KR102489236B1 - Porous-organic-polymer-based ammonia adsorbents and their preparation - Google Patents

Abstract

The present invention relates to a porous organic polymer (POP) based ammonia adsorbent and a manufacturing method thereof.
According to the present invention, the porous organic polymer-based ammonia adsorbent into which a large amount of sulfonic acid group or alkyl group is introduced is not only easy to synthesize, but also significantly improves ammonia adsorption performance, so it can be usefully used in various fields requiring ammonia adsorption. .

Description

Porous-organic-polymer-based ammonia adsorbents and their preparation method {Porous-organic-polymer-based ammonia adsorbents and their preparation}

The present invention relates to a porous organic polymer (POP) based ammonia adsorbent and a manufacturing method thereof.

Its uses are diverse, such as fertilizer raw materials, petrochemical, electronic, and textile industries, and domestic ammonia consumption continues to increase due to industrial development. Ammonia is an intermediate raw material for fertilizer production along with sulfuric acid and phosphoric acid. Besides fertilizer, it is widely used in chemical industries such as military chemistry, synthetic fibers such as caprolactam and acrylonitrile monomer, refrigeration, soda industry, and ammonium bicarbonate production.

On the other hand, anaerobic digestion treatment of solid organic waste is increasing due to problems such as landfill shortage, atmospheric emission of landfill gas, and landfill saturation. However, in order to remove high-concentration ammonia using microorganisms, a huge amount of blowing power is required, which has become an obstacle to energy self-sufficiency at sewage treatment plants.

Ammonia, like hydrogen, has an eco-friendly feature of not emitting greenhouse gases, and at the same time, it is easy to liquefy even at low pressure, so it is easier to store and transport than hydrogen. contains By utilizing these characteristics of ammonia, ammonia released into the atmosphere is recovered and applied to the nitrogen oxide removal process, thereby separating wastewater containing high concentrations of ammonia into ammonia and liquid wastewater, thereby reducing ammonia contained in liquid wastewater. .

In general, high-purity ammonia gas is recovered through an adsorption and desorption reaction after stripping ammonia from livestock wastewater or high-concentration nitrogen-containing digestion and desorption liquid generated in the biogasification process without pre-treatment of solids.

Accordingly, although activated carbon or zeolite is usually used to recover ammonia by adsorption and desorption, there is a problem in that the use time is shortened due to the limitation of adsorption capacity, so the development of a new adsorbent that can compensate for this is required.

Republic of Korea Patent No. 10-1653382

The present invention has been made to solve the above problems, and in the present invention, it is intended to provide a porous organic polymer-based ammonia adsorbent with significantly improved ammonia adsorption performance through the introduction of a large amount of sulfonic acid groups and alkyl groups, and a method for preparing the same.

The present invention, in order to solve the above problems,

It provides an ammonia adsorbent comprising: a porous organic polymer-based framework represented by the following [Chemical Formula 1]:

[Formula 1]

In the above [Formula 1],

X is hydrogen or any one selected from the following [Structural Formula 1],

[Structural Formula 1]

,

,

R is any one selected from hydrogen, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

n is 1 or 2;

According to the present invention, the porous organic polymer-based ammonia adsorbent into which a large amount of sulfonic acid group or alkyl group is introduced is not only easy to synthesize, but also significantly improves ammonia adsorption performance, so it can be usefully used in various fields requiring ammonia adsorption. .

1 shows the results of measuring the ammonia adsorption performance of porous organic polymer skeleton compounds (1, 1S, 1E and 1ES) synthesized according to an embodiment of the present invention.
Figure 2 shows the results of measuring the water contact angle after post-synthetic transformation of the porous organic polymer scaffold compounds (1SC _x and 1ESC _x ) synthesized according to an embodiment of the present invention.
3 shows the results of measuring infrared spectroscopy data of porous organic polymer skeleton compounds (1S, 1SC _x , 1ES, 1ESC _x ) synthesized according to an embodiment of the present invention.
4 and 5 show ¹³ C NMR data of porous organic polymer skeleton compounds (1SC _x and 1ESC _x ) synthesized according to an embodiment of the present invention.
6 shows nitrogen adsorption (77 K) data of porous organic polymer scaffold compounds (1SC _x , 1ESC _x ) synthesized according to an embodiment of the present invention.
7 shows ammonia adsorption (298 K) data of porous organic polymer scaffold compounds (1SC _x , 1ESC _x ) synthesized according to an embodiment of the present invention.
8 is a breakthrough measurement curve of ammonia gas (500 ppm) measured in a dry condition of 0% relative humidity for porous organic polymer skeleton compounds 1, 1S, and 1SC ₉ synthesized according to an embodiment of the present invention. ) (a is an adsorption curve, b is a desorption curve).
9 shows breakthrough curves of ammonia gas (500 ppm) measured under dry conditions of 0% relative humidity for porous organic polymer skeleton compounds 1E, 1ES, and 1ESC ₉ synthesized according to an embodiment of the present invention ( a is an adsorption curve, b is a desorption curve).
FIG. 10 shows the result of observing changes in adsorption performance when the porous organic polymer skeleton compounds 1ES and 1ESC ₉ synthesized according to an embodiment of the present invention are reused 5 times.
11 shows breakthrough curves of ammonia gas (500 ppm) measured under moisture conditions of 80% relative humidity for porous organic polymer skeleton compounds 1, 1S, and 1SC ₉ synthesized according to an embodiment of the present invention ( a is an adsorption curve, b is a desorption curve).
12 shows breakthrough curves of ammonia gas (500 ppm) measured under moisture conditions of 80% relative humidity for porous organic polymer skeleton compounds 1E, 1ES, and 1ESC ₉ synthesized according to an embodiment of the present invention ( a is an adsorption curve, b is a desorption curve).
FIG. 13 shows the result of observing the change in adsorption performance when the porous organic polymer skeleton compound 1ESC ₉ synthesized according to an embodiment of the present invention is reused 5 times under moisture conditions.

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 one well known and commonly used in the art.

In the present invention, it is intended to provide a porous organic polymer-based ammonia adsorbent and a method for preparing the same, in which ammonia adsorption performance is significantly improved by introducing a large amount of sulfonic acid groups and alkyl groups.

To this end, the present invention provides an ammonia adsorbent comprising: a porous organic polymer-based skeleton represented by the following [Formula 1]:

[Formula 1]

In the above [Formula 1],

X is hydrogen or any one selected from the following [Structural Formula 1],

[Structural Formula 1]

,

,

R is any one selected from hydrogen, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

n is 1 or 2;

According to the present invention, 'substituted' in substituted or unsubstituted in the definition of R may mean substituted with one or more substituents selected from heavy hydrogen, an alkyl group, a carbonyl group, and an aryl group.

The present invention also provides a porous organic polymer-based framework represented by the following [Formula 1] by reacting a compound represented by the following [Formula 2] with an aldehyde solution in an aqueous HCl solution according to the following [Reaction Formula 1] Preparing; Provides a method for producing an ammonia adsorbent comprising:

[Scheme 1]

[Formula 2] [Formula 1]

X is any one selected from the following [Structural Formula 1],

[Structural Formula 1]

,

,

R is any one selected from hydrogen, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

n is 1 or 2;

According to the present invention, the compound represented by [Formula 2] may be prepared by reacting a compound represented by [Formula 3] with chlorosulfonic acid according to [Reaction Formula 2]:

[Scheme 2]

[Formula 3] [Formula 2]

n is 1 or 2;

The present invention also provides a method for adsorbing ammonia using the ammonia adsorbent.

[Example]

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as being limited by these examples. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

synthesis example . sulfonic acid group and the synthesis of porous organic polymers into which an alkyl group has been introduced.

Preparation of compound 1

Polymer compound 1 (corresponding to the case where n is 1 in [Formula 3]) was synthesized according to the following [Scheme 3]. Specifically, phloroglucinol (0.5 g, 3.96 mmol) and terephthaldehyde (0.4 g, 2.98 mmol) were completely dissolved in 15 mL of 1,4-dioxane solvent. After transferring this solution to a 35 mL microwave reaction pyrex cell, 1 mL of 35% HCl was added and the inlet was closed with a PTFE cap. After reacting in a microwave reactor (CEM Discover) at 160 ° C for 2 hours, the product was stirred in 200 mL of THF / MeOH for 1 hour, filtered, washed with THF, water, methanol, and acetone, and dried in an oven at 100 ° C. , Compound 1 was synthesized by removing solvent molecules present in the inner cavity for 12 hours using a vacuum pump at 120 °C.

[Scheme 3]

Preparation of compound 1E

Polymeric compound 1E (corresponding to the case where n is 2 in [Formula 3]) was synthesized according to the following [Scheme 4]. Specifically, phloroglucinol (0.5 g, 3.96 mmol) and 4,4'-biphenyldicarboxaldehyde (0.625 g, 2.98 mmol) were completely dissolved in 15 mL of 1,4-dioxane solvent. After transferring this solution to a 35 mL microwave reaction pyrex cell, 1 mL of 35% HCl was added and the inlet was closed with a PTFE cap. After reacting in a microwave reactor (CEM Discover) at 160 ° C for 2 hours, the product was stirred in 200 mL of THF / MeOH for 1 hour, filtered, washed with THF, water, methanol, and acetone, and then dried in an oven at 100 ° C. Then, compound 1E was synthesized by removing solvent molecules present in the inner cavity for 12 hours using a vacuum pump at 120 °C.

[Scheme 4]

Preparation of compound 1S

Polymeric compound 1S (corresponding to the case where n is 1 in [Formula 2]) was synthesized according to the following [Scheme 5]. Specifically, 120 mL of methylene chloride and 1 g of Compound 1 were put in a 250 mL round bottom flask and stirred for 1 hour. The flask was placed in an ice water bucket and 12 mL of chlorosulfonic acid was slowly dropped drop by drop using a dropping funnel and reacted for 4 days. After the reaction, the resultant was poured into a 1000 mL beaker containing ice and water, stirred for 6 hours, filtered, washed with water and methanol until the pH reached 7, and dried in an oven at 100 °C overnight. Then, compound 1S was synthesized by removing solvent molecules present in the inner cavity at 120 °C for 10 hours.

[Scheme 5]

compound 1ES's Produce

Polymer compound 1ES (corresponding to the case where n is 2 in [Formula 2]) was synthesized according to the following [Scheme 6]. Specifically, 120 mL of methylene chloride and 1 g of Compound 1E were put in a 250 mL round bottom flask and stirred for 1 hour. The flask was placed in an ice water bucket and 12 mL of chlorosulfonic acid was slowly dropped drop by drop using a dropping funnel and reacted for 4 days. After the reaction, the resultant was poured into a 1000 mL beaker containing ice and water, stirred until the ice melted, filtered, washed with water, methanol, and acetone until the pH reached 7, and dried in an oven at 100 ° C overnight. Then, compound 1ES was synthesized by removing solvent molecules present in the inner cavity using a pump at 120 °C for 12 hours.

[Scheme 6]

compound 1SC _x of Produce

According to the following [Scheme 1], the polymer compound 1SC _x (corresponding to the case where n is 1 in [Formula 1]) was synthesized. Specifically, 10 mL of an aldehyde solvent with x number of carbons (x = an integer of 1 or more) and 200 mg of 1S were put in a 20 mL vial, 0.2 mL of 35% HCl aqueous solution was added, and when x was 3 or more, 12 at 80 ° C. reacted over time. When x is less than 3, it was reacted at 50 °C for 12 hours. After completion of the reaction, it was thoroughly washed with hexane and acetone and dried in an oven at 100 ° C overnight. Then, compound 1SC _x was synthesized by removing solvent molecules present in the inner cavity at 120 °C for 10 hours.

[Scheme 1]

[Formula 2] [Formula 1]

X is any one selected from the following [Structural Formula 1],

[Structural Formula 1]

,

,

R is any one selected from hydrogen, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

n is 1.

In this embodiment, compounds represented by Structural Formula 2 were used as aldehyde solvents, and the synthesized compounds were compound 1SC ₃ , compound 1SC ₅ , compound 1SC _x7 , compound 1SC _x9 , compound 1SC _x10 , and compound according to the number of carbon atoms in the aldehyde solvent. Marked as 1SC _x 12.

[Structural Formula 2]

compound 1ESC _x of Produce

According to the following [Scheme 1], the polymer compound 1ESC _x (corresponding to the case where n is 2 in [Formula 1]) was synthesized. Specifically, 10 mL of an aldehyde solvent with x number of carbons (x = an integer of 1 or more) and 200 mg of 1S were put in a 20 mL vial, 0.2 mL of 35% HCl aqueous solution was added, and when x was 3 or more, 12 at 80 ° C. reacted over time. When x is less than 3, it was reacted at 50 °C for 12 hours. After completion of the reaction, it was thoroughly washed with hexane and acetone and dried in an oven at 100 ° C overnight. Then, compound 1ESC _x was synthesized by removing solvent molecules present in the inner cavity at 120 °C for 10 hours.

[Scheme 1]

[Formula 2] [Formula 1]

X is any one selected from the following [Structural Formula 1],

[Structural Formula 1]

,

,

R is any one selected from hydrogen, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

n is 2.

In this embodiment, compounds represented by the following Structural Formula 2 were used as aldehyde solvents, and the synthesized compounds were compound 1ESC ₃ , compound 1ESC ₅ , compound 1ESC _x7 , compound 1ESC _x9 , compound 1ESC _x10 , and compound according to the number of carbon atoms in the aldehyde solvent. Marked as _{1ESC x} 12.

[Structural Formula 2]

Experimental example 1. Ammonia adsorption capacity evaluation

1 shows the results of measuring the ammonia adsorption performance of the porous organic polymer skeleton compounds 1, 1S, 1E, and 1ES prepared according to the Synthesis Example.

As shown in FIG. ¹ , compounds 1S and 1ES showed a high adsorption amount of ammonia even at a low pressure of about 0.5 mbar. It was confirmed that it exhibited the best adsorption performance among porous material-based adsorbents.

Experimental example 2. Observation of hydrophobicity

Figure 2 is a porous organic polymer skeleton compound 1SC _x (x is 3, 5, 7, 9, 10, 12) prepared according to the synthesis example, 1ESC _x (x is 3, 5, 7, 9, 10, 12 ) shows the result of measuring the water contact angle after post-synthetic transformation.

Through the results of FIG. 2, when the alkyl chain is functionalized in 1S and 1ES functionalized with sulfonic acid, a water contact angle that was not previously present occurred and an angle of up to 120 degrees or more was observed. It was confirmed that it was sanctified.

Experimental example 3. Porous Organic Polymers skeletal body Characterization of compounds

Figure 3 shows the results of measuring infrared spectroscopy data of the porous organic polymer skeleton compounds (1S, 1SC _x , 1ES, 1ESC _x ) prepared according to the synthesis example.

Through the results of FIG. 3, when the alkyl chain is functionalized in the sulfonic acid-functionalized compounds 1S and 1ES, a CH stretching peak around 2900 cm ^-1 is observed, and in particular, the intensity of the peak increases as the length of the alkyl chain of aldehyde increases. confirmed that.

4 and 5 show ¹³ C NMR data of the porous organic polymer skeleton compounds (1SC _x and 1ESC _x ) prepared according to the Synthesis Example.

Through the results of FIGS. 4 and 5, when the alkyl chain is functionalized in 1S and 1ES functionalized with sulfonic acid, a peak related to the carbon of the alkyl chain is observed near 30 ppm, especially as the length of the alkyl chain of aldehyde increases. It was also confirmed that the intensity of

Experimental example 4. Analysis of gas adsorption characteristics

Figure 6 shows the nitrogen adsorption (77 K) data of the porous organic polymer skeleton compounds (1SC _x , 1ESC _x ) prepared according to the synthesis example, and Figure 7 shows their ammonia adsorption (298 K) data. will be.

Through the results of FIGS. 6 and 7 , it was confirmed that the adsorption performance decreased when the unit weight of the adsorbent increased in the case of materials functionalized with an alkyl group. In addition, it was confirmed that the 1S-based compound functionalized with an alkyl group exhibited a specific surface area value of up to 50 m ² g ^-1 , and the specific surface area value exhibited with a maximum of 10 m ² g ^-1 in the case of a 1ES-based compound functionalized with an alkyl group.

In addition, as shown in Table 1 below, compounds 1, 1E, 1S, 1ES, 1SC _x and 1ESC _x have specific surface areas of 4 - 1100 m ² / g, ammonia at a pressure of 0.5 mbar, 0.5 - 5.0 mmol / g, , it was confirmed that the adsorption amount was in the range of 5 - 20 mmol/g at 1 bar of ammonia.

Sample adsorbed NH ₃
around 5 mbar
(mmol g ^-1 ) adsorbed NH ₃
around 1 bar
(mmol g ^-1 ) BET surface area
(m ² g ^-1 ) One 1.63 (0.67 mbar) 13.99 902 1S 4.03 12.92 31 1SC ₃ 0.95 7.71 51 1SC ₅ 0.72 6.61 42 1SC ₇ 0.63 6.09 33 1SC ₉ 0.53 5.39 33 1SC ₁₀ 0.55 5.48 25 1SC ₁₂ 0.57 5.61 23 1E 1.08 (0.61 mbar) 14.13 1030 1ES 3.51 12.35 16 1ESC ₃ 0.80 5.76 8 1ESC ₅ 0.69 5.48 6 1ESC ₇ 0.68 5.59 5 1ESC ₉ 0.84 5.66 6 1ESC ₁₀ 0.86 5.81 5 1ESC ₁₂ 0.86 6.02 4

Experimental example 5. breaking equipment Analysis of ammonia gas adsorption characteristics under dry and moist conditions using

Breakthrough measurement curves of ammonia gas with a concentration of 500 ppm were observed for 1, 1S, 1SC ₉ , 1E, 1ES, and 1ESC ₉ under dry conditions (relative humidity: 0%) using breakthrough equipment. The results are shown in FIGS. 8 and 9 below (where a is an adsorption curve and b is a desorption curve in FIGS. 8 and 9 ).

Through the results of FIGS. 8 and 9, 1S (4460 min g ^-1 ) and 1ES (3890 min g ^{-1 )} functionalized with a sulfonic acid group were higher than 1 (3760 min g ^-1 ) and 1E (3030 min g ^{-1 )} . It was confirmed that the normalized adsorption time was much longer, and through this, the adsorption amounts of compounds 1S and 1ES were higher, and these results were consistent with the trend of the gas adsorption isotherm of FIG. 1.

Through this, it was found that the functionalization of the sulfonic acid group is actually advantageous for the removal of low-concentration ammonia gas, and in the case of 1SC ₉ and 1ESC ₉ functionalized with alkylation, as shown in FIGS. It was confirmed that the desorption of ammonia gas was performed.

Figure 10 will observe the performance change using the adsorbents of compounds 1ES and 1ESC ₉ repeated 5 times. Normal adsorbents are regenerated using a vacuum pump at high temperature, but in the case of alkylated adsorbents, almost all regeneration is achieved only by permeating helium gas at room temperature for a sufficient period of time, which is significantly different from 1ES without alkylation. can Therefore, it was confirmed that the alkylation reaction can be a useful synthesis strategy to increase the reusability of the adsorbent by solving the desorption problem of the existing ammonia adsorbents.

Next, breakthrough curves of ammonia gas with a concentration of 500 ppm were observed with respect to 1, 1S, 1SC ₉ , 1E, 1ES, 1ESC ₉ under moisture (80% relative humidity) conditions using breakthrough equipment, and the results It is shown in FIGS. 11 and 12 (at this time, in FIGS. 11 and 12, a represents an adsorption curve and b represents a desorption curve).

Through the results of FIGS. 11 and 12, selective adsorption of ammonia could be observed in all samples under moisture conditions, and in the case of alkylated 1SC ₉ and 1ESC ₉ , ammonia was rapidly absorbed by passing helium gas as in dry conditions. It was confirmed that desorption of the gas took place.

Figure 13 will observe the change in performance by repeatedly using the adsorbent of compound 1ESC ₉ 5 times under moisture conditions. Through the results of FIG. 13, it was confirmed that the adsorbent can be easily regenerated even under moisture conditions.

Having described specific parts of the present invention in detail above, it is clear that these specific descriptions are only preferred embodiments for those skilled in the art, and the scope of the present invention is not limited thereby. something to do. Accordingly, the substantial scope of the invention will be defined by the appended claims and their equivalents.

Claims (5)

An ammonia adsorbent comprising: a porous organic polymer-based skeleton represented by the following [Chemical Formula 1]:
[Formula 1]

In the above [Formula 1],
X is hydrogen or any one selected from the following [Structural Formula 1],
[Structural Formula 1]

,

Wherein R is any one selected from hydrogen and an unsubstituted alkyl group having 1 to 30 carbon atoms,
n is 1 or 2; delete Preparing a porous organic polymer-based framework represented by the following [Formula 1] by reacting a compound represented by the following [Formula 2] with an aldehyde solution in an HCl aqueous solution according to the following [Reaction Formula 1]; Ammonia adsorbent comprising Manufacturing method:
[Scheme 1]

[Formula 2] [Formula 1]
X is any one selected from the following [Structural Formula 1],
[Structural Formula 1]

,

Wherein R is any one selected from hydrogen and an unsubstituted alkyl group having 1 to 30 carbon atoms,
n is 1 or 2; According to claim 3,
The compound represented by [Formula 2] is prepared by reacting the compound represented by [Formula 3] with chlorosulfonic acid according to the following [Reaction Formula 2] Method for producing an ammonia adsorbent:
[Scheme 2]

[Formula 3] [Formula 2]
n is 1 or 2; A method of adsorbing ammonia using the ammonia adsorbent according to claim 1.

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