TWI886674B - Adsorbent composition and manufacturing method thereof - Google Patents

Abstract

An adsorbent composition and a manufacturing method thereof provided. The adsorbent composition includes 100 parts by weight of a first particle and 3 to 450 parts by weight of a second particle. The first particle is base particle with an amine group and has a first heat release amount. The second particle is base particle with an amine group and an epoxy group, and has a second heat release amount. Wherein, 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.

Description

Adsorbent composition and method for producing the same

The present disclosure relates to an adsorbent composition and a method for making the same, and in particular to an adsorbent composition comprising particles having different exothermic values and a method for making the same.

Adsorbents are often used as packing materials in reactors such as fixed-bed reactors (also known as packed bed reactors) to adsorb and desorb gases such as carbon dioxide. However, during the adsorption and desorption period, local high temperatures may occur in the reactor, causing the adsorbent to deteriorate, resulting in reduced adsorption efficiency and failure of the adsorbent composition. In addition, when a dispersed material is added as part of the packing material, the material may be stratified during adsorption and desorption due to density differences, resulting in reduced adsorption efficiency. Furthermore, the dispersed material will occupy the volume in the reactor, which will reduce the total amount of adsorbent filled, and also lead to a problem of reduced total adsorption of the system.

Therefore, although the existing adsorbent compositions and their manufacturing methods have gradually met their intended uses, they still do not fully meet the requirements in all aspects. Therefore, there are still some problems to be overcome regarding the adsorbent compositions and their manufacturing methods.

The adsorbent composition disclosed herein may include adsorbent particles with different exothermic amounts, which can improve the adsorption efficiency and/or avoid the failure of the adsorbent composition. The adsorption efficiency may include the balance adsorption amount, the working adsorption amount, the balance adsorption recovery rate, and the working adsorption recovery rate, etc.

In some embodiments, an adsorbent composition is provided. The adsorbent composition includes 100 parts by weight of a first particle and 3 to 450 parts by weight of a second particle. The first particle is a base particle having an amino group and has a first heat release amount. The second particle is a base particle having an amino group and an epoxy group and has 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.

In some embodiments, a method for manufacturing an adsorbent composition is provided. The manufacturing method includes providing a first particle, wherein the first particle is a substrate particle having an amine group, and the first particle has a first exothermic amount. The first exothermic amount is greater than 90 J/g and less than or equal to 130 J/g. A second particle is provided, wherein the second particle is a substrate particle having an amine group and an epoxy group, and the second particle has a second exothermic amount. The second exothermic amount is greater than or equal to 35 J/g and less than or equal to 90 J/g. The first particle and the second particle are mixed to obtain an adsorbent composition. The first particle is 100 parts by weight, and the second particle is 3 to 450 parts by weight.

The adsorbent composition disclosed herein can be applied to various types of adsorption equipment. In order to make the components and advantages of the present disclosure more clearly understandable, various embodiments are specifically cited below, and the attached drawings are used for detailed description as follows.

S1, S2, S3: Steps

The present disclosure can be more fully understood from the following detailed description when read together with the drawings. It is worth noting that, in accordance with standard practice in the industry, the components are not drawn to scale. In fact, the size of the components may be arbitrarily enlarged or reduced for the sake of clarity.

FIG. 1 shows a flow chart of a method for manufacturing an adsorbent composition according to some embodiments of the present disclosure.

Figure 2 shows a Fourier transform infrared spectrum (FTIR) analysis diagram according to some embodiments of the present disclosure.

FIG. 3 is a schematic diagram showing penetration curves according to some embodiments of the present disclosure.

The following is a detailed description of the adsorbent composition and its manufacturing method of each embodiment of the present disclosure. It should be understood that the following description provides many different embodiments for implementing different aspects of some embodiments of the present disclosure. The specific elements and arrangements described below are only for simple and clear description of some embodiments of the present disclosure. Of course, these are only used for example and not for limitation of the present disclosure. In addition, similar and/or corresponding element symbols may be used in different embodiments to indicate similar and/or corresponding elements to clearly describe the present disclosure. However, the use of these similar and/or corresponding element symbols is only for simple and clear description of some embodiments of the present disclosure, and does not represent any correlation between the different embodiments and/or structures discussed.

It should be understood that the ordinal numbers used in the specification and patent application, such as "first", "second", etc., are used to modify the elements. They are not intended to imply or represent any previous ordinal numbers of the (or those) elements, nor do they represent the order of one element and another element, or the order of the manufacturing method. The use of these ordinal numbers is only used to make a clear distinction between an element with a certain name and another element with the same name. The patent application and the specification may not use the same terms. For example, the first element in the specification may be the second element in the patent application.

In the text, the terms "approximate", "about", and "substantially" usually mean within 10%, within 5%, within 3%, within 2%, within 1%, or within 0.5% of a given value or range. The quantities given here are approximate quantities, that is, in the absence of specific description of "about", "approximately", and "substantially", the meanings of "about", "approximately", and "substantially" can still be implied. The term "ranging from a first value to a second value" or "a first value~a second value" means that the range includes the first value, the second value, and other values therebetween. Furthermore, any two values used for comparison may have a certain error. If a first number is equal to a second number, it implies that there may be an error between the first number and the second number of about 10%, or within 5%, or within 3%, or within 2%, or within 1%, or within 0.5%. The term "ratio of a first number to a second number" means the ratio of the first number as the numerator and the second number as the denominator (first number/second number). The term "ratio of a first number to a second number" means the ratio of the first number: the second number.

In the following description and patent application, the words "include", "contain", "have" and the like are open-ended words, and therefore should be interpreted as "including but not limited to..." Therefore, when the terms "include", "contain" and/or "have" are used in the description of the present disclosure, they specify the existence of corresponding parts, regions, steps, operations and/or elements, but do not exclude the existence of one or more corresponding parts, regions, steps, operations and/or elements.

It should be understood that the following embodiments can replace, reorganize, and combine components in multiple different embodiments to complete other embodiments without departing from the spirit of the present disclosure. As long as the components between the embodiments do not violate the spirit of the invention or conflict with each other, they can be combined and used in any way.

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

In the following, the "heat release amount" of the adsorbent particles is the heat release (joule (J)) per gram (g) of the adsorbent particles in a gas environment of 10% volume percent (vol%) carbon dioxide (90vol% inert gas), so the unit of the heat release amount of the adsorbent particles can be J/g, and the value is the pure value of the heat released. In detail, when the "heat release amount (A J/g)" of the adsorbent particles is described below, it means that each gram of the adsorbent particles releases an absolute value of A joule of heat to the gas environment. Furthermore, the heat release amount of the adsorbent particles can be changed according to the composition of the gas environment. For example, when the same adsorbent particles are placed in different gas environments, the heat release amount of the adsorbent particles will change. Among them, the heat release of adsorbed particles can be measured by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).

Hereinafter, the "average heat release amount" of the adsorbent composition is calculated 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 of the first particle (a dimensionless) and the heat release of the first particle (A J/g) and the product of the weight of the second particle (b dimensionless) and the heat release of the second particle (B J/g), divided by the total weight of the first particle and the second particle ((a*A+b*B)/(a+b)). For example, the average heat release can be the sum of the product of the weight percentage of the first particle in the adsorbent composition (a wt%) and the heat release of the first particle (A J/g) and the product of the weight percentage of the second particle in the adsorbent composition (b wt%) and the heat release of the second particle (B J/g) (a wt%* A+b wt%* B).

Referring to Figure 1, there is shown a flow chart of a method for manufacturing an adsorbent composition according to some embodiments of the present disclosure.

In step S1, a first particle is provided. In some embodiments, the first particle is a substrate particle having an amine group, and the first particle has a first exothermic amount. In some embodiments, the first exothermic amount may be greater than 90 J/g and less than or equal to 130 J/g. For example, the first exothermic 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 the aforementioned values or a numerical range consisting of any values, but the present disclosure is not limited thereto. For example, the first heat release may be 90.1 J/g~130 J/g, 100 J/g~119.6 J/g, or 110 J/g~115 J/g, but the present disclosure is not limited thereto.

In some embodiments, providing the first particle may include: step a, mixing the substrate particles and the metal chelating agent to obtain a first powder; step b, mixing the amine-containing material and the first powder to obtain a second powder; and step c, mixing the second powder and the adhesive to obtain the first particle.

In some embodiments, the base particles may include silicon dioxide, aluminum oxide, titanium oxide, calcium silicate, carbon nanotubes, activated carbon, acetate fiber, the like or a combination thereof, but the present disclosure is not limited thereto. In some embodiments, the base particles may be porous or non-porous powder materials. In some embodiments, the particle size of the base particles may be 1um to 500um. For example, the particle size of the base particles may be 1um, 50um, 100um, 200um, 300um, 400um, 500um, or any value between the aforementioned values or a numerical range consisting of any values, but the present disclosure is not limited thereto.

In some embodiments, a metal chelating agent may be used to chelate metal elements in substrate particles to prevent metal ions in the substrate particles from interfering as impurities. 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.

In some embodiments, the amine group material may include a compound or polymer having a primary amine group (-NH ₂ ), a secondary amine group (-NHR) or a tertiary amine group (-NR ₂ ). In some embodiments, the molecular weight of the amine group material may be greater than or equal to 500 and less than 10000. For example, the molecular weight of the amine group material may be 500-9999, 3000-9999, 5000-8000, 600-3000 or 800-1200, 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.

In some embodiments, in the first particle, the ratio of the weight of the material containing an amine group to the weight of the substrate particle may be 0.5 to 0.75. For example, in the first particle, the ratio of the weight of the material containing an amine group to the weight of the substrate particle may be 0.5, 0.55, 0.6, 0.64, 0.65, 0.7, 0.75, or any value or a range of values composed of any values between the aforementioned values, but the present disclosure is not limited thereto. For example, in the first particle, the ratio of the weight of the material containing an amine group to the weight of the substrate particle may be 0.55 to 0.7 or 0.6 to 0.65, but the present disclosure is not limited thereto.

In some embodiments, the adhesive may include nitrile butadiene rubber, chloroprene rubber, styrene-butadiene rubber, the like or a combination 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 particle. 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 particle, or any value or a range of values consisting of any of the foregoing values, but the present disclosure is not limited thereto.

In step S2, a second particle is provided. In some embodiments, the second particle is a substrate particle having an amino group and an epoxy group, and the second particle has a second exothermic amount. In some embodiments, the second exothermic amount may be greater than or equal to 35 J/g and less than or equal to 90 J/g. For example, the second heat release may be 35J/g, 40J/g, 45J/g, 45.1J/g, 46J/g, 50J/g, 55J/g, 60J/g, 63J/g, 63.3J/g, 64J/g, 65J/g, 69J/g, 69.2J/g, 70J/g, 75J/g, 76J/g, 76.3J/g, 77J/g, 80J/g, 85J/g, 90J/g, or any value or a range of values composed of any values between the aforementioned values, but the disclosure is not limited thereto. For example, the second heat release may be 35J/g~90J/g, 40J/g~85J/g, or 45J/g~80J/g, but the disclosure is not limited thereto.

In some embodiments, the second particle may include a third particle and a fourth particle. The third particle may have a third heat release, and the fourth particle may have a fourth heat release different from the third heat release. In some embodiments, the third heat release may be greater than 65 J/g and less than or equal to 90 J/g. For example, the third heat release 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 value or a range of values consisting of any values therebetween, but the present disclosure is not limited thereto. For example, the third heat release 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 disclosure is not limited thereto. In some embodiments, the fourth heat release may be greater than or equal to 35 J/g and less than 65 J/g. For example, the fourth heat release 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 value or a range of values consisting of any value therebetween, but the disclosure is not limited thereto. For example, the fourth heat release may be 35 J/g~64.9 J/g, 40 J/g~64 J/g, or 45 J/g~64 J/g, but the present disclosure is not limited thereto.

In some embodiments, providing the second particle may include: step d, mixing the amine-containing material and the epoxide to obtain a solution; step e, mixing the solution with the first powder to obtain a third powder; and step f, mixing the third powder with an adhesive to obtain the second particle.

In some embodiments, the epoxide may include ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-epoxypentane, 1,2-epoxyhexane, the like or a combination thereof, but the present disclosure is not limited thereto. In some embodiments, the ratio of the weight of the epoxide to the weight of the material containing the amine group may be greater than 0. In some embodiments, the ratio of the weight of the epoxide to the weight of the material containing the amine group is 0.01-0.8. For example, the ratio of the weight of the epoxide to the weight of the material containing the amine group is 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 value or a range of values consisting of any values between the aforementioned values, but the present disclosure is not limited thereto.

In some embodiments, the third and fourth particles can be obtained by adjusting the weight ratio of the epoxide to the weight of the material containing the amine group. For example, in the third particle, the weight ratio of the epoxide to the weight of the material containing the amine group can be 0.4-0.7, 0.5-0.6 or 0.594, but the present disclosure is not limited thereto. For example, in the fourth particle, the weight ratio of the epoxide to the weight of the material containing the amine group can be 0.4-0.7, 0.5-0.6 or 0.594, but the present disclosure is not limited thereto.

In some embodiments, in the second particle, the weight of the material containing an amine group to the weight of the substrate particle may be a ratio of 0.2 to 0.65. For example, in the second particle, the weight of the material containing an amine group to the weight of the substrate particle 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 or a range of values composed of any values between the aforementioned values, but the present disclosure is not limited thereto. For example, in the second particle, the weight of the material containing an amine group to the weight of the substrate particle may be 0.2 to 0.55, or 0.25 to 0.53, but the present disclosure is not limited thereto.

In some embodiments, the third particle and the fourth particle can be obtained by adjusting the weight ratio of the material containing an amine group to the weight of the substrate particle. For example, in the third particle, the weight ratio of the material containing an amine group to the weight of the substrate particle can be 0.45-0.65 or 0.5-0.55, but the present disclosure is not limited thereto. For example, in the fourth particle, the weight ratio of the material containing an amine group to the weight of the substrate particle can be 0.2-0.45, 0.25-0.4, or 0.3-0.35, but the present disclosure is not limited thereto.

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 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 value or a numerical range consisting of any value between the aforementioned values, but the present disclosure is not limited thereto. When the weight of the second particle is less than 3, the adsorbent composition may be damaged by heat during adsorption and desorption and degraded. When the weight of the second particle is greater than 450, the adsorption amount of the adsorbent composition may be too low.

In some embodiments, the weight of the first particle is 20% to 90% of the total weight of the adsorbent composition, and the weight of the second particle is 10% to 80% of the total weight of the adsorbent composition. For example, the weight of the first particle is 20%, 23%, 28%, 30%, 40%, 48%, 50%, 60%, 70%, 80%, 88%, 90%, or any value or a range of values composed of any values therein, but the disclosure is not limited thereto. When the weight of the first particle accounts for more than 80% of the total weight of the adsorbent composition, the adsorbent composition may be damaged by heat and degraded during adsorption and desorption. When the weight of the first particle accounts for less than 20% of the total weight of the adsorbent composition, the adsorption amount of the adsorbent composition may be too low. In some embodiments, the weight of the first particle and the weight of the second particle are in a ratio of 20-90:10-80. For example, the weight of the first particle and the weight of the second particle may be in a ratio of 20-50:50-80.

In some embodiments, the second particle may include 0 to 330 parts by weight of the third particle and 0 to 150 parts by weight of the fourth particle, and the third particle and the fourth particle are not both 0 parts by weight. In other words, the second particle may include at least the third particle or the fourth particle. For example, the weight of the third particle 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 value or a numerical range consisting of any value between the aforementioned values, but the present disclosure is not limited thereto. For example, the weight of the fourth particle can 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 value or a numerical range composed of any values between the aforementioned values, but the present disclosure is not limited thereto. When the weight of the third particle is greater than 330 or the weight of the fourth particle is greater than 150, the adsorption amount of the adsorbent composition may be too low.

In some embodiments, the average heat release of the adsorbent composition may be greater than or equal to 65 J/g and less than or equal to 120 J/g. For example, the average heat release 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. When the average heat release of the adsorbent composition is greater than 120 J/g, the adsorbent composition may be damaged by heat and degraded during adsorption and desorption. When the average heat release of the adsorbent composition is less than 65 J/g, the adsorption amount of the adsorbent composition may be too low.

In some embodiments, the first particle may include an amine group, and the second particle may include an amine group and an epoxy group. In some embodiments, the content of the amine group in the first particle may be greater than the content of the amine group in the second particle, so 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 include an amine group and an epoxy group, and the content of the amine group in the third particle may be greater than the content of the amine group in the fourth particle.

Among them, when there are more amine groups in the adsorption particles, it is easier to adsorb (capture) carbon dioxide, and the adsorption amount of carbon dioxide is increased. Among them, the epoxy group will produce a cross-linking reaction with the amino group, thereby reducing the content of the amino group that can adsorb carbon dioxide. Therefore, when there are more epoxy groups in the adsorption particles, it is more difficult for the adsorption particles to adsorb carbon dioxide, and the adsorption amount of carbon dioxide is reduced. Correspondingly, when the adsorption amount of carbon dioxide is higher, it is easier to produce an exothermic reaction, causing the temperature in the reactor to at least partially increase, causing the adsorption particles to deteriorate. For example, it can be observed that the appearance of the adsorption particles changes from white to yellow, indicating that the adsorption particles are deteriorating.

In some embodiments, the density of the first particle and the second particle may be 0.3 g/cm ³ -0.8 g/cm ³ . For example, the density of the first particle and the second particle may be 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 ³ , or any value therebetween or a numerical range consisting of any values, but the present disclosure is not limited thereto. In some embodiments, the density of the first particle may be 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 may be 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 .

In some embodiments, the adsorbent composition disclosed herein can be used to adsorb and desorb gases. For example, the gas can be carbon dioxide or other suitable gases, but the disclosure is not limited thereto. In some embodiments, the adsorbent composition disclosed herein can be used as a filling material for a reactor. For example, the reactor can be a fixed-bed reactor (fixed-bed reactor) or other suitable reactors, but the disclosure is not limited thereto.

In the following, the method for preparing the adsorbent composition is described by way of example.

In some embodiments, the average particle size of the substrate particles in step a is 35um silica powder, and the metal chelating agent is phosphate. Specifically, at a temperature of 100°C, the water in the silica powder is removed. The phosphate is dissolved in water, and after mixing and stirring with the silica powder after the water is removed, a vacuum oven is used to remove the water at a temperature of 100°C to obtain a first powder.

In some embodiments, the amine-containing material in step b is polyethyleneimine (molecular weight: 1200). Specifically, polyethyleneimine is added to a solvent (e.g., alcohol) to obtain a polyethyleneimine solution. The polyethyleneimine solution is mixed and stirred with the first powder and then dried to obtain a second powder. The drying can be performed under negative pressure and at a temperature of 40°C to 50°C.

In some embodiments, the adhesive in step c is chloroprene rubber (containing about 50 wt% of 2,3-dichloro-1,3-butadiene and 2-chloro-1,3-butadiene polymer (1,3-butadiene, 2,3-dichloro-, polymer with 2-chloro-1,3-butadiene), or containing about 45 wt% of 2-methyl-2-acrylic acid and 2-chloro-1,3-butadiene polymer (2-propenoic acid, 2-methyl-, polymer with 2-chloro-1,3-butadiene)). In detail, the second powder can be wetted with deionized water, and then the adhesive is added, mixed and stirred, and then the water is removed under vacuum at a temperature of 105° C. to obtain the first granules. In some embodiments, granulation can be further performed by a syringe or a granulator. In other embodiments, the granulation process can be omitted.

In some embodiments, the epoxide in step d is butylene oxide. Specifically, butylene oxide is added dropwise to the polyethyleneimine solution, and the mixture is stirred uniformly at room temperature (e.g., 25°C) to perform a crosslinking reaction to obtain a transparent and clear solution.

In some embodiments, in step e, after the transparent clear liquid is mixed and stirred with the first powder, a milky white liquid including a white suspension is obtained. The milky white liquid is dried to obtain a third powder. The milky white liquid can be dried under negative pressure and at a temperature of 40°C to 50°C.

In some embodiments, in step f, the third powder can be moistened with deionized water, and then after adding an adhesive and mixing and stirring, the water can be removed under vacuum and at a temperature of 105°C to obtain a second granule. In some embodiments, a granulation process can be further performed or the granulation process can be omitted.

Accordingly, the present disclosure can adjust the heat release of the adsorption particles during the adsorption and/or desorption of carbon dioxide by adjusting the ratio of polyethyleneimine (providing amine groups) to butylene oxide (providing epoxide groups) (amine-epoxide modification amount), and the ratio of polyethyleneimine to silica powder (amine group coating amount on the surface of silica powder). Thus, adsorption particles with similar density but different heat release can be obtained.

In some embodiments, an example is provided in which the adsorbent composition includes a first particle and a second particle, and the second particle includes a third particle and a fourth particle.

First particle: 50g of porous silicon powder was dried at 100℃ to remove moisture, then mixed with 260g of 0.79wt.% sodium phosphate aqueous solution and stirred for 2 hours, and then vacuum dried at 100℃ to remove moisture to obtain white powder. 94g of 34wt.% polyethyleneimine aqueous solution was prepared, mixed with white powder and stirred for 2 hours, and the solution was removed at negative pressure at 40℃ to obtain amine-modified white powder. 5g of amine-modified white powder was moistened with deionized water, and then 0.65g of adhesive was added and mixed and stirred. Then, vacuum dried at 105℃ to obtain the first white particle with high heat release and high carbon dioxide adsorption. Among them, the ratio of the weight of the material containing the amine group to the weight of the substrate particles is about 0.64.

The third particle: 50g of porous silicon powder was dried at 100℃ to remove moisture, and then mixed with 260g of 0.79wt.% sodium phosphate aqueous solution and stirred for 2 hours, and then vacuum dried at 100℃ to remove moisture to obtain white powder. 94g of 34wt.% polyethyleneimine aqueous solution was prepared, and 19g of butylene oxide was added dropwise, mixed and stirred at 25℃ for 20 hours, and then mixed and stirred with white powder for 2 hours, and the solution was removed at negative pressure at 40℃ to obtain amino-epoxy modified white powder. 5g of amino-epoxy modified white powder was taken and moistened with deionized water, and then 0.65g of adhesive was added, mixed and stirred. Then, it was dried by vacuum dehydration at 105℃ to obtain the third white particle with medium heat release and medium carbon dioxide adsorption. The ratio of the weight of the material containing the amine group to the weight of the substrate particles is about 0.64. The ratio of the weight of the epoxide to the weight of the material containing the amine group is about 0.594.

Fourth particle: 50g of porous silicon powder was dried at 100℃ to remove moisture, and then mixed with 260g of 0.79wt.% sodium phosphate aqueous solution and stirred for 2 hours, and then vacuum dried at 100℃ to remove moisture to obtain white powder. 47g of 34wt.% polyethyleneimine aqueous solution was prepared, and 9.5g of butylene oxide was added dropwise, mixed and stirred at 25℃ for 20 hours, and then mixed and stirred with white powder for 2 hours, and the solution was removed at negative pressure at 40℃ to obtain amino-epoxy modified white powder. 5g of amino-epoxy modified white powder was taken and moistened with deionized water, and then 0.65g of adhesive was added, mixed and stirred. Then, it was dried by vacuum dehydration at 105℃ to obtain the fourth white particle with low heat and low carbon dioxide adsorption. Wherein, the ratio of the weight of the material containing an amine group to the weight of the substrate particle is about 0.32. Accordingly, the amount of amine group coating on the surface of the fourth particle may be less than the amount of amine group coating on the surface of the third particle. Wherein, the ratio of the weight of the epoxide to the weight of the material containing an amine group is about 0.594. Accordingly, the amount of amine-epoxy modification of the third particle may be similar to the amount of amine-epoxy modification of the fourth particle.

Referring to FIG. 2, it shows a Fourier transform infrared spectrum (FTIR) analysis diagram according to some embodiments of the present disclosure. The adsorbed particles were placed in an oven at 105°C to remove water, and then ground and analyzed by FTIR. The test wavelength was 4000 cm ^-1 to 400 cm ^-1 . As shown in FIG. 2, the first particle, the third particle, and the fourth particle have a peak representing _-NH2 (primary amine) at 1564 cm ^-1 to 1587 cm ^-1 , and a peak representing -NHR (secondary amine) at 3275 cm ^-1 . As shown in FIG. 2, the content of primary amine in the first particle is greater than the content of primary amine in the third particle and the fourth particle, and the content of primary amine in the third particle is greater than the content of primary amine in the fourth particle. As shown in FIG. 2 , the content of the secondary amine in the first particle is greater than the content of the secondary amine in the third particle and the fourth particle, and the content of the secondary amine in the third particle is greater than the content of the secondary amine in the fourth particle.

In some embodiments, the thermal properties of the adsorbed particles are analyzed by a thermogravimetric analyzer (TGA) and a thermal differential scanning calorimeter (DSC) in a 10% CO ₂ gas environment. In addition, the particle density can be calculated by measuring the particle volume and weighing it with a balance. The results are shown in Table 1.

As shown in Table 1, the first particle has a high carbon dioxide adsorption capacity. If it is directly used to fill the carbon dioxide adsorption fixed bed reactor, it is easy to produce local high temperature due to the high adsorption heat release, resulting in the degradation of the first particle and reduced adsorption performance. On the contrary, although the second particle has a low heat release, the carbon dioxide adsorption capacity is too low, which will reduce the total carbon dioxide adsorption capacity in the reactor. In addition, the density of particles with different heat release is similar, ranging from about 0.58 to 0.72 g/ ^cm3 , indicating that the adsorption particles can be evenly mixed and dispersed, and it is not easy to produce a stratification effect due to airflow disturbance and lose the dispersion function.

In contrast, when 10g of the first particle (particle density: 0.58~0.65g/cm ³ ) and 10g of quartz sand (particle density: 2.65g/cm ³ ) were mixed in a beaker and stirred with a glass rod, the first particle and the quartz sand were separated within 30 seconds of stirring. This means that when the adsorbed particles are mixed with traditional dispersion materials (e.g., quartz sand, ceramic balls, steel balls, ceramic rings, metal rings), they cannot be evenly dispersed because of the large difference in particle density.

Adsorption particle fixed bed column adsorption/desorption cycle test (I):

According to Table 2, the adsorbent compositions of Examples 1 to 10 and Comparative Examples 1 and 2 were prepared as samples. The average heat release was calculated by the ratio of the adsorbed particles and the heat release. For example, the heat release of the first particle can be 112.9 J/g, and the adsorption amount can be 2.01 mmol CO ₂ /g. For example, the heat release of the third particle can be 76.3 J/g, and the adsorption amount can be 1.21 mmol CO ₂ /g. For example, the heat release of the fourth particle can be 63.3 J/g, and the adsorption amount can be 0.84 mmol CO ₂ /g.

15g of sample was filled in a fixed bed column. A mixed gas of 10vol.% CO ₂ and 10vol.% H ₂ O was used as the target gas. The adsorption conditions were an inlet temperature of 50°C and a flow rate of 0.4 liters/minute (L/min). The desorption conditions were a desorption temperature of 100°C and a pressure of 0.2 bar, and the desorption process was terminated after the CO ₂ concentration was desorbed to 2%~3%. The above adsorption/desorption process was one cycle, and a total of 5 cycles were performed. The results are shown in Table 3.

In addition, observe and record the appearance of the samples before and after 5 adsorption/desorption cycles. The "-" in the appearance means there is no significant difference in appearance.

Refer to Figure 3, which shows a schematic diagram of a penetration curve according to some embodiments of the present disclosure. The adsorption amount may include a working adsorption amount and an equilibrium adsorption amount, and the measurement and calculation methods are described as follows. At the initial time ( _t0 ), _CO2 flows into the fixed bed column at a fixed inlet concentration ( _Cin ). _CO2 is initially adsorbed by the adsorption particles, causing the _CO2 concentration in the output gas to decrease. As time increases, the adsorption particles continue to adsorb _CO2 until saturation. Therefore, the _CO2 concentration in the output gas can be measured to increase with time until the _CO2 concentration in the output gas is equal to that in the input gas, indicating that the adsorption has reached saturation and the adsorption reaction has reached equilibrium. As shown in Figure 3, the S-shaped curve obtained by plotting the _CO2 concentration of the outflow gas against time is called the breakthrough curve (BTC). At the breakthrough time (t _b ), the outflow concentration is 10% of the inflow concentration (C _out =0.1 C _in ). At the equilibrium time ( _te ), the outflow concentration is equal to the inflow concentration (C _out =C _in ), and adsorption equilibrium is reached. _{The CO2} adsorption amount is obtained by integrating the difference between the product of the inflow concentration (C _in ) and the inflow flow rate (Q _in ), and the product of the outflow concentration (C _out ) and the outflow flow rate (Q _out ) over time. The adsorption amount integrated from t ₀ to t _b is called the working adsorption amount. The adsorption amount integrated from t ₀ to _te is called the equilibrium adsorption amount.

The equilibrium adsorption recovery rate (recovery, %) is: the 5th equilibrium adsorption amount/the 1st equilibrium adsorption amount x 100%

The working adsorption recovery rate is: The 5th working adsorption amount/the 1st working adsorption amount x 100%

As shown in Tables 2 and 3, the average heat release of Examples 2-5, 6-8, 9 and 10 is 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 particle is 28% to 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.

As shown in Tables 2 and 3, Comparative Example 1 uses a single high exothermic adsorption particle to adsorb carbon dioxide, and 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 yellowing appearance of Comparative Example 1 indicates that the amine groups in the adsorption particles are degraded by high temperature and discolored. On the contrary, Examples 9 and 10 can significantly improve the adsorption efficiency without adding additional dispersing materials by mixing adsorption particles with different exothermic amounts, and there is no change in appearance. It means that the adsorbent composition including adsorption particles with different exothermic amounts can improve the cyclic adsorption/desorption performance of the material and avoid local high temperature degradation.

As shown in Table 2 and Table 3, it can be seen from the observation of Example 1, Example 2 and Example 6 that when the proportion of the third particle and the fourth particle in the sample is increased to 10%, the working adsorption amount and the working adsorption recovery rate can be increased at the same time.

The adsorbent composition disclosed herein includes particles with different exothermic amounts, thereby improving the adsorption efficiency (e.g., equilibrium adsorption amount, working adsorption amount, equilibrium adsorption recovery rate, and working adsorption recovery rate) and/or avoiding the failure of the adsorbent composition. The manufacturing method disclosed herein can change the exothermic amount of the particles by adjusting the amino group content in different particles to obtain the adsorbent composition.

For example, the heat release of the first particle can be greater than that of the second particle, and the first particle and the second particle can be mixed in a specific ratio to form an adsorbent composition. Therefore, the average heat release of the adsorbent composition can be adjusted to avoid high temperatures in the reactor. Furthermore, the deterioration of the adsorbent composition can be effectively avoided, and the adsorption efficiency can be improved and/or the adsorbent composition can be prevented from failing. For example, the adsorbent composition disclosed in the present invention can be used alone without being used in combination with a dispersing material. Therefore, stratification in the reactor can be avoided, and the content of the adsorbent composition in the reactor can be increased, thereby improving the adsorption efficiency.

The scope of protection of this disclosure is not limited to the processes, machines, manufacturing, material compositions, devices, methods and steps in the specific embodiments described in the specification. Any person with ordinary knowledge in the relevant technical field can understand from the content of this disclosure the processes, machines, manufacturing, material compositions, devices, methods and steps currently or developed in the future. As long as they can implement substantially the same functions or obtain substantially the same results in the embodiments described here, they can be used according to this disclosure. Therefore, the scope of protection of this disclosure includes the aforementioned processes, machines, manufacturing, material compositions, devices, methods and steps. Any embodiment or claim of this disclosure does not need to achieve all the purposes, advantages and/or features disclosed in this disclosure.

Several embodiments are summarized above so that those with ordinary knowledge in the art to which the present disclosure belongs can better understand the viewpoints of the embodiments of the present disclosure. Those with ordinary knowledge in the art to which the present disclosure belongs should understand that they can design or modify other processes and structures based on the embodiments of the present disclosure to achieve the same purpose and/or advantages as the embodiments introduced herein. Those with ordinary knowledge in the art to which the present disclosure belongs should also understand that such equivalent processes and structures do not violate the spirit and scope of the present disclosure, and they can make various changes, substitutions and replacements without violating the spirit and scope of the present disclosure.

S1, S2, S3: Steps

Claims (9)

An adsorbent composition comprises: 100 parts by weight of a first particle, which is a first substrate particle modified by an amine group and has a first exothermic amount; and 3 to 450 parts by weight of a second particle, which is a second substrate particle modified by an amine group and an epoxy group and has a second exothermic amount, wherein, in a gas environment of 10% by volume carbon dioxide and 90% by volume inert gas, the first exothermic amount is greater than 90 J/g and less than or equal to 130 J/g, and the second exothermic amount is greater than or equal to 35 J/g and less than or equal to 90 J/g. The adsorbent composition as described in claim 1, wherein the content of amine groups in the first particles is greater than the content of amine groups in the second particles. The adsorbent composition as described in claim 1, wherein the second particle comprises: 0 to 330 parts by weight of a third particle, having a third exothermic amount, which is greater than 65 J/g and less than or equal to 90 J/g in a gas environment of 10% by volume carbon dioxide and 90% by volume inert gas; and 0 to 150 parts by weight of a fourth particle, having a fourth exothermic amount different from the third exothermic amount, which is greater than or equal to 35 J/g and less than 65 J/g in a gas environment of 10% by volume carbon dioxide and 90% by volume inert gas, wherein the third particle and the fourth particle are not both 0 parts by weight. The adsorbent composition as described in claim 3, wherein the content of amine groups in the third particle is greater than the content of amine groups in the fourth particle. The adsorbent composition as described in claim 1, wherein in a gas environment of 10 volume % carbon dioxide and 90 volume % inert gas, the average heat release of the adsorbent composition is greater than or equal to 65 J/g and less than or equal to 120 J/g. A method for manufacturing an adsorbent composition, comprising: Providing a first particle, wherein the first particle is a first substrate particle modified by an amine group, the first particle has a first exothermic amount, and in a gas environment of 10% by volume carbon dioxide and 90% by volume inert gas, the first exothermic amount is greater than 90 J/g and less than or equal to 130 J/g; Providing a second particle, wherein the second particle is a second substrate particle modified by an amine group and an epoxy group, the second particle has a second exothermic amount, and in a gas environment of 10% by volume carbon dioxide and 90% by volume inert gas, the second exothermic amount is greater than or equal to 35 J/g and less than or equal to 90 J/g; The first particle and the second particle are mixed to obtain the adsorbent composition, wherein the first particle is 100 parts by weight and the second particle is 3 to 450 parts by weight. The manufacturing method as described in claim 6, wherein providing the first particle comprises: Mixing the first substrate particle with a metal chelating agent to obtain a first powder; Mixing an amine-containing material with the first powder to obtain a second powder; and Mixing the second powder with an adhesive to obtain the first particle, wherein the ratio of the weight of the amine-containing material to the weight of the first substrate particle is 0.5-0.75. The manufacturing method as described in claim 6, wherein providing the second particle comprises: Mixing the second substrate particle with the metal chelating agent to obtain a third powder; Mixing the amine-containing material and the epoxide to obtain a solution; Mixing the solution with the third powder to obtain a fourth powder; and Mixing the fourth powder with the adhesive to obtain the second particle, wherein the ratio of the weight of the epoxide to the weight of the amine-containing material is 0.01-0.8. A manufacturing method as described in claim 8, wherein the ratio of the weight of the amino-containing material to the weight of the second substrate particles is 0.2~0.65.

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