WO2017090825A1 - Diamine-zeolite composite and method for preparing same - Google Patents

Diamine-zeolite composite and method for preparing same Download PDF

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WO2017090825A1
WO2017090825A1 PCT/KR2016/000388 KR2016000388W WO2017090825A1 WO 2017090825 A1 WO2017090825 A1 WO 2017090825A1 KR 2016000388 W KR2016000388 W KR 2016000388W WO 2017090825 A1 WO2017090825 A1 WO 2017090825A1
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diamine
zeolite
method
carbon dioxide
zeolite composite
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Korean (ko)
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최민기
김채훈
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한국과학기술원
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/62Carbon oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16Alumino-silicates
    • B01J20/18Synthetic zeolitic molecular sieves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection
    • Y02A50/20Air quality improvement or preservation
    • Y02A50/23Emission reduction or control
    • Y02A50/234Physical or chemical processes, e.g. absorption, adsorption or filtering, characterised by the type of pollutant
    • Y02A50/2342Carbon dioxide [CO2]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C10/00CO2 capture or storage
    • Y02C10/04Capture by chemical separation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C10/00CO2 capture or storage
    • Y02C10/08Capture by adsorption

Abstract

The present invention relates to a method for preparing a diamine-zeolite composite, the method being characterized in that a positive ion of zeolite is replaced with an ammonium ion (NH4+), followed by heat treatment to remove ammonia (NH3), and then the heat-treated zeolite is treated with a diamine, followed by heat treatment to remove an unreacted diamine, wherein the diamine-zeolite composite exhibits high carbon dioxide adsorption ability even in the presence of water due to the amine present in the zeolite pores in a post-combustion carbon dioxide capture process, and achieves very high regeneration stability even under high-temperature adsorbent regeneration conditions by allowing the water adsorbed inside the pores to suppress urea formation. In addition, the diamine-zeolite composite of the present invention is low in synthesis cost since the composition is a zeolite-based material, and is expected to also have a very high possibility of practical use since the composition has excellent hydrothermal stability and can be molded into a desired form.

Description

Diamine-zeolite composite and preparation method thereof

The present invention relates to a diamine-zeolite composite and a method for manufacturing the same, and more particularly, to replace the cation of the zeolite with ammonium ions (NH 4 + ), and then heat-treat to remove ammonia (NH 3 ). The present invention relates to a method for producing a diamine-zeolite composite, which comprises adding a diamine to a zeolite and reacting the same, followed by heat treatment to remove unreacted diamine.

Global warming due to greenhouse gases has been expected to threaten human survival in the future, and carbon dioxide is a representative greenhouse gas, which accounts for about 77% of the global greenhouse gas. It is true that the development of renewable energy to replace fossil fuels can solve the problem of climate change caused by global warming.However, until the development of economical renewable energy, the stable development of fossil fuels considering the sustainable development of humankind is required. Development of collection technology is urgently needed.

CO2 capture technology can be divided into three major technologies: 1) oxy-combustion capture, which burns fuel using only oxygen instead of air; 2) pre-combustion capture technology that separates carbon dioxide by reacting the fuel prior to burning the fuel; And 3) post-combustion capture technology for capturing carbon dioxide from a gas mixture generated after combustion of fossil fuels. Among the carbon dioxide capture technologies, the most promising technologies that can be easily applied to industrial sites that are already in operation, and economical efficiency and efficiency are considered post-combustion capture when considering commercialization.

Post-combustion capture, which captures carbon dioxide from the gas mixture generated after combustion of fossil fuels, includes wet absorption, dry adsorption, membrane separation, deep cooling, and wet amines using monoethanolamine (MEA). Absorption is the most widely used. The wet amine absorption method using MEA is a method in which carbon dioxide contained in exhaust gas after combustion is reacted with MEA diluted to 30% or less and adsorbed, followed by heating a solvent to separate high concentrations of carbon dioxide. However, this method requires a lot of energy in the regeneration of the absorbent, which is very uneconomical at the present time due to cost and scale-up problems in large industrial sites. Thus, dry adsorbents with less energy needed for adsorbent regeneration have emerged as a new alternative.

As a representative example of a dry adsorbent, studies of the "Molecular Basket" concept of supporting an amine-based absorbent on an adsorbent have been actively conducted at home and abroad. Typically, polyethyleneimine was supported on a silica carrier having mesopores to confirm high carbon dioxide adsorption performance (Zhang, H. et al., Royal Society of Chemistry 4, 19403-19417. 2014). However, according to an announcement from the Sayari, A. group at Ottawa University, polyethyleneimine is exposed to carbon dioxide dried at high temperatures (> 393 K), which is the desorption condition of the Temperature swing adsorption (TSA) process. It has been confirmed that severe inactivation occurs due to the formation of urea (Heydari-Gorji, A. et al., Industrial & Engineering Chemistry Research, 51, 6887-6894, 2012). Therefore, post-combustion capture of post-combustion capture, in which the regeneration of the adsorbent takes place under dry, high temperature carbon dioxide conditions, is not yet applicable to the actual process because it acts as the main cause of low regeneration stability in the continuous adsorption and desorption process. It is in an inadequate stage, and further studies are needed to show stable regeneration while suppressing element formation.

Another dry adsorbent is zeolite, a microporous material. Zeolites have constant micro pores and are well known pore structures and have been actively studied in the field of gas adsorption and separation. In particular, it is widely used in various industrial fields because the synthetic unit price is low, mass production is possible, and the particles can be formed into a desired shape, which has many advantages in scale-up. Zeolite physically adsorbs carbon dioxide through strong interaction of carbon dioxide with the electric field inside the micro-pores, and has the advantage of less thermal energy required for regeneration than the amine-based dry adsorbent. However, since moisture and carbon dioxide molecules compete for the same adsorption site in the micropores, carbon dioxide adsorption capacity is significantly decreased when water is present, which makes it difficult to use in post-combustion capture technology in which water exists in adsorption conditions. (Harlick, PJE et al., Indesterial & Engineering Chemistry Research 45, 3248-3255, 2006).

Thus, the present inventors, in order to apply the zeolite to the post-combustion trapping technology in which water is present, replaces the cation of the zeolite with ammonium ions (NH 4 + ), and then heat-treats to remove ammonia (NH 3 ) When a diamine is treated with diamine and then heat treated to remove unreacted diamine, an amine group capable of selectively absorbing carbon dioxide through a chemical reaction inside the zeolite is prepared. It was confirmed that the adsorption material having a high carbon dioxide adsorption capacity can be produced even in the process containing water to complete the present invention.

Summary of the Invention

It is an object of the present invention to provide a method for preparing diamine-zeolite which can selectively absorb carbon dioxide through chemical reaction even in the presence of moisture.

Another object of the present invention is to provide the diamine-zeolite.

Another object of the present invention to provide a carbon dioxide adsorption method using the diamine-zeolite complex.

Still another object of the present invention is to provide a carbon dioxide adsorbent containing the diamine-zeolite composite.

In order to achieve the above object, the present invention comprises the steps of (a) replacing the cation of the zeolite with ammonium ions (NH 4 + ), and then heat-treating to remove ammonia (NH 3 ); (b) adding and reacting diamine to the heat treated zeolite; And (c) provides a method for producing a diamine-zeolite composite comprising a heat treatment to remove the unreacted diamine.

The present invention also provides a diamine-zeolite composite prepared by the above method and thermally stable at temperatures below 500K.

The present invention also provides a carbon dioxide adsorption method using a diamine-zeolite composite prepared by the above method.

The present invention also provides a carbon dioxide adsorbent containing the diamine-zeolite composite prepared by the above method.

1 is a schematic diagram illustrating a manufacturing process and a structure of a diamine-zeolite composite according to an embodiment of the present invention.

Figure 2 shows the results of the elemental analysis (Elemental Analysis, EA) of the diamine-zeolite composite according to an embodiment of the present invention.

3 is a graph showing the results of X-ray diffraction analysis (X-Ray Diffraction, XRD) of the diamine-zeolite composite according to an embodiment of the present invention.

4 is a graph showing a mass spectrometer result of the diamine-zeolite composite according to an embodiment of the present invention.

5 is a graph showing the results of carbon dioxide adsorption and regeneration stability measured by thermogravimetric-mass spectrometry (TGA-MS) using a diamine-zeolite composite according to an embodiment of the present invention.

Detailed description and specifics of the invention Embodiment

The present invention can all be achieved by the following description. The following description should be understood to describe preferred specific examples of the invention, but the invention is not necessarily limited thereto. In addition, the accompanying drawings are for ease of understanding, and the present invention is not limited thereto. Details of individual components may be appropriately understood by specific gist of the related description to be described later.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

In the present invention, when preparing a diamine-zeolite composite by stably introducing an amine through the reaction of hydrogen cation (H + ) and diamine in the zeolite pores, the silicon (Si) / aluminum (Al) in the zeolite skeleton It was confirmed that the amount of hydrogen cation (H + ) inside the zeolite pores can be adjusted by adjusting the ratio, and therefore, the amount of amine in the diamine-zeolite complex can be controlled.

As shown in FIG. 1, the cation of the zeolite was replaced with ammonium ions (NH 4 + ), and then ammonia (NH 3 ) was removed and the diamine was treated to obtain a diamine-zeolite complex.

Therefore, in one aspect, the present invention comprises the steps of: (a) replacing the cation of the zeolite with ammonium ions (NH 4 + ), followed by heat treatment to remove ammonia (NH 3 ); (b) adding and reacting diamine to the heat treated zeolite; And (c) relates to a method for producing a diamine-zeolite composite comprising the step of heat treatment to remove unreacted diamine.

In another aspect, the present invention relates to a diamine-zeolite composite prepared by the above method and thermally stable at a temperature of 500 K or less.

More specifically, in the present invention, the zeolite is preferably zeolite having a skeleton structure of FAU, EMT, MOR, LTL, MTW or a complex thereof, and can be used without limitation as long as it is a zeolite structure. In addition, it is preferable to use the thing whose molar ratio of silicon (Si) / aluminum (Al) of a zeolite is 1-100.

In the present invention, it is preferable to replace the cation of the zeolite with ammonium ion (NH 4 + ) through ion exchange, and ion exchange can be used without limitation as long as it is an aqueous solution in which a salt of ammonium ion (NH 4 + ) is dissolved. Most preferred is an aqueous solution of ammonium nitrate (NH 4 NO 3 ).

In the present invention, the heat treatment temperature for removing ammonia (NH 3 ) is preferably 373K to 1073K.

In the present invention, the diamine treatment is preferably performed in a gas phase or a liquid phase. Treatment of the diamine in the gas phase may be carried out in contact with an inert gas mixture comprising diamine molecules in the gas phase, the inert gas being helium (He), argon (Ar), nitrogen (N 2 ) or their It is preferable that it is a mixed gas. In addition, the solvent used in the process of treating diamine in the liquid phase includes all polar organic solvents in which the diamine can be dissolved, and includes water, methanol, ethanol, chloroform and aceto. Nitrile (acetonitrile), tetrahydrofuran (tetrahydrofuran) or a mixed solvent thereof is preferable. Moreover, it is preferable that diamine treatment temperature is 283K-473K.

In the present invention, the diamine is preferably a compound of formula (I),

Formula I

Figure PCTKR2016000388-appb-I000001

In the above formula, R 1 to R 4 are each independently H, CH 3 , or C 2 H 5 .

In the present invention, the unreacted diamine is a diamine which is physically adsorbed to the zeolite skeleton without reacting with hydrogen cation (H + ) inside the zeolite pores, and the heat treatment temperature for removing the unreacted diamine is from 283K to It is preferable that it is 473K. In addition, the heat treatment for removing the unreacted diamine is preferably heat treatment in an inert gas atmosphere containing water, the inert gas is helium (He), argon (Ar), nitrogen (N 2 ) or a mixed gas thereof Is preferably.

In the present invention, the diamine-zeolite composite preferably has a molar ratio of nitrogen (N) / aluminum (Al) of 0.1 to 10.

Diamine-zeolite composite prepared in the present invention and when it is used as a carbon dioxide adsorbent under the post-combustion capture process conditions, conditions in which water is present through a specific chemical reaction of the amine functional group and carbon dioxide inside the zeolite pores In addition, it showed an effective carbon dioxide adsorption capacity, and because the generation of urea is suppressed by the moisture present in the zeolite pores, it was confirmed that the very high stability during the regeneration of the adsorbent. That is, the equilibrium adsorption amount of the diamine-zeolite composite of the present invention is 5.2 wt% (EDA-Y), 3.8 wt% (DMEDA-Y), 1.2 wt% (TMEDA-Y), depending on the type of amine used. It was confirmed that it is stable even if repeated 10 times adsorption / regeneration.

Therefore, in another aspect, the present invention relates to a carbon dioxide adsorption method using a diamine-zeolite composite prepared by the above method.

In yet another aspect, the present invention relates to a carbon dioxide adsorbent containing a diamine-zeolite composite prepared by the above method.

More specifically, carbon dioxide adsorption using the diamine-zeolite composite of the present invention is capable of adsorbing or desorbing carbon dioxide in wet or dry conditions.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited to these examples.

Example 1: Preparation of diamine-zeolite composites (gas phase diamine treatment)

Preparation of the diamine-zeolite complex began with the ammonium ion (NH 4 + ) exchange of zeolites. An ion-exchange process is put NaY 5g of ammonium nitrate (NH 4 NO 3) 1M aqueous solution 1L exchanged as was stirred for 6 hours at a constant speed of 400rpm, ammonium ion (NH 4 +) via the above process Y zeolite " NH 4 -Y ".

The "NH 4 -Y" was introduced into a plug-flow quartz reactor and heated at 573K for 6 hours under flowing dry air (200 mL / min) and cooled to room temperature under flowing He (200 mL / min). Samples that have undergone the above procedure are designated as "HY".

He (200 mL / min) flowing through a bubbler containing ethylenediamine for 6 hours was introduced into the zeolite pores for 3 hours to graf the "H-Y" amine functional group. Subsequently, He (200 mL / min) was flowed to remove diamine physically adsorbed to the zeolite skeleton without reacting with “H-Y” and treated at 373K for 24 hours to synthesize a diamine-zeolite composite. Samples prepared as above were designated as "EDA-Y (G)".

Except for using N, N'-dimethylethylenediamine instead of ethylenediamine as a material for reacting "HY" and amine in the manufacturing process of "EDA-Y (G)". And a diamine-zeolite composite was synthesized in the same manner, and the sample thus prepared was designated as "DMEDA-Y (G)".

In addition, N, N, N ', N'-tetramethylethylenediamine (N, N, instead of ethylenediamine as a material for reacting "HY" and an amine in the manufacturing process of "EDA-Y (G)". Diamine-zeolite composites were synthesized in the same manner except that N ', N'-tetramethylethylenediamine) was used, and the samples thus prepared were designated as "TMEDA-Y (G)".

Example 2: Preparation of Diamine-zeolite Composite (Liquid Diamine Treatment)

Preparation of the diamine-zeolite complex began with the ammonium ion (NH 4 + ) exchange of zeolites. An ion-exchange process is put NaY 5g of ammonium nitrate (NH 4 NO 3) 1M aqueous solution 1L exchanged as was stirred for 6 hours at a constant speed of 400rpm, ammonium ion (NH 4 +) via the above process Y zeolite " NH 4 -Y ".

The "NH 4 -Y" was introduced into a plug-flow quartz reactor and heated at 573K for 6 hours under flowing dry air (200 mL / min) and cooled to room temperature under flowing He (200 mL / min). Samples that have undergone the above procedure are designated as "HY".

To react the "HY" with the amine, 3 g of "HY" was added to 100 mL of 25% ethylenediamine aqueous solution, stirred at 333 K for 6 hours, recovered, and dried at 373 K for 12 hours to diamine-zeolite complex. Was synthesized. Samples prepared as above were designated as "EDA-Y (L)".

Except for using N, N'-dimethylethylenediamine instead of ethylenediamine as a material for reacting "HY" and amine in the manufacturing process of "EDA-Y (L)". And a diamine-zeolite composite was synthesized in the same manner, and the sample thus prepared was designated as "DMEDA-Y (L)".

In addition, N, N, N ', N'-tetramethylethylenediamine (N, N, instead of ethylenediamine as a material for reacting "HY" and an amine in the manufacturing process of "EDA-Y (L)". Diamine-zeolite composites were synthesized in the same manner except that N ', N'-tetramethylethylenediamine) was used, and the samples thus prepared were designated as "TMEDA-Y (L)".

Example 3: Physicochemical Properties of Diamine-zeolite Composites

Physicochemical characterization of "NH 4 -Y", "HY" and diamine-zeolite composites prepared in Examples 1 and 2 was performed in the following manner, with reference to FIGS. 2 to 4 as follows. It describes in detail.

Figure 2 shows the content of nitrogen (N) measured by elemental analysis (EA) of the diamine-zeolite composites prepared in Examples 1 and 2. The nitrogen content of the sample treated with diamine in the gas phase is EDA-Y (G); 5.64 mmol N / g, DMEDA-Y (G); 3.99 mmol N / g, TMEDA-Y (G); Sample EDA-Y (L) treated with diamine in a liquid phase at 2.37 mmol N / g; 4.92 mmol N / g, DMEDA-Y (L); 3.16 mmol N / g, TMEDA-Y (L); It was confirmed that the nitrogen content is higher than 1.54 mmol N / g. This indicates that when diamine is treated in the gas phase, it can be introduced into the micro pores more effectively, and the larger the size of the diamine molecules to be treated, the more limited the diffusion into the zeolite skeleton and the proportion of amine grafted into the zeolite pores. It was confirmed that this decreases.

3 is a graph showing the results of X-ray diffraction analysis (XRD) of "NH 4 -Y", "HY" and diamine-zeolite composites prepared in Examples 1 and 2. All samples showed strong crystallinity at 2θ at the same position, which confirmed that the zeolite skeleton did not collapse during the preparation of the diamine-zeolite composite.

Figure 4 shows the mass spectrometer results of the diamine-zeolite composites prepared in Examples 1 and 2, and is a graph measuring the thermal stability of amines in the diamine-zeolite complex. All samples were found to amine drop or start to decompose at temperatures above 500K and stable at temperatures below that. In addition, these results indicate that when the diamine-zeolite composite is used as a carbon dioxide adsorbent, the decomposition of the amine does not occur in a post-combustion capture process where adsorption and regeneration occurs at a temperature range lower than 500K, resulting in high regeneration stability. It is believed to have.

Example 4 Evaluation of Adsorption / Regeneration of Carbon Dioxide Using Diamine-zeolite Composites

The carbon dioxide adsorption capacity and regeneration stability of the "NH 4 -Y", "HY" and diamine-zeolite composites prepared in Examples 1 and 2 under the post-combustion capture process conditions including moisture were evaluated. With reference to Figure 5, it will be described in detail as follows.

FIG. 5A shows the (gas phase) diamine-zeolite composite prepared in Example 1, and FIG. 5B shows the (liquid) diamine-zeolite composite prepared in Example 2, under the post-combustion capture process conditions containing water. The adsorption capacity of carbon dioxide was measured by thermogravimetric analysis (TGA-MS), and the "HY" prepared in Example 1 and the fumed silica "PEI (50) / fumed silica" loaded with polyethyleneimine were used as a control. It was. The PEI (50) / fumed silica adsorbent was prepared by dissolving 1 g of PEI having a molar mass of 1200 g / mol in 10 g of methanol and then supporting 1 g of fumed silica for 6 hours in a 323 K vacuum oven. The increase in mass due to carbon dioxide and water adsorption of each adsorbent was measured by thermogravimetric analysis, and the mass increase due to adsorption of carbon dioxide alone was confirmed by correcting the mass increase due to moisture adsorption through mass spectrometry. As a post-combustion capture process containing water, a gas consisting of 15 vol.% Carbon dioxide (CO 2 ), 0.6 vol.% Moisture, 84.4 vol.% Nitrogen (N 2 ) was used, and about 20 mg. Adsorbent was placed in a TGA pan and the mixed gas was flowed at 50 sccm (standard cubic centimeters per minute) and maintained at 313 K for 1 hour. During desorption (regeneration), dried 100% carbon dioxide (CO 2 ) was flowed at 50 sccm and maintained at 423 K for 1 hour. The adsorption and desorption were repeated 10 times with one cycle.

In the case of "H-Y" used as a control, it can be seen that the adsorption capacity of carbon dioxide is very low in the presence of moisture, because the carbon dioxide and water compete for the same adsorption site.

As another control, "PEI (50) / fumed silica" loaded with polyethyleneimine on fumed silica showed very low regeneration stability, which was formed by reuse of urea under high temperature dried carbon dioxide conditions. This is because there is less amine available.

On the other hand, in the diamine-zeolite composites prepared in Examples 1 and 2, due to the specific chemical reaction of the amine (amine) and carbon dioxide inside the zeolite pores it was confirmed that the high carbon dioxide adsorption capacity in the presence of water. In addition, the carbon dioxide adsorption capacity is stable over several cycles because water adsorbed in the zeolite micropores inhibits the formation of urea in the reaction of amine and carbon dioxide. Among the diamine-zeolite composite samples, the diamine-treated sample (FIG. 5A) shows higher adsorption capacity than the diamine-treated sample (FIG. 5B) in the liquid phase. As shown in FIG. It is confirmed that more diamine can be introduced into the pores when the diamine is treated. In addition, it can be seen that the sample using ethylenediamine (EDA) having the smallest molecular weight among the types of diamines used exhibits high carbon dioxide adsorption capacity with the highest amine content.

As described above in detail specific parts of the present invention, it will be apparent to those skilled in the art that these specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. will be. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

The diamine-zeolite composite according to the present invention can stably introduce amine through the reaction of hydrogen cation (H + ) and diamine in the zeolite pores, and silicon (Si) / aluminum (Al) in the zeolite skeleton. The amount of hydrogen cation (H + ) inside the zeolite pores can be adjusted by adjusting the mole ratio, and thus, the amount of amine in the diamine-zeolite complex can be controlled. When the diamine-zeolitic complex of the present invention is used as a carbon dioxide adsorbent under post-combustion capture conditions, the carbon dioxide adsorption ability is effective despite the presence of water through a specific chemical reaction of carbon dioxide with an amine functional group in the zeolite pores. Since the formation of urea is suppressed by the moisture adsorbed inside the micropores, it shows very high stability during regeneration of the adsorbent. In addition, since the diamine-zeolite composite of the present invention is a zeolite-based material, the diamine-zeolite composite may be manufactured through an economic process and may be molded into a desired form.

Claims (15)

  1. Method for preparing a diamine-zeolite composite comprising the following steps:
    (a) replacing the cation of the zeolite with ammonium ions (NH 4 + ) and then heat-treating to remove ammonia (NH 3 );
    (b) adding and reacting diamine to the heat treated zeolite; And
    (c) heat treatment to remove unreacted diamine.
  2. The method of claim 1, wherein the zeolite has at least one skeleton structure selected from the group consisting of FAU, EMT, MOR, LTL, and MTW.
  3. The method of claim 1, wherein the zeolite has a molar ratio of silicon (Si) / aluminum (Al) of 1 to 100, characterized in that the manufacturing method of the diamine-zeolite composite.
  4. The compound of claim 1 wherein the diamine is a compound of formula (I),
    Formula I
    Figure PCTKR2016000388-appb-I000002
    Wherein R 1 to R 4 are each independently H, CH 3 , or C 2 H 5 .
  5. According to claim 1, wherein the heat treatment temperature of the step (a) is a method for producing a diamine-zeolite composite, characterized in that 373K to 1073K.
  6. The method of claim 1, wherein the diamine treatment is a gas phase or a liquid phase process for producing a diamine-zeolite composite.
  7. The method of claim 1, wherein the reaction temperature of step (b) is 283K to 473K.
  8. The method for producing a diamine-zeolite composite according to claim 1, wherein the unreacted diamine is a diamine which is physically adsorbed to the zeolite skeleton without reacting.
  9. The method of claim 1, wherein the heat treatment of step (c) is performed in an inert gas atmosphere containing water.
  10. According to claim 1, wherein the heat treatment temperature of the step (c) is a method for producing a diamine-zeolite composite, characterized in that 283K to 473K.
  11. A diamine-zeolite composite prepared by the method of any one of claims 1 to 10 and thermally stable at temperatures of up to 500K.
  12. The diamine-zeolite composite according to claim 11, wherein the molar ratio of nitrogen (N) / aluminum (Al) of the diamine-zeolite composite is 0.1 to 10.
  13. Carbon dioxide adsorption method using the diamine-zeolite complex of claim 11.
  14. The method of claim 13, wherein the diamine-zeolite composite is capable of adsorbing or desorbing carbon dioxide under wet or dry conditions.
  15. A carbon dioxide adsorbent containing the diamine-zeolite complex of claim 11.
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