KR20230099182A - Macro bead, nox absorbent comprising same, elimination method for nox, reactor comprising same and manufacturing method for same - Google Patents

Abstract

The present specification includes macro beads comprising two or more impregnated micro beads, wherein the micro beads include a complex of chitosan and an alcohol amine compound modified with a carboxylic acid functional group, nitrogen compound adsorbent including the same, removal of nitrogen compounds It relates to a method, a reactor including the same, and a manufacturing method thereof.

Description

Macro bead, nitrogen compound adsorbent containing the same, method for removing nitrogen compounds, reactor including the same, and manufacturing method thereof

The present specification relates to a macro bead, a nitrogen compound adsorbent including the same, a nitrogen compound removal method, a reactor including the same, and a manufacturing method thereof.

Nitrogen oxides (NOx), which are the main cause of atmospheric environmental problems, mean NO ₂ and NO, and sulfur oxides (SOx) mean SO ₂ and SO ₃ . Nitrogen oxide is generated during the combustion process in power plants, automobiles, small and medium-sized businesses, and electronic industrial processes. 90% of nitrogen oxides from combustion are emitted in the form of NO, and about 10% of NO ₂ is emitted, but NO is converted back into NO ₂ in the atmosphere. NO ₂ is about 5-10 times more toxic than NO, destroys respiratory cells at high concentrations and combines with blood hemoglobin to form methahemoglobin, causing respiratory distress. It has carcinogenicity and long-term exposure can cause fatal effects such as bronchitis, emphysema, gastrointestinal disease, insomnia, and blood sugar reduction due to chronic poisoning. When it combines with water vapor in the atmosphere, it turns into nitrous acid or nitric acid and falls to the ground to form acid rain. It is affected by hydrocarbons (CH) in the air and ultraviolet rays in sunlight to cause a photochemical reaction to form secondary pollutants such as aldehyde, acrolein, and PAN (Peroxy Acetly Nitrate), which can cause ozone layer destruction or greenhouse effect. may also bring

In recent years, NOx emission regulations have been strengthened, and the need to reduce emission concentrations from major emission facilities is gradually increasing. Nitrogen oxides are mainly generated by the reaction of nitrogen and oxygen in the combustion air at high temperatures. To reduce their occurrence, low-oxygen combustion, low-temperature combustion, combustion part cooling, exhaust gas recirculation, two-stage combustion, burner and combustion chamber structural improvement Several methods are being used. Treatment technologies for removing generated 　NOx include oxidation absorption method, Selective Non-Catalytic Reduction (SNCR), Selective Catalytic Reduction (SCR), dry adsorption method, and wet absorption method.

Selective Catalytic Reduction (SCR) systems are most commonly used to remove nitrogen oxides (NOx) from exhaust gases emitted from combustion facilities. In the selective catalytic reduction system, exhaust gas and a reducing agent such as ammonia gas are passed together through a reactor in which a catalyst is installed, and the nitrogen oxide contained in the exhaust gas reacts with the reducing agent to reduce nitrogen and water vapor. The selective catalytic reduction method proceeds by the following reaction.

4NO + 4NH ₃ + O ₂ → 4N ₂ + 6H ₂ O

NO + NO ₂ + 2NH ₃ → 2N ₂ + 3H ₂ O

2NO ₂ + 4NH ₃ + O ₂ → 3N ₂ + 6H ₂ O

6NO ₂ + 8NH ₃ → 7N ₂ + 12H ₂ O

The selective catalytic reduction system exhibits relatively high treatment efficiency by using a catalyst, but requires high maintenance costs due to high installation costs, cost of exchanging precious metal catalysts, and fuel costs.

Selective non-catalytic reduction (SNCR) is a method of decomposing NOx into N ₂ and H ₂ O by directly injecting a reducing agent such as ammonia, aqueous ammonia, or urea solution into high-temperature exhaust gas without using a catalyst. Compared to the SCR method, since a separate reactor or expensive catalyst is not used, the process is relatively simple and can be applied to existing facilities relatively easily, so the investment cost is low. However, there are disadvantages in that the reaction temperature is as high as 900~1,000℃ and the NOx removal efficiency is as low as 50~70%. Selective non-catalytic reduction proceeds by the following reaction.

4NO + 4NH ₃ + O ₂ → 4N ₂ + 6H ₂ O

In the adsorption method using activated carbon, adsorption and SCR reactions are performed at 120 to 150 ° C because activated carbon is easily combustible, and desorption of sulfur dioxide is easily achieved by heating activated carbon without oxygen. The adsorption method has problems with activated carbon regeneration, fire and explosion.

The radiation method is a method using a so-called electron beam. The electron beam has the property of converting a substance with different physical and chemical properties from existing substances by changing the molecular structure, and is characterized in that the reaction proceeds in a short time (within 108 to 101 seconds). Electron beam radiation from flue gas containing NOx and SOx generates negative ions of nitrate and sulfate, and when solids such as NH ₄ NO ₃ and (NH ₄ ) ₂ SO ₄ are produced by adding water and ammonia to the flue gas, they are separated. and use it The copying method has disadvantages in that the device is complicated and it is difficult to process a large amount.

Korea Patent Registration 10-2096862

The present specification provides a macro bead having excellent nitrogen compound adsorption performance, a nitrogen compound adsorbent including the same, a nitrogen compound removal method, a reactor including the same, and a manufacturing method thereof.

An exemplary embodiment of the present invention provides a macro bead comprising two or more impregnated microbeads, wherein the microbeads include a complex of chitosan modified with a carboxylic acid functional group and an alcohol amine compound.

In addition, another embodiment of the present invention provides a nitrogen compound adsorbent including the macro beads described above.

In addition, another embodiment of the present invention provides a nitrogen compound removal method comprising the step of adsorbing the nitrogen compound to the alcohol amine compound of the above-described macro beads.

In addition, another embodiment of the present invention provides a reactor including the nitrogen compound adsorbent described above.

In addition, another embodiment of the present invention comprises preparing two or more microbeads by combining chitosan and an alcohol amine compound modified with a carboxylic acid functional group; and impregnating the two or more microbeads into the macrobeads.

Macro beads according to an exemplary embodiment of the present invention have excellent nitrogen compound adsorption performance, and thus have an effect suitable for use as a nitrogen compound adsorbent.

1 shows a macro bead structure according to an exemplary embodiment of the present invention.
Figure 2 shows a solution containing the triethylamine compound used in Examples 1 to 3.
Figure 3 shows the microbead particles prepared in Examples 1 to 3.

Hereinafter, this specification will be described in detail.

An exemplary embodiment of the present invention provides a macro bead comprising two or more impregnated microbeads, wherein the microbeads include a complex of chitosan modified with a carboxylic acid functional group and an alcohol amine compound. The macrobeads have a large amount of impregnated microbeads compared to the same volume, so that adsorption performance for nitrogen oxides is improved. In addition, since microbeads are stably impregnated into macrobeads, structural stability is improved.

In the present specification, 'bead' means a bead particle.

In the present specification, 'macro bead' means a bead larger than 'micro bead' in size, and may have a structure in which micro beads are impregnated into the macro bead. The above structure is illustrated in FIG. 1. In FIG. 1, triethylamine (1), chitosan (2) containing a carboxylic acid functional group, a chitosan aggregate (4) containing two or more chitosans, and the chitosan Alternatively, macro beads 3 impregnated with chitosan aggregates are shown.

In the present specification, 'chitosan' is a linear polysaccharide composed of D-glucosamine and N-acetylglucosamine . It can usually be obtained by treating crab, shrimp and crustacean shells with sodium hydroxide base. The chitosan may be represented by Chemical Formula 1 below, and n is a repeating unit and may be 1 to 1,000.

[Formula 1]

In the present specification, 'chitosan modified with a carboxylic acid functional group' means chitosan to which a carboxylic acid functional group is imparted.

In one embodiment of the present invention, the composite may include an ester bond between the carboxylic acid functional group and the alcohol group of the alcohol amine compound. An esterification reaction may occur between the carboxylic acid functional group of chitosan modified with the carboxylic acid functional group and the alcohol group (-OH) of the alcohol amine compound. The structure of the macro bead can be stably maintained through the ester bond, and the adsorption performance of the alcohol amine compound can be maintained.

In one embodiment of the present invention, the alcohol-amine compound refers to a compound containing both an alcohol group and an amine group, and may function as an 'adsorbent'.

In one embodiment of the present invention, the alcohol amine compound may be represented by Formula 2 below.

[Formula 2]

In Formula 2,

R1, R2 and R3 are the same as or different from each other,

each hydrogen; a straight-chain or branched-chain C1-C6 alkyl group; C1 to C6 alcohol group; or a straight-chain or branched-chain ether group;

At least one of R1, R2 and R3 is a C1 to C6 alcohol group.

In one embodiment of the present invention, R1 is a C1 to C6 alcohol group, R2 and R3 are each hydrogen; a straight-chain or branched-chain C1-C6 alkyl group; Or it may be a straight-chain or branched-chain ether group.

In an exemplary embodiment of the present invention, R1 and R2 are C1 to C6 alcohol groups, R3 is hydrogen; a straight-chain or branched-chain C1-C6 alkyl group; Or it may be a straight-chain or branched-chain ether group.

In an exemplary embodiment of the present invention, R3 in R1 may be a C1 to C6 alcohol group.

In one embodiment of the present invention, the C1 to C6 alcohol group may be methanol, ethanol, propanol or butanol. Preferably it may be methanol or ethanol.

In one embodiment of the present invention, the alcohol amine compound is monoethanolamine, diethanolamine, diglycolamine, diisopropanolamine, methyldiethanolamine, triethanolamine, N-methyl-2-amino-1-propanol, N-ethyl-2-amino-1-propanol, N-isopropyl-2-amino-1-propanol, N-methyl-2-amino-1-butanol, N-methyl-2-amino-1-pentanol, N-isopropyl-2-amino-1-pentanol, 2-amino-1-propanol, 2-amino-1-butanol, 2-amino-3-methylbutanol, 2-amino-1-pentanol, 2-amino -1-hexanol, 2-amino-1-propanol, 3-amino-1-butanol, 4-amino-1-pentanol, 5-amino-1-hexanol, 3-amino-1-pentanol, 3 -Amino-1-hexanol, and may be any one or more selected from the group consisting of piperazine (piperazine).

In one embodiment of the present invention, the alcohol amine compound may be trimethanolamine or triethanolamine.

In one embodiment of the present invention, 60 vol% or more of the microbeads may be included based on the total volume of the macrobeads. Preferably, it may contain 60 vol% or more and 80 vol% or less, or 60 vol% or more and 99 vol% or less. When the above numerical range is satisfied, the nitrogen compound adsorption effect by the microbeads is maintained, and the structural stability of the macrobeads is also excellent. The volume of the macro bead and micro bead may be understood as a volume when it is assumed that the macro bead and the micro bead are virtual spheres, respectively. The imaginary sphere may refer to a spherical structure having an average diameter of the beads as a diameter.

In one embodiment of the present invention, 1 million to 20 million micro beads may be included based on one macro bead. Preferably, it may include 2 million to 18 million, or 5 million to 15 million. When the above numerical range is satisfied, the nitrogen compound adsorption effect by the microbeads is maintained, and the structural stability of the macrobeads is also excellent.

In one embodiment of the present invention, the microbeads may have a diameter of 1 um to 100 um. Preferably, it may be 2um to 50um or 5um to 20um. When the above numerical range is satisfied, there is an effect of maintaining the nitrogen compound adsorption effect by the microbeads.

In one embodiment of the present invention, the macro bead may have a diameter of 1 mm to 100 mm. Preferably, it may be 1 mm to 100 mm, or 1 mm to 100 mm. When the above range is satisfied, a sufficient number of microbeads can be impregnated into the macrobeads, so that the nitrogen oxide adsorption effect by the microbeads is excellent.

In one embodiment of the present invention, the macro bead may include a support and a micro bead, and the micro bead may have a structure impregnated in the support.

In one embodiment of the present invention, the support may have a porous structure. The porous structure may mean a space in which the microbeads are impregnated into the support.

In one embodiment of the present invention, the porosity of the support may be 10% or more and 90% or less, 20% or more and 80% or less, or 20% or more and 70% or less. Within the above range, a sufficient space in which microbeads are impregnated is secured, so that a sufficient number of microbeads can be impregnated.

In one embodiment of the present invention, the support may be at least one selected from the group consisting of zeolite, alumina, chitosan, and polyvinyl alcohol. Preferably, it may be chitosan or polyvinyl alcohol. When using a chitosan support, there is an effect of excellent compatibility with microbeads.

An exemplary embodiment of the present invention provides a nitrogen compound adsorbent including the macro beads described above. The macro beads may perform an adsorbent function by using an alcohol amine compound included in the micro beads as an adsorbent. For example, when the alcohol amine compound is triethyleneamine, the reaction formula for adsorbing a nitrogen compound is as follows.

[reaction formula]

(HOCH ₂ CH ₂ ) ₃ N + 2NO ₂ → (HOCH ₂ CH ₂ ) ₃ NNO+HNO ₃ ^-

In one embodiment of the present invention, the nitrogen compound may mean nitrogen monoxide, nitrogen dioxide, or a mixture thereof.

On the other hand, conventional chitosan macro beads have a problem of being difficult to regenerate after use and must be discarded, but in the case of macro beads according to an exemplary embodiment of the present invention, it can be used as a slow-acting fertilizer by using a nitrogen compound adsorbed to an alcohol amine compound. . At this time, the support included in the macro bead may be used as a carrier of fertilizer.

An exemplary embodiment of the present invention provides a nitrogen compound removal method comprising the step of adsorbing a nitrogen compound to the alcohol amine compound of the above-described macro beads. The nitrogen compound is removed through a chemical reaction with the alcohol amine compound of the macro bead. The chemical reaction at this time is as shown in the above chemical formula.

In one embodiment of the present invention, the method of removing the nitrogen compound includes preparing the above-described macro beads; Passing a nitrogen compound through the macro beads; and reacting the alcohol amine compound of the macrobead with the nitrogen compound. At this time, the macro beads may be provided as a nitrogen compound adsorbent included in a reactor to be described later.

In one embodiment of the present invention, the nitrogen compound in the step of passing the nitrogen compound through the macro beads may reach the alcohol amine compound through pores of the carrier of the macro beads.

In one embodiment of the present invention, the nitrogen compound in the step of passing the nitrogen compound through the macro beads may be provided in the form of exhaust gas containing the nitrogen compound.

An exemplary embodiment of the present invention provides a reactor including the nitrogen compound adsorbent described above. The reactor may have a structure in which two or more reactors are connected in series or parallel, and when one reactor reaches the end of its life or deteriorates in performance, the remaining reactors may be used in place of it.

An exemplary embodiment of the present invention comprises preparing two or more microbeads by combining chitosan and an alcohol amine compound; and impregnating the two or more microbeads into the macrobeads.

In one embodiment of the present invention, preparing two or more microbeads by combining chitosan modified with a carboxylic acid functional group and an alcohol amine compound may include combining the chitosan and alcohol amine compound.

In one embodiment of the present invention, combining the carboxylic acid functional group-modified chitosan and the alcohol amine compound may include mixing the carboxylic acid functional group-modified chitosan and the alcohol amine compound.

In one embodiment of the present invention, the step of mixing the carboxylic acid functional group-modified chitosan and the alcohol amine compound comprises a solution containing the carboxylic acid functional group-modified chitosan and a solution containing the alcohol amine compound. Mixing may be included.

In one embodiment of the present invention, the step of mixing the solution containing the chitosan modified with the carboxylic acid functional group and the solution containing the alcohol amine compound is a solution containing the chitosan modified with the carboxylic acid functional group It may be carried out by a method of dropping (dropping) on the alcohol amine compound.

In one embodiment of the present invention, the concentration of the solution containing the alcohol amine compound may be 1 wt% to 30 wt%, 5 wt% to 25 wt%, or 10 wt% to 30 wt%. When the above numerical range is satisfied, an ester bond may be sufficiently formed through a reaction between the carboxylic acid functional group of chitosan and the alcohol group of the alcohol amine compound.

In one embodiment of the present invention, before mixing the solution containing chitosan modified with the carboxylic acid functional group and the solution containing the alcohol amine compound, blocking the amine group of the alcohol amine compound Further steps may be included. This step is to prevent formation of a peptide bond due to a reaction between the amine group of the alcohol amine compound and the carboxylic acid group of the chitosan by binding another functional group to the amine group of the alcohol amine compound. In this case, the alcohol group of the alcohol amine compound reacts with the carboxylic acid group of the chitosan to form an ester bond, thereby improving the yield and selectivity of the process.

In one embodiment of the present invention, the step of blocking the amine group of the alcohol amine compound is the alcohol amine compound and di-tert-butyl dicarbonate compound (Di-tert-butyl decarbonate: t-BOC) Mixing may be included. The di-tert-butyl dicarbonate compound may be represented by Formula 3 below.

[Formula 3]

In one embodiment of the present invention, a step of modifying the chitosan with a modifier having a carboxylic acid functional group may be included. At this time, an acid may be used in the reforming step.

In one embodiment of the present invention, the step of modifying the chitosan with a modifier having a carboxylic acid functional group may include exposing it to an environment of pH 1 to 6.

In one embodiment of the present invention, the modifier having a carboxylic acid functional group may be acetic acid.

In one embodiment of the present invention, the step of modifying the chitosan with a modifier having a carboxylic acid functional group may include mixing a solution containing the chitosan and a solution containing the modifier having the carboxylic acid functional group. can

In one embodiment of the present invention, the concentrations of the solution containing chitosan and the solution containing the modifier having a carboxylic acid functional group are the same as or different from each other, and are 0.1wt% to 10wt% and 0.5wt% to 8wt, respectively. % or 1wt% to 5wt%.

In one embodiment of the present invention, drying the microbeads may be included. The drying may be performed in an environment of 25 °C to 100 °C or 25 °C to 80 °C. Within the above numerical range, moisture from the microbeads can be sufficiently removed, and damage to the microbeads can be prevented.

In one embodiment of the present invention, the step of drying the microbeads may be performed for 1 minute to 48 hours, 10 minutes to 24 hours, or 1 hour to 10 hours. Within the above numerical range, moisture from the microbeads can be sufficiently removed, and damage to the microbeads can be prevented.

Hereinafter, the present invention will be described in more detail through examples.

Example One

( 1) Micro bead manufacturing

Chitosan at a concentration of 2 to 5 wt% was dissolved in a solution of 1 to 5 wt% acetic acid to modify the chitosan with a carboxylic acid functional group. Then, the chitosan solution was transferred to a syringe having a diameter of 0.1 mm.

A solution containing 10wt% of a triethylamine compound at 30° C. was prepared, and microbeads were prepared by dropping the chitosan solution using a syringe pump. At this time, the average diameter of the microbeads was 10 to 20um.

Then, the microbeads were taken out and dried in a dryer at 60°C.

( 2) Macrobead's manufacturing

The microbeads were mixed with 1 to 5 wt% acetic acid solution in which 3 wt% chitosan was dissolved and transferred to a syringe. Thereafter, the mixture was dropped into a solution containing 10wt% of a triethylamine compound at 30° C. to prepare macro beads.

The macro beads were taken out and dried in a dryer at 60°C. The average diameter of the macro beads was 4 mm to 7 mm.

Example 2

Macro beads were prepared in the same manner as in Example 1, except that the content of the triethylamine compound was changed to 15 wt%.

Example 3

Macro beads were prepared in the same manner as in Example 1, except that the content of the triethylamine compound was changed to 20 wt%.

The solution containing the triethylamine compound used in Examples 1 to 3 is shown in FIG. 2, and the prepared microbead particles are shown in FIG.

Experimental example

100 cc of the prepared macro beads were filled in a reactor.

A nitrogen dioxide/air mixture (NO ₂ /air) was injected into the reactor, and the nitrogen monoxide adsorption amount was calculated by measuring the amount of nitrogen dioxide in the gas mixture discharged through the reactor.

At this time, the flow rate of the mixed gas injected into the reactor was 1,000 sccm, the inflow concentration of nitrogen dioxide in the mixed gas was 5,000 ppm, and the experiment was conducted at room temperature (25° C.). Also, the injection speed of the mixed gas was 98 cm/min. The total injection time was 500 minutes, and the outlet NO ₂ concentration increased rapidly after 500 minutes. The size of the adsorption reactor was 3.6 cm in diameter and 10 cm in length and filled with beads.

Using stoichiometry, the volume (Liter) of adsorbed nitrogen dioxide compared to the filling amount (Liter) of the macro beads was calculated to be 25 l/l.

Claims (9)

Including two or more impregnated microbeads,
Wherein the microbeads include a complex of chitosan and an alcohol amine compound modified with a carboxylic acid functional group. The method of claim 1,
The complex is a macro bead comprising an ester bond of the carboxylic acid functional group and the alcohol group of the alcohol amine compound. The method of claim 1,
The alcohol amine compound is a macro bead represented by the following formula.
[chemical formula]

Here, R1, R2 and R3 are the same as or different from each other,
each hydrogen; a straight-chain or branched-chain C1-C6 alkyl group; C1 to C6 alcohol group; or a straight-chain or branched-chain ether group;
At least one of R1, R2 and R3 is a C1 to C6 alcohol group. The method of claim 1,
The alcohol amine compound is monoethanolamine, diethanolamine, diglycolamine, diisopropanolamine, methyldiethanolamine, triethanolamine, N-methyl-2-amino-1-propanol, N-ethyl-2-amino-1 -Propanol, N-isopropyl-2-amino-1-propanol, N-methyl-2-amino-1-butanol, N-methyl-2-amino-1-pentanol, N-isopropyl-2-amino- 1-Pentanol, 2-amino-1-propanol, 2-amino-1-butanol, 2-amino-3-methylbutanol, 2-amino-1-pentanol, 2-amino-1-hexanol, 2-amino -1-propanol, 3-amino-1-butanol, 4-amino-1-pentanol, 5-amino-1-hexanol, 3-amino-1-pentanol, 3-amino-1-hexanol, and A macro bead that is at least one selected from the group consisting of piperazine. A nitrogen compound adsorbent comprising the macro beads according to any one of claims 1 to 4. A method for removing a nitrogen compound comprising the step of adsorbing a nitrogen compound to the alcohol amine compound of the macro beads according to any one of claims 1 to 4. A reactor comprising the nitrogen compound adsorbent according to claim 5 preparing two or more microbeads by combining chitosan modified with a carboxylic acid functional group and an alcohol amine compound; and
The method of manufacturing a macro bead according to any one of claims 1 to 4, comprising the step of impregnating the two or more micro beads into the macro bead. The method of claim 8,
Method for producing a macro bead comprising the step of modifying the chitosan with a modifier having a carboxylic acid functional group.

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