Adsorbent composition and method for producing same

Abstract

The invention discloses an adsorbent composition and a preparation method thereof. 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 material particles having an amino group and have a first heat release amount. The second particles are base material particles having an amino group and an epoxy group, and have 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

Technical Field

[0001] The present invention relates to an adsorbent composition and a method for making the same, and more particularly to an adsorbent composition comprising particles having different exothermic heat and a method for making the same. Background Art

[0002] 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 adsorption and desorption, 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 also occupy the volume in the reactor, thereby reducing the total adsorbent filling amount, which also leads to a problem of reduced total adsorption capacity of the system.

[0003] Therefore, although the existing adsorbent compositions and methods for making the same 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 methods for making the same. Summary of the invention

[0004] The adsorbent composition of the present invention may include adsorbent particles with different heat releases, thereby improving adsorption efficiency and / or preventing the adsorbent composition from failing. The adsorption efficiency may include balance adsorption amount, working adsorption amount, balance adsorption recovery, working adsorption recovery, etc.

[0005] 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.

[0006] 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 heat. The first exothermic heat 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 heat. The second exothermic heat 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. Wherein, the first particle is 100 parts by weight, and the second particle is 3 to 450 parts by weight.

[0007] The adsorbent composition of the present invention can be applied to various types of adsorption equipment. In order to make the components and advantages of the present invention more clearly understood, various embodiments are given below and described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] When with Figure 1 The present invention can be more fully understood from the following detailed description when reading together. It is worth noting that, in accordance with standard practice in the industry, the components are not drawn to scale. In fact, for the sake of clarity, the size of each component can be arbitrarily enlarged or reduced.

[0009] Figure 1 A flow chart showing a method of making an adsorbent composition according to some embodiments of the present invention.

[0010] Figure 2 A Fourier transform infrared spectroscopy (FTIR) analysis graph is shown according to some embodiments of the present invention.

[0011] Figure 3 Schematic diagram showing a penetration curve according to some embodiments of the present invention.

[0012] Wherein, the reference numerals are:

[0013] S1, S2, S3: Steps DETAILED DESCRIPTION

[0014] The following is a detailed description of the adsorbent composition and the method for making the same in each embodiment of the present invention. It should be understood that the following description provides many different embodiments for implementing different aspects of some embodiments of the present invention. The specific elements and arrangements described below are only for a simple and clear description of some embodiments of the present invention. Of course, these are only used for exemplification and are not limitations of the present invention. In addition, similar and / or corresponding element symbols may be used in different embodiments to indicate similar and / or corresponding elements in order to clearly describe the present invention. However, the use of these similar and / or corresponding element symbols is only for a simple and clear description of some embodiments of the present invention, and does not represent any correlation between the different embodiments and / or structures discussed.

[0015] It should be understood that the ordinal numbers used in the specification and claims, such as "first", "second", etc., are used to modify the elements, and are not intended to imply any previous ordinal numbers of the element (or 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 claims and the specification may not use the same words, for example, the first element in the specification may be the second element in the claim.

[0016] In the text, the terms "approximate", "about", "substantially" usually mean within 10%, or within 5%, or within 3%, or within 2%, or within 1%, or within 0.5% of a given value or range. The quantity given here is an approximate quantity, that is, in the absence of a specific description of "about", "approximately", "substantially", the meaning of "about", "approximately", "substantially" can still be implied. The term "range is between a first value and a second value" or "first value ~ second value" means that the range includes the first value, the second value and other values ​​between them. Furthermore, there may be a certain error between any two values ​​used for comparison. If the first value is equal to the second value, it implies 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 value and the second value. The term "ratio of a first value to a second value" means a ratio of a first value as a numerator and a second value as a denominator (first value / second value). The term "proportion of a first value to a second value" means a ratio of a first value: a second value.

[0017] In the following description and claims, words such as "include", "contain", "have" and the like are open-ended words, and therefore should be interpreted as meaning "including but not limited to..." Therefore, when the terms "include", "contain" and / or "have" are used in the description of the present invention, 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.

[0018] It should be understood that the following embodiments may replace, reorganize, or combine components in different embodiments to complete other embodiments without departing from the spirit of the present invention. Components between embodiments may be used in any combination as long as they do not violate the spirit of the invention or conflict with each other.

[0019] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meanings as commonly understood by those with common knowledge 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 invention, and should not be interpreted in an idealized or overly formal manner unless specifically defined in the embodiments of the present invention.

[0020] In the following text, the "heat release amount" of the adsorbed particles is the amount of heat (joule (J)) released by each gram (g) of the adsorbed particles in a gas environment of 10% volume percent (vol%) carbon dioxide (90 vol% inert gas), so the unit of the heat release of the adsorbed particles can be J / g, and the value is the pure value of the heat released. In detail, when the "heat release amount (AJ / g)" of the adsorbed particles is described below, it means that each gram of the adsorbed particles releases an absolute value of A joule of heat to the gas environment. Furthermore, the heat release amount of the adsorbed particles can be changed according to the composition of the gas environment. For example, when the same adsorbed particles are placed in different gas environments, the heat release amount of the adsorbed particles will change. Among them, the heat release amount of the adsorbed particles can be measured by a thermogravimetric analysis (TGA) and a differential scanning calorimetry (DSC).

[0021] 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 may be the sum of the product of the weight fraction of the first particle (a dimensionless) and the heat release amount of the first particle (A J / g) and the product of the weight fraction of the second particle (b dimensionless) and the heat release amount of the second particle (B J / g) divided by the total weight fraction of the first particle and the second particle ((a*A+b*B) / (a+b)). For example, the average heat release amount may be the sum of the product of the weight percentage of the first particle in the adsorbent composition (a wt%) and the heat release amount 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 amount of the second particle (B J / g) (a wt%*A+b wt%*B).

[0022] Reference Figure 1 , which shows a flow chart of a method for manufacturing an adsorbent composition according to some embodiments of the present invention.

[0023] 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 heat. In some embodiments, the first exothermic heat may be greater than 90 J / g and less than or equal to 130 J / g. For example, the first exothermic heat 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 composed of any values, but the present invention is not limited thereto. For example, the first exothermic heat 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 invention is not limited thereto.

[0024] In some embodiments, providing the first particle may include:

[0025] Step a, mixing substrate particles and a metal chelating agent to obtain a first powder;

[0026] Step b, mixing the material containing an amine group with the first powder to obtain a second powder; and

[0027] Step c: mixing the second powder and the adhesive to obtain first particles.

[0028] 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 invention 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 invention is not limited thereto.

[0029] In some embodiments, a metal chelating agent can be used to chelate metal elements in the substrate particles to prevent metal ions in the substrate particles from interfering as impurities. In some embodiments, the metal chelating agent can be an inorganic metal chelating agent, an organic metal chelating agent, or a combination thereof. In some embodiments, the inorganic metal chelating agent can include sodium phosphate.

[0030] In some embodiments, the amine group material may include a primary amine group (-NH 2 ), secondary amine group (-NHR) or tertiary amine group (-NR 2 ) compounds or polymers. In some embodiments, the molecular weight of the material containing an amine group may be greater than or equal to 500 and less than 10,000. For example, the molecular weight of the material containing an amine group may be 500-9,999, 3,000-9,999, 5,000-8,000, 600-3,000, or 800-1,200, but the present invention is not limited thereto. In some embodiments, the material containing an amine group may include linear polyethyleneimine (PEI), branched polyethyleneimine, or a combination thereof, but the present invention is not limited thereto.

[0031] 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 between the aforementioned values ​​or a numerical range consisting of any values, but the present invention 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 invention is not limited thereto.

[0032] In some embodiments, the adhesive may include nitrile butadiene rubber, chloroprene rubber, styrene-butadiene rubber, the like or a combination thereof, but the present invention 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 value between the aforementioned values ​​or a range of values ​​consisting of any values, but the present invention is not limited thereto.

[0033] 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 heat. In some embodiments, the second exothermic heat may be greater than or equal to 35 J / g and less than or equal to 90 J / g. For example, the second exothermic heat 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 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 value between the aforementioned values ​​or a numerical range consisting of any value, but the present invention is not limited thereto. For example, the second heat release 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 invention is not limited thereto.

[0034] 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 between the aforementioned values ​​or a numerical range composed of any values, but the present invention 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 present invention 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 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 value between the aforementioned values ​​or a numerical range consisting of any values, but the present invention is not limited thereto. For example, the fourth heat release 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 invention is not limited thereto.

[0035] In some embodiments, providing the second particle may include:

[0036] Step d, mixing the material containing an amine group and the epoxide to obtain a solution;

[0037] Step e, mixing the solution and the first powder to obtain a third powder; and

[0038] Step f: mixing the third powder and the adhesive to obtain second particles.

[0039] 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 invention is not limited thereto. In some implementations, 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 implementations, the ratio of the weight of the epoxide to the weight of the material containing the amine group is 0.01 to 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 between the foregoing values ​​or a numerical range consisting of any values, but the present invention is not limited thereto.

[0040] In some embodiments, the third particle and the fourth particle can be obtained by adjusting the weight ratio of the epoxide to the weight of the material containing an amine group. For example, in the third particle, the weight ratio of the epoxide to the weight of the material containing an amine group can be 0.4-0.7, 0.5-0.6, or 0.594, but the present invention is not limited thereto. For example, in the fourth particle, the weight ratio of the epoxide to the weight of the material containing an amine group can be 0.4-0.7, 0.5-0.6, or 0.594, but the present invention is not limited thereto.

[0041] In some embodiments, in the second particles, the weight of the material containing an amine group to the weight of the substrate particles may be a ratio of 0.2 to 0.65. For example, in the second particles, the weight of the material containing an amine group to the weight of the substrate 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 the foregoing values ​​or a numerical range consisting of any values, but the present invention is not limited thereto. For example, in the second particles, the weight of the material containing an amine group to the weight of the substrate particles may be a ratio of 0.2 to 0.55, or 0.25 to 0.53, but the present invention is not limited thereto.

[0042] 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 to 0.65 or 0.5 to 0.55, but the present invention 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 to 0.45, 0.25 to 0.4, or 0.3 to 0.35, but the present invention is not limited thereto.

[0043] 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 number between the foregoing values ​​or a range of values ​​composed of any number, but the present invention is not limited thereto. When the weight of the second particles is less than 3, the adsorbent composition may be damaged by heat during adsorption and desorption and degraded. When the weight of the second particles is greater than 450, the adsorption amount of the adsorbent composition may be too low.

[0044] 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 is 20%, 23%, 28%, 30%, 40%, 48%, 50%, 60%, 70%, 80%, 88%, 90% of the total weight of the adsorbent composition, or any value between the foregoing values ​​or a numerical range consisting of any values, but the present invention is not limited thereto. When the weight of the first particles accounts for more than 80% of the total weight of the adsorbent composition, the adsorbent composition may be damaged by heat during adsorption and desorption and degraded. When the weight of the first particles 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 particles is in a ratio of 20 to 90:10 to 80 to the weight of the second particles. For example, the weight of the first particles is in a ratio of 20 to 50:50 to 80 to the weight of the second particles.

[0045] In some embodiments, the second particles may include 0 to 330 parts by weight of the third particles and 0 to 150 parts by weight of the fourth particles, and the third particles and the fourth particles are not 0 parts by weight at the same time. In other words, the second particles may include at least the third particles or the fourth particles. For example, the 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 value between the aforementioned values ​​or a numerical range consisting of any value, but the present invention is not limited thereto. For example, the weight of the fourth particle 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 value therebetween or a numerical range consisting of any values, but the present invention 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 capacity of the adsorbent composition may be too low.

[0046] 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 invention 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 during adsorption and desorption and degraded. 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.

[0047] 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.

[0048] Among them, the more amine groups there are in the adsorption particles, the easier it is to adsorb (capture) carbon dioxide, and the amount of carbon dioxide adsorbed is increased. Among them, the epoxy group will produce a cross-linking reaction with the amine group, thereby reducing the content of the amine group that can adsorb carbon dioxide. Therefore, the more epoxy groups there are in the adsorption particles, the less likely the adsorption particles are to adsorb carbon dioxide, and the amount of carbon dioxide adsorbed is reduced. Correspondingly, when the amount of carbon dioxide adsorbed 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.

[0049] In some embodiments, the density of the first particles and the second particles may be 0.3 g / cm 3 ~0.8g / cm 3 For example, the density of the first particles and the second particles may be 0.3 g / cm 3 , 0.4g / cm 3 , 0.5g / cm 3 、0.58g / cm 3 , 0.6g / cm 3 , 0.63g / cm 3 , 0.65g / cm 3 , 0.67g / cm 3 , 0.7g / cm 3 , 0.72g / cm 3 , 0.8g / cm 3 , or any value between the aforementioned values ​​or a numerical range consisting of any values, but the present invention is not limited thereto. In some embodiments, the density of the first particle may be 0.58 g / cm 3 ~0.65g / cm 3 , and the density of the second particle can be 0.6 g / cm 3 ~0.72g / cm 3 In some embodiments, the density of the third particles may be 0.67 g / cm 3 ~0.72g / cm 3 , and the density of the fourth particle may be 0.6 g / cm 3 ~0.63g / cm 3 .

[0050] In some embodiments, the adsorbent composition of the present invention can be used to adsorb and desorb gases. For example, the gas can be carbon dioxide or other suitable gases, but the present invention is not limited thereto. In some embodiments, the adsorbent composition of the present invention can be used as a filling material for a reactor. For example, the reactor can be a fixed-bed reactor or other suitable reactor, but the present invention is not limited thereto.

[0051] Hereinafter, a method for producing the adsorbent composition is described by way of example.

[0052] In some embodiments, the substrate particles in step a are silica powder with an average particle size of 35 μm, 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, mixed with the silica powder after the water is removed, and then the water is removed in a vacuum oven at a temperature of 100° C. to obtain a first powder.

[0053] In some embodiments, the amine-containing material in step b is polyethyleneimine (average molecular weight: 1200). Specifically, polyethyleneimine is added to a solvent (e.g., alcohol) to obtain a polyethyleneimine solution. The polyethyleneimine solution is mixed with the first powder and then dried to obtain a second powder. The drying may be performed under negative pressure and at a temperature of 40°C to 50°C.

[0054] 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 with2-chloro-1,3-butadiene)). In detail, the second powder can be moistened with deionized water, and then the adhesive is added and mixed and stirred, and then the water is removed under vacuum at a temperature of 105° C. to obtain the first particles. In some embodiments, granulation can be further performed by a syringe or a granulator. In other embodiments, the granulation process can be omitted.

[0055] In some embodiments, the epoxide in step d is butylene oxide. Specifically, butylene oxide is added dropwise to the polyethyleneimine solution, and stirred evenly at room temperature (eg, 25° C.) to perform a cross-linking reaction to obtain a transparent and clear solution.

[0056] In some embodiments, in step e, after the transparent clear liquid is mixed and stirred with the first powder, a milky white liquid including white suspended matter 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.

[0057] In some embodiments, in step f, the third powder may be moistened with deionized water, and then a binder may be added and mixed, and then the water may be removed under vacuum at a temperature of 105° C. to obtain second particles. In some embodiments, a granulation process may be further performed or omitted.

[0058] Accordingly, the present invention can adjust the heat release of the adsorption particles when adsorbing and / or desorbing carbon dioxide by adjusting the ratio of polyethyleneimine (providing amine groups) to butylene oxide (providing epoxy groups) (amine-epoxy 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.

[0059] In some embodiments, an example is provided in which the sorbent composition includes first particles and second particles, and the second particles include third particles and fourth particles.

[0060] First particles: 50g of porous silicon powder was dried at 100°C to remove moisture, and then mixed with 260g of 0.79wt.% sodium phosphate aqueous solution for 2 hours, and then vacuum dried at 100°C to remove moisture to obtain white powder. 94g of 34wt.% polyethyleneimine aqueous solution was prepared, mixed with the white powder for 2 hours, and the solution was removed at a negative pressure of 40°C to obtain an 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. Then, the first white particles with high heat release and high carbon dioxide adsorption were obtained by vacuum dehydration and drying at 105°C. 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.

[0061] Third particles: 50g of porous silicon powder was dried at 100°C to remove moisture, and then mixed with 260g of 0.79wt.% sodium phosphate aqueous solution for 2 hours, and then vacuum dried at 100°C 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°C for 20 hours, and then mixed and stirred with white powder for 2 hours, and the solution was removed at negative pressure of 40°C to obtain amino-epoxy modified white powder. 5g of amino-epoxy modified white powder was moistened with deionized water, and then 0.65g of adhesive was added and mixed and stirred. Then, it was dried by vacuum dehydration at 105°C to obtain white third particles with medium heat release and medium carbon dioxide adsorption. Among them, the ratio of the weight of the material containing the amino group to the weight of the substrate particles is about 0.64. Among them, the ratio of the weight of the epoxide to the weight of the material containing the amino group is about 0.594.

[0062] 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 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 of 40℃ to obtain amino-epoxy modified white powder. 5g of amino-epoxy modified white powder was wetted with deionized water, and then 0.65g of adhesive was added, mixed and stirred. Then, it was dried at 105℃ to remove water in vacuum, and white fourth particles with low heat and low carbon dioxide adsorption were obtained. Among them, the ratio of the weight of the material containing amino groups to the weight of the substrate particles is about 0.32. Accordingly, the amount of amino group coating on the surface of the fourth particle can be less than the amount of amino group coating on the surface of the third particle. The ratio of the weight of the epoxy to the weight of the material containing the amine group is about 0.594. Therefore, the amount of the amine-epoxy modification of the third particle can be similar to the amount of the amine-epoxy modification of the fourth particle.

[0063] Reference Figure 2 , which shows the Fourier transform infrared spectroscopy (FTIR) analysis diagram according to some embodiments of the present invention. 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 4000cm -1 ~400cm -1 .like Figure 2 As shown, the first, third and fourth particles are at 1564 cm -1 ~1587cm -1 Department has representatives-NH 2 (primary amine) peak at 3275 cm -1 There is a peak representing -NHR (secondary amine) at Figure 2 As shown, the content of primary amine in the first particle is greater than that in the third particle and the fourth particle, and the content of primary amine in the third particle is greater than that in the fourth particle. Figure 2 As shown, the content of secondary amine in the first particle is greater than the content of secondary amine in the third particle and the fourth particle, and the content of secondary amine in the third particle is greater than the content of secondary amine in the fourth particle.

[0064] In some embodiments, the samples were analyzed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) at 10% CO 2 The thermal properties of the adsorbed particles were analyzed under a gas environment. In addition, the particle density was calculated by measuring the volume of the particles and weighing them on a balance. The results are shown in Table 1.

[0065] Table 1

[0066]

[0067]

[0068] As can be seen from Table 1, the first particle has a high carbon dioxide adsorption capacity. If it is directly used to fill a carbon dioxide adsorption fixed bed reactor, it is easy to generate local high temperature due to the high adsorption heat, causing the first particle to deteriorate and reduce the 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 releases is similar, ranging from approximately 0.58 to 0.72 g / cm 3 It means that the adsorbed particles can be evenly mixed and dispersed, and it is not easy to produce stratification effect due to air flow disturbance and lose the dispersion function.

[0069] In contrast, when 10 g of the first particles (particle density: 0.58-0.65 g / 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 particles and the quartz sand were separated within 30 seconds of stirring. This means that when the adsorbed particles were mixed with traditional dispersion materials (e.g., quartz sand, ceramic balls, steel balls, ceramic rings, metal rings), the particle density difference was too large to be evenly dispersed.

[0070] Adsorption particle fixed bed column adsorption / desorption cycle test (I):

[0071] According to Table 2, Examples 1 to 10 and Comparative Examples 1 and 2 of the adsorbent composition were prepared as samples. The average heat release is 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 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 For example, the heat release of the fourth particle can be 63.3 J / g, and the adsorption amount can be 0.84 mmolCO 2 / g.

[0072] Table 2

[0073]

[0074]

[0075] Take 15g of sample and fill it into a fixed bed column. 2 With 10vol.%H2 The target gas was a mixture of CO and N. The adsorption conditions were an inlet 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, a pressure of 0.2 bar, and CO 2 The desorption process was terminated after the concentration was desorbed to 2% to 3%. The above adsorption / desorption process was one cycle, and a total of 5 cycles were performed. The results are shown in Table 3.

[0076] In addition, the appearance of the samples before and after 5 adsorption / desorption cycles was observed and recorded. The "-" in the appearance means that there is no significant difference in appearance.

[0077] Reference Figure 3 , which shows a schematic diagram of a penetration curve according to some embodiments of the present invention. The adsorption amount may include a working adsorption amount and an equilibrium adsorption amount, and the measurement and calculation methods are as follows. 0 ), CO 2 With a fixed inflow concentration (C in ) flows into the fixed bed column. 2 Initially, the CO in the output gas is adsorbed by the adsorbent particles. 2 The concentration decreases. As time goes by, the adsorption particles continue to adsorb CO 2 To saturation. Therefore, CO can be measured in the outflow gas 2 The concentration increases with time until the CO in the outflow gas is equal to that in the inflow (input) gas. 2 When the concentrations are equal, it means that the adsorption has reached saturation and the adsorption reaction has reached equilibrium. Figure 3 As shown, the outflow gas CO 2 Plotting the concentration against time yields an S-shaped curve, called a breakthrough curve (BTC). b ), the outflow concentration is 10% of the inflow concentration (C out =0.1C in ). At the equilibrium time (t e ), the outflow concentration is equal to the inflow concentration (C out =C in ) and reaches adsorption equilibrium. CO 2 The adsorption amount is determined by the inlet concentration (C in ) multiplied by the inflow flow rate (Qin), and the outflow concentration (C out ) and outflow rate (Q out ) is obtained by integrating the difference of the product of 0 to b The integrated adsorption capacity is called the working adsorption capacity. 0 to e The integrated adsorption amount is called the equilibrium adsorption amount.

[0078] The equilibrium adsorption recovery rate (recovery, %) is:

[0079] The 5th equilibrium adsorption amount / the 1st equilibrium adsorption amount x 100%

[0080] The working adsorption recovery rate is:

[0081] The 5th working adsorption amount / the 1st working adsorption amount x 100%

[0082] Table 3

[0083]

[0084] As shown in Table 2 and Table 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 particles 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.

[0085] 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 capacity and equilibrium adsorption capacity are both 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 is yellowish, indicating 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 heat, and there is no change in appearance. This indicates that the adsorbent composition including adsorption particles with different exothermic heat can improve the cyclic adsorption / desorption performance of the material and avoid local high-temperature degradation.

[0086] As shown in Table 2 and Table 3, it can be seen from 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 capacity and the working adsorption recovery rate can be increased at the same time.

[0087] The adsorbent composition of the present invention includes particles with different heat releases, thereby improving adsorption efficiency (e.g., equilibrium adsorption capacity, working adsorption capacity, equilibrium adsorption recovery rate, and working adsorption recovery rate) and / or avoiding failure of the adsorbent composition. The manufacturing method of the present invention can change the heat release of the particles by adjusting the amine content in different particles to obtain the adsorbent composition.

[0088] For example, the heat release of the first particle may be greater than that of the second particle, and the first particle and the second particle may be mixed in a specific ratio to form an adsorbent composition. Therefore, the generation of high temperature in the reactor can be avoided by adjusting the average heat release of the adsorbent composition. Furthermore, the deterioration of the adsorbent composition is effectively avoided, and the adsorption efficiency can be improved and / or the failure of the adsorbent composition can be avoided. For example, the adsorbent composition of 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 is increased, thereby improving the adsorption efficiency.

[0089] The scope of protection of the present invention is not limited to the processes, machines, manufactures, material compositions, devices, methods and steps in the specific embodiments described in the specification. Anyone with common knowledge in the relevant technical field can understand the current or future developed processes, machines, manufactures, material compositions, devices, methods and steps from the disclosure of the present invention. As long as substantially the same functions can be implemented or substantially the same results can be obtained in the embodiments described herein, they can all be used according to the present invention. Therefore, the scope of protection of the present invention includes the aforementioned processes, machines, manufactures, material compositions, devices, methods and steps. Any embodiment or claim of the present invention is not required to achieve all the objects, advantages and / or features disclosed in the present invention.

[0090] Several embodiments are summarized above so that those with common knowledge in the technical field to which the present invention belongs can better understand the concept of the embodiments of the present invention. Those with common knowledge in the technical field to which the present invention belongs should understand that they can design or modify other processes and structures based on the embodiments of the present invention to achieve the same purpose and / or advantages as the embodiments introduced herein. Those with common knowledge in the technical field to which the present invention belongs should also understand that such equivalent processes and structures do not deviate from the spirit and scope of the present invention, and they can make various changes, substitutions and replacements without violating the spirit and scope of the present invention.

Claims

1. An adsorbent composition, include: 100 parts by weight of a first particle, wherein the first particle is a base material particle having an amino group and having a first heat release amount; and 3 to 450 parts by weight of the second particle, the second particle is the substrate particle having an amino group and an epoxy group and having a second exothermic heat, Wherein, the first heat release 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. 2 . The adsorbent composition according to claim 1 , wherein the content of amine groups in the first particles is greater than the content of amine groups in the second particles.

3. The adsorbent composition according to claim 1, wherein the second particle include: 0 to 330 parts by weight of third particles having a third heat release amount greater than 65 J / g and less than or equal to 90 J / g; and 0 to 150 parts by weight of the fourth particle, having a fourth heat release amount different from the third heat release amount, the fourth heat release amount being greater than or equal to 35 J / g and less than 65 J / g, wherein the third particle and the fourth particle are not simultaneously 0 parts by weight. 4 . The adsorbent composition according to claim 3 , wherein the content of amine groups in the third particles is greater than the content of amine groups in the fourth particles.

5. The adsorbent composition according to claim 1, wherein 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.

6. A method for producing an adsorbent composition, include: Providing a first particle, wherein the first particle is a substrate particle having an amino group, and the first particle has a first exothermic value, and the first exothermic value is greater than 90 J / g and less than or equal to 130 J / g; Providing a second particle, wherein the second particle is the substrate particle having an amino group and an epoxy group, and the second particle has a second exothermic value, and the second exothermic value is greater than or equal to 35 J / g and less than or equal to 90 J / g; mixing the first particles and the second particles to obtain the adsorbent composition, in, The first particles are 100 parts by weight, and The second particles are 3 to 450 parts by weight.

7. The manufacturing method according to claim 6, wherein the first particle is provided include: Mixing the substrate particles with a metal chelating agent to obtain a first powder; Mixing the material containing an amine group with the first powder to obtain a second powder; and mixing the second powder with a binder to obtain the first particles, Wherein, the ratio of the weight of the material containing amino groups to the weight of the substrate particles is 0.5-0.

75.

8. The manufacturing method according to claim 7, wherein the second particle is provided include: mixing the amine-containing material and the epoxide to obtain a solution; Mixing the solution with the first powder to obtain a third powder; and mixing the third powder and the adhesive to obtain the second particles, 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 manufacturing method according to claim 8 , wherein the ratio of the weight of the material containing an amino group to the weight of the substrate particles is 0.2 to 0.65.

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