shown in Table 1.

[0055]

Table 1

[0056] As can be seen from Table 1, the first particles have a high carbon dioxide adsorption capacity. If they are directly used as the filling for a carbon dioxide adsorption fixed bed reactor, the heat release amount due to adsorption becomes excessively high and the local area becomes high temperature, which not only deteriorates the first particles but also easily reduces the adsorption performance. In contrast, the second particles have a low heat release amount, but the carbon dioxide adsorption amount is excessively low, and the total carbon dioxide adsorption amount in the reactor may decrease. Also, the densities of particles with different heat release amounts are similar, about 0.58 - 0.72 g / cm3 Although it is in between, it indicates that the adsorbed particles can be uniformly mixed and dispersed, and it is less likely that a stratification effect will occur due to the turbulent flow of the air current and the dispersion function will be lost.

[0057] On the other hand, 10 g of the first particles (particle density: 0.58 - 0.65 g / cm 3 ) and 10 g of silica sand (particle density: 2.65 g / cm 3 ) were mixed and placed in a flask, and when they were mixed and stirred with a glass rod, the first particles and the silica sand stratified within 30 seconds after stirring. This shows that when the adsorbed particles and conventional dispersion materials (for example, silica sand, ceramic balls, steel balls, ceramic rings, metal rings) are mixed, due to the excessive difference in particle density, they cannot be uniformly dispersed.

[0058] Adsorbed particle fixed bed column adsorption / desorption cycle test (one):

[0059] Based on Table 2, the adsorbent compositions of Examples 1 - 10 and Comparative Examples 1 and 2 were prepared as samples. The average heat release amount was calculated from the ratio of the adsorbed particles and the heat release amount. For example, the heat release amount of the first particles can be 112.9 J / g and the adsorption amount can be 2.01 mmol CO2 / g. For example, the heat release amount of the third particles can be 76.3 J / g and the adsorption amount can be 1.21 mmol CO2 / g. For example, the heat release amount of the fourth particles can be 63.3 J / g and the adsorption amount can be 0.84 mmol CO2 / g.

[0060]

Table 2

[0061] 15 g of the sample was taken and packed into a fixed-bed column. A mixed gas of 10 vol.% CO2 and 10 vol.% H2O was used as the target gas. The adsorption conditions were a gas supply temperature of 50 °C and a flow rate of 0.4 liters per minute (L / min). The desorption conditions were a desorption temperature of 100 °C and a pressure of 0.2 bar. The desorption process was terminated when the CO2 concentration reached 2% - 3%. The above adsorption / desorption process was defined as one cycle, and a total of 5 cycles were performed. The results are shown in Table 3.

[0062] Also, the appearance of the sample before and after 5 cycles of adsorption / desorption was observed and recorded. The "-" in the appearance indicates that there was no obvious difference in the appearance.

[0063] Please refer to Figure 3. It is a diagram of the breakthrough curve according to some embodiments of the present disclosure. The adsorbed amount may include the working adsorbed amount and the equilibrium adsorbed amount. The methods of measurement and calculation are as follows. At the start time (t0), CO2 was flowed into the fixed-bed column at a constant inlet concentration (C in ). CO2 was adsorbed by the adsorption particles at the initial stage, and the CO2 concentration in the outlet gas decreased. Over time, the adsorption particles continued to adsorb CO2 until saturation was reached. Therefore, it was measured that the CO2 concentration in the outlet gas increased over time. When the CO2 concentrations in the outlet gas and the inlet gas became equal, it indicated that the adsorption had reached saturation and the adsorption reaction had reached equilibrium. As shown in Figure 3, when the CO2 concentration of the outlet gas is plotted against time, an S-shaped curve is obtained, which is called the breakthrough curve (BTC). At the breakthrough time (t b ), the outlet concentration was 10% of the inlet concentration (C out = 0.1C in ). At the equilibrium time (t e ), the outlet concentration was equal to the inlet concentration (C out = C in ), and the adsorption equilibrium was reached. The CO2 adsorption amount is the product of the inlet concentration (C in ) and the inlet flow rate (Q in ), and the product of the outlet concentration (C out ) and the outlet flow rate (Q outThe value of the difference from the product of ()) is integrated with respect to time. The adsorption amount integrated from t0 to t b is referred to as the working adsorption amount. The adsorption amount integrated from t0 to t e is referred to as the equilibrium adsorption amount. Equilibrium adsorption recovery rate (recovery, %): 5th equilibrium adsorption amount / 1st equilibrium adsorption amount × 100% Working adsorption recovery rate: 5th working adsorption amount / 1st working adsorption amount × 100%

[0064]

Table 3

[0065] As shown in Table 2 and Table 3, the average heat release amounts of Examples 2 - 5, 6 - 8, 9 and 10 are between 80 J / g and 105 J / g, and their working adsorption recovery rates are all greater than 80%, their equilibrium adsorption recovery rates are all greater than 86%, their equilibrium adsorption amounts are greater than 41 mg / g, and their equilibrium adsorption amounts are greater than 28 mg / g. In Examples 2 - 4, 6, 7, 9 and 10, the weight of the first particles is 28% - 88% of the total weight of the adsorbent composition, and their equilibrium adsorption recovery rates are all greater than 86%, their equilibrium adsorption amounts are greater than 52 mg / g, and their equilibrium adsorption amounts are greater than 33 mg / g.

[0066] As shown in Table 2 and Table 3, Comparative Example 1 adsorbs carbon dioxide using a single high heat release amount adsorbing particle, and both its working adsorption amount and equilibrium adsorption amount are lower than those of Examples 9 and 10, and its working adsorption recovery rate and equilibrium adsorption recovery rate are also lower than those of Examples 9 and 10. Furthermore, the appearance of Comparative Example 1 has a yellowish tint, which indicates that the amino groups in the adsorbing particles have deteriorated and discolored due to high temperature. In contrast, Examples 9 and 10 mix adsorbing particles with different heat release amounts, and without adding a dispersion material additionally, the adsorption efficiency is significantly improved and there is no change in appearance. This shows that the adsorbent composition containing adsorbing particles with different heat release amounts can enhance the repeated adsorption / desorption performance of the material and avoid deterioration due to local high temperature.

[0067] As shown in Table 2 and Table 3, as can be seen from observing Example 1, Example 2, and Example 6, when the ratios of the third particles and the fourth particles in the sample are increased to 10% respectively, the working adsorption capacity and the working adsorption recovery rate can be improved simultaneously.

[0068] Since the adsorbent composition of the present disclosure contains particles with different heat dissipation amounts, the adsorption efficiency (for example, equilibrium adsorption capacity, working adsorption capacity, equilibrium adsorption recovery rate, and working adsorption recovery rate) can be increased, and / or the loss of the effect of the adsorbent composition can be avoided. The manufacturing method of the present disclosure can obtain an adsorbent composition by changing the heat dissipation amount of the particles by adjusting the amino group content in different particles.

[0069] For example, the heat dissipation amount of the first particles can be made larger than that of the second particles, and the first particles and the second particles can be mixed at a specific ratio to form an adsorbent composition. Therefore, by adjusting the average heat dissipation amount of the adsorbent composition, the occurrence of high temperature in the reactor can be avoided. Furthermore, the deterioration of the adsorbent composition can be effectively avoided, the adsorption efficiency can be improved, and / or the loss of the effect of the adsorbent composition can be avoided. For example, the adsorbent composition of the present disclosure can be used alone without being combined with a dispersion material. Thereby, the occurrence of stratification in the reactor can be avoided, the content of the adsorbent composition in the reactor can be increased, and the adsorption efficiency can be improved.

[0070] The protection scope of the present disclosure is not limited to the processes, machines, manufactures, compositions of matter, apparatuses, methods, and steps of the specific embodiments described in the specification. For those with ordinary knowledge in the relevant technical field, from the content of the present disclosure, they can understand existing or future-developed processes, machines, manufactures, compositions of matter, apparatuses, methods, and steps. As long as they can perform substantially the same functions or achieve substantially the same results as those in the embodiments described in this specification, they can all be used based on the present disclosure. Therefore, the protection scope of the present disclosure includes the above-mentioned processes, machines, manufactures, compositions of matter, apparatuses, methods, and steps. All embodiments or claims of the present disclosure do not need to achieve all the objectives, advantages, and / or features disclosed by the present disclosure.

[0071] As described above, a plurality of embodiments have been briefly described so that those with ordinary knowledge in the technical field to which the present disclosure pertains can better understand the perspectives of the embodiments of the present disclosure. Those with ordinary knowledge in the technical field to which the present disclosure pertains should understand that they can design or modify other processes and structures based on the embodiments of the present disclosure and achieve the same objectives and / or advantages as those introduced in this specification. Also, those with ordinary knowledge in the technical field to which the present disclosure pertains should understand that such equivalent processes and structures do not deviate from the spirit and scope of the present disclosure, and they can make various changes, substitutions, and replacements without contravening the spirit and scope of the present disclosure.

Description of Reference Numerals

[0072] Steps S1, S2, S3…

Claims

1. 1. An adsorbent composition comprising: 100 g of a first particle, which is a first base particle modified with an amino group and has a first heat dissipation amount; 3 to 450 parts by weight of second particles, the second particles being second base particles modified with amino groups and epoxy groups and having a second heat dissipation amount; Including, 1. An adsorbent composition, wherein in a gas environment of 10% by volume carbon dioxide and 90% by volume of an inert gas, the first heat release is greater than 90 J / g and less than or equal to 130 J / g, and the second heat release is greater than or equal to 35 J / g and less than or equal to 90 J / g.

2. 2. The adsorbent composition of claim 1, wherein the content of amino groups in the first particles is greater than the content of amino groups in the second particles.

3. The second particles are 0 to 330 parts by weight of third particles having a third heat release amount, the third heat release amount being greater than 65 J / g and less than or equal to 90 J / g in a gas environment of 10% by volume of carbon dioxide and 90% by volume of an inert gas; 0 to 150 parts by weight of fourth particles having a fourth heat release amount different from the third heat release amount, the fourth heat release amount being 35 J / g or more and less than 65 J / g in a gas environment of 10% by volume of carbon dioxide and 90% by volume of an inert gas. Including, 2. The adsorbent composition of claim 1, wherein the third particles and the fourth particles are not simultaneously 0 parts by weight.

4. The adsorbent composition of claim 3 , wherein the content of amino groups in said third particles is greater than the content of amino groups in said fourth particles.

5. 2. The sorbent composition of claim 1, wherein the average heat release of the sorbent composition is 65 J / g or more and 120 J / g or less in a gas environment of 10% by volume carbon dioxide and 90% by volume of an inert gas.

6. 1. A method for producing an adsorbent composition, comprising: providing a first base particle modified with an amino group, the first particle having a first heat release, the first heat release being greater than 90 J / g and less than or equal to 130 J / g in a gas environment of 10% by volume carbon dioxide and 90% by volume of an inert gas; preparing a second base particle modified with an amino group and an epoxy group, the second particle having a second heat release amount, the second heat release amount being 35 J / g or more and 90 J / g or less in a gas environment of 10% by volume of carbon dioxide and 90% by volume of an inert gas; mixing the first particles and the second particles to obtain the sorbent composition; Including, The first particles are 100 parts by weight, The second particles are 3 to 450 parts by weight. Manufacturing method.

7. The step of providing first particles further comprises: mixing the first base particles with a metal chelating agent to obtain a first powder; mixing a material containing an amino group with the first powder to obtain a second powder; mixing the second powder with an adhesive to obtain the first particles; Including, The method according to claim 6, wherein the ratio of the weight of the material containing an amino group to the weight of the first base particle is 0.5 to 0.

75.

8. The step of providing second particles further comprises: mixing the second base particles with the metal chelating agent to obtain a third powder; mixing the amino group-containing material and an epoxide to obtain a solution; mixing the solution with the third powder to obtain a fourth powder; mixing the fourth powder with the adhesive to obtain the second particles; Including, The method according to claim 6, wherein the ratio of the weight of the epoxide to the weight of the material containing an amino group is 0.01 to 0.

8.

9. The method according to claim 8, wherein the ratio of the weight of the material containing amino groups to the weight of the second base particles is 0.2 to 0.65.

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