KR20180034173A - Apparatus to generate and discharge ammonia - Google Patents

Abstract

The present invention relates to an apparatus for generating ammonia, which comprises a chamber (100) containing an ammonia generating material, wherein the chamber (100) as a heat transfer member, comprises at least one heat plate (110) and at least one heat pipe (120). The at least one heat transfer plate (110) is arranged parallel to each other in the longitudinal direction of the chamber (100), and the at least one heat transfer tube (120) is arranged to pass through the heat transfer plate (110). An object of the present invention is to provide the apparatus for generating ammonia having high efficiency of ammonia generation by comprising the heat transfer plate (110) and the heat pipe (120).

Description

[0001] Apparatus to generate and discharge ammonia [

The present invention relates to an apparatus for generating and releasing ammonia by heating an ammonia generating material to a predetermined temperature.

As part of efforts to reduce air pollutant emissions both domestically and internationally, the amendment of relevant laws and amendments to the Enforcement Regulations of the Air Quality Preservation Act have been reinforcing pollution regulations.

These legal amendments are very effective in regulating air pollutant emissions, which dramatically reduces the emissions of major air pollutants.

However, despite these long-standing regulatory measures, emissions reductions to nitrogen oxides remain an unsatisfactory performance.

This is because the control of nitrogen oxides among the various air pollutants generated in the combustion process is not easy compared with other contaminants from the technical point of view.

However, in spite of this situation, the emission standard of nitrogen oxides is expected to be strengthened gradually, and the emission regulation, which was mainly applied to large-scale pollution facilities, is being applied to small-sized emission facilities such as ships, small boilers and automobiles.

SCR (Selective Catalytic Reduction) system is typically used as a post-treatment facility for treating nitrogen oxides contained in the exhaust gas. The SCR system has a disadvantage in that initial facility cost and operation cost due to the addition of a reducing agent are large, It is widely applied because it has the advantage of being able to operate the system with stable and high abatement efficiency against gas.

In addition, the SCR system is a method in which nitrogen oxides are selectively reacted with ammonia on a catalyst to reduce them to nitrogen and water. Therefore, the supply of ammonia is the most important factor in the SCR system, because the SCR system will remove 80-95% of the nitrogen oxides contained in the exhaust gas by the supply of ammonia as the reducing agent.

On the other hand, ammonia is a promising high-capacity hydrogen storage material capable of storing a large amount of hydrogen produced from renewable energy, and can store about 17.7 wt% of hydrogen by weight.

Also, in order to solve the ammonia toxicity and safety problem, when a solid ammine complex is manufactured and applied, handling, storage, and movement are easier than liquid ammonia, and toxicity and volatility of ammonia can be controlled. Such a solid ammonia storage material releases high purity ammonia gas at a mild condition of about 60 to 100 DEG C, and this gas can be modified and used as hydrogen.

 Here, ammonia is capable of releasing hydrogen at a relatively high mild condition and can be used for hydrogen station fuel and energy storage for hydrogen fuel cell vehicle supply through dehydrogenation reaction, Since it can produce electricity in connection with the battery, it can be utilized in various applications such as power generation and portable use.

In addition, ammonia can be applied to clean hydrogen fuel cells, where high purity ammonia production is essential.

In order to drive hydrogen fuel cells, innovative technologies for the production, storage and utilization of hydrogen can be combined. Among the hydrogen storage and production technologies, physical hydrogen storage technologies include storage of compressed hydrogen using a high-pressure hydrogen tank, Liquefied hydrogen storage, and storage using metal hydrogen compounds.

Among them, the high-pressure compressed hydrogen storage method and the liquefied hydrogen storage method have problems such as explosion risk, energy consumption due to the weight and price of the tank, and low boiling point of hydrogen. On the other hand, Has high stability as well as high energy density, but it is expensive and has a very low hydrogen storage capacity in weight.

On the other hand, in the case of the chemical hydrogen storage method, hydrogen is stored using various compounds such as ammonia, formic acid, and methanol, and the hydrogen is effectively released through a dehydrogenation reaction when necessary. It is known for its superior technology due to its much higher weight or volume of hydrogen storage capacity.

Korean Patent No. 925242 (Ammonia production apparatus and method) discloses a system and a method for generating ammonia for producing ammonia for removal of nitrogen oxides as a prior art related to ammonia generation and release apparatus for producing ammonia Korean Patent No. 492112 (a method of controlling the formation of ammonia from urea for the removal of nitrogen oxides) hydrolyzes urea in an aqueous solution in a closed reactor to obtain a rate which is essentially balanced with the amount required in the combustion gas stream To provide a pressurized gas stream useful for removing nitrogen oxides from a combustion gas stream by releasing gaseous ammonia.

However, the conventional ammonia generating and discharging apparatus must be operated at a high temperature in order to increase ammonia generating efficiency, and the heat transfer and heat emission efficiency in the apparatus is low, so that the process cost is high and an additional apparatus is required.

In order to solve the above-described problems, the present invention has an object to provide an ammonia generator having a high efficiency of generating ammonia by including the heat transfer plate 110 and the heat transfer tube 120.

It is a further object of the present invention to improve the heat transfer and heat emission efficiency of the apparatus by using aluminum as the material of the heat transfer plate 110 and the heat transfer tube 120 and ultimately to improve the efficiency of ammonia generation, We want to reduce.

According to one embodiment of the present invention, a chamber 100 comprising an ammonia-generating material; The chamber 100 is a heat transfer member and includes at least one heat plate 110 and at least one heat pipe 120. The heat transfer plate 110 is connected to each other in the longitudinal direction of the chamber 100, And the heat transfer tubes (120) are arranged to pass through the heat transfer plate (110).

In one embodiment of the present invention, the heat transfer plate 110 is a porous structure and includes at least one hole 111. [

In an embodiment of the present invention, the material of the chamber 100, the heat transfer plate 110, and the heat transfer tube 120 may be stainless steel or aluminum.

In an embodiment of the present invention, the material of the chamber 100, the heat transfer plate 110, and the heat transfer tube 120 may be aluminum.

In one embodiment of the present invention, the ammonia-generating material is preferably a solid material that reversibly desorbs and adsorbs ammonia gas, but is not limited thereto.

In one embodiment of the present invention, the ammonia generating material may be a metal amine complex.

In one embodiment of the present invention, the metal amine complex comprises SrCl ₂揃 1-8 (NH ₃ ), CaCl ₂揃 1-2 (NH ₃ ), CaCl ₂揃 2-4 (NH ₃ ), CaCl ₂揃 4 (NH ₃ ), CaBr ₂ 2-6 (NH ₃ ), CoCl ₂ 2-6 (NH ₃ ), FeCl ₂ 2-6 (NH ₃ ), FeBr ₂ 2-6 (NH ₃ ) , BaCl ₂ and 0-8 (NH _3), CaI ₂ and 2-6 (NH _3), MgBr ₂ and 2-6 (NH _3), MrBr ₂ and 2-6 (NH _3), MnCl ₂ and 2 6 (NH _3), and MgCl ₂ and 2-6 may be at least one selected from the group consisting of (NH _3).

In one embodiment of the present invention, the metal amine complex is a mixture of CaCl ₂ ½ (NH ₃ ), CaCl ₂ / (NH ₃ ), CaCl ₂揃 4/8 (NH ₃ ) Is an amine complex comprising CaCl ₂ , but is not limited thereto.

In one embodiment of the present invention, the apparatus may further include a temperature controller for controlling the temperature of the heat transfer plate 110 and the heat transfer tube 120 so as to heat or cool the ammonia generating material in the chamber 100.

In one embodiment of the present invention, a discharge portion 130 for discharging the generated ammonia in the chamber 100 may be connected to one end of the chamber 100.

In an embodiment of the present invention, the flow-in and discharge of the discharge part 130 may be controlled by a one-touch valve.

In one embodiment of the present invention, the ammonia generator comprises i) a catalytic removal device of nitrogen oxides (NO _x ), ii) a hydrogen fuel cell system; And iii) an internal combustion engine using ammonia as a raw material.

According to another embodiment of the present invention, there is provided a cartridge system comprising the at least one ammonia generating device.

In one embodiment of the present invention, the cartridge system may additionally include pressure control means 210 in the chamber, temperature control means 220 in the chamber, and ammonia flow rate control means 230.

In one embodiment of the present invention, in the cartridge system, at least one ammonia generating device may be arranged in a single layer and in a multilayer manner in parallel with each other.

According to the present invention, the efficiency of heat transfer and heat dissipation of the ammonia generating apparatus can be improved, and ultimately, the ammonia generating efficiency can be improved, the process can be simplified, and the cost can be reduced.

According to the present invention there is provided a cartridge system comprising at least one ammonia generating device by simple detachment, said cartridge system being capable of continuous use by charging of the ammonia generating device.

The ammonia generator or cartridge system may also include i) a catalytic removal device of nitrogen oxides (NO _x ), ii) a hydrogen fuel cell system; And iii) an internal combustion engine using ammonia as a raw material, so that it can be used for nitrogen oxide removal and hydrogen supply apparatus with high efficiency.

1 is a view showing an ammonia generating apparatus 1 according to an embodiment of the present invention.
2 is a front view of the heat transfer plate 110 according to one embodiment of the present invention.
3 is a view showing a cartridge system 2 including an ammonia generating device according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Further, the embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

The present invention relates to an apparatus for generating and releasing ammonia by heating an ammonia generating material to a predetermined temperature.

In particular, according to one embodiment of the present invention, a chamber 100 comprising an ammonia-generating material; The chamber 100 is a heat transfer member and includes at least one heat plate 110 and at least one heat pipe 120. The heat transfer plate 110 is connected to each other in the longitudinal direction of the chamber 100, And the heat transfer tubes (120) are arranged to pass through the heat transfer plate (110).

Since the at least one heat transfer plate 110 and the at least one heat transfer tube 120 pass through the interior of the chamber 100 and use a material having a high contact area with the ammonia generating material and a high thermal conductivity, Respectively.

In an embodiment of the present invention, the material of the chamber 100, the heat transfer plate 110, and the heat transfer tube 120 may be stainless steel or aluminum. But is not limited to, aluminum, which has a high thermal conductivity and is easy to control the temperature inside the device and easily releases heat to cause a temperature drop of the device within a short time.

The material of the chamber 100, the heat transfer plate 110, and the heat transfer pipe 120 is made of stainless steel or aluminum, so that the efficiency of generating ammonia can be improved and the process cost can be reduced. In addition, the ammonia generating device according to the present invention is light in weight, which makes it easy to move the apparatus, and is convenient when connecting the SCR system and the hydrogen supply device of the fuel cell, which are other devices and systems.

In one embodiment of the present invention, the heat transfer plate 110 is a porous structure and may include at least one hole 111. [ The generated ammonia in the chamber 100 can freely move through the holes, thereby keeping the pressure in the apparatus constant.

In an embodiment of the present invention, the chamber 100 includes at least one heat transfer plate 110 so that the heat transfer plates 110 are arranged at regular intervals in the chamber 100 to uniformly flow into the chamber 100 Heat can be transferred.

In an embodiment of the present invention, the chamber 100 has a cylindrical shape, which is preferable, but not limited, to solve the blind spot phenomenon in which the flow of the ammonia-generating material and ammonia in the outer edge portion is stagnated.

In an embodiment of the present invention, the heat transfer plate 110 may be in the shape of a disc because heat transfer efficiency can be increased, but the present invention is not limited thereto.

In one embodiment of the present invention, the heat transfer tube 120 is preferably cylindrical in shape to penetrate the heat transfer plate 110 in order to increase heat transfer efficiency.

The cylindrical shape is preferable because it can increase heat transfer efficiency, but is not limited thereto.

In one embodiment of the present invention, the ammonia-generating material is not limited as long as it is a solid material capable of reversibly desorbing and adsorbing ammonia gas, but a metal-amine complex is most preferable.

In one embodiment of the present invention, the metal amine complex means a metal complex containing at least one ammonia as a ligand. Preferred examples thereof include SrCl ₂揃 1-8 (NH ₃ ), CaCl ₂揃 1-2 (NH ₃ ), CaCl ₂揃 2-4 (NH ₃ ), CaCl ₂揃 4-8 (NH ₃ ), CaBr ₂揃 2-6 (NH ₃ ), CoCl ₂揃 2-6 (NH ₃ ), FeCl ₂揃 2 -6 (NH _3), FeBr ₂ and 2-6 (NH _3), BaCl ₂ and 0-8 (NH _3), CaI ₂ and 2-6 (NH _3), MgBr ₂ and 2-6 (NH ₃₎ , MrBr ₂ and 2-6 (NH _3), MnCl ₂ and 2-6 (NH _3), and MgCl ₂ and 2-6 (NH ₃₎ one or more compounds, and the most preferred example is selected from the group consisting of CaCl ₂ and 1/2 (NH _3), CaCl ₂ and 2/4 (NH _3), an amine complex comprising CaCl ₂ in a CaCl ₂ and 4/8 (NH ₃₎ or mixtures thereof coordinated step.

The temperature regulating unit may regulate the temperature of the heat transfer plate 110 and the heat transfer pipe 120 in the embodiment of the present invention, Thereby controlling the temperature of the entire ammonia generator. In addition, by further including the temperature control unit, the metal amine complex can be easily heated to generate ammonia.

In an exemplary embodiment of the present invention, a discharge unit 130 for discharging ammonia generated in the chamber 100 may be connected to one end of the chamber 100, and the discharge unit 130 may be configured to inject or discharge ammonia And may preferably be controlled by a one-touch valve, but is not limited thereto. Accordingly, the discharge of the discharge part 130 can be controlled by the one-touch valve, and can be opened and closed according to the pressure inside the chamber 100, and the pressure in the chamber 100 can be controlled.

In addition, when the ammonia generating apparatus of the present invention is connected to another apparatus by controlling the flow of ammonia in the discharge unit 130 by a one-touch valve, it is easy to connect and can be easily replaced .

The ammonia generator of the present invention comprises i) a catalytic removal device for nitrogen oxide (NOx), ii) a hydrogen fuel cell system; And iii) an internal combustion engine using ammonia as a raw material.

The present invention can be applied to a clean hydrogen fuel cell and can generate and discharge ammonia, which is a hydrogen storage material, with high purity.

Here, in order to drive the hydrogen fuel cell, innovative technology development for the production, storage, and utilization of hydrogen may be performed in parallel, and the present invention can be applied to hydrogen storage and production technology.

Since the ammonia generating apparatus according to the present invention includes ammonia generating material, ammonia is stored using a compound capable of adsorbing ammonia as a part of a chemical hydrogen storing technique, and if necessary, high purity ammonia is removed through desorption of ammonia Can be released. Here, the released ammonia can produce high purity hydrogen through the ammonia reforming catalytic reaction and purification process, and can be used as a raw material of a conventional hydrogen fuel cell.

Another embodiment of the present invention provides a cartridge system comprising at least one ammonia generating device. Within the cartridge system, the at least one ammonia generating device may be arranged in a single layer and a multilayer in parallel with each other. The cartridge system may further include a pressure control means 210 in the chamber, a temperature control means 220 in the chamber, and an ammonia flow rate control means 230. The pressure control means 210 and the temperature control means 220 regulate the pressure and temperature inside the chamber of the ammonia generator, respectively. The ammonia flow rate regulating unit 230 regulates the release rate and amount of ammonia generated by the discharge unit 130 of the ammonia generator. The discharge portion 130 of the ammonia generating device may be a one-touch valve type, in which case the ammonia generating device may be easily detached and attached to the cartridge system.

In one embodiment of the present invention, the temperature in the chamber 100 may be in the range of 100 to 120 ° C. When the chamber 100 is heated to the temperature range, the rate at which ammonia is released from the metal amine complex and the production efficiency .

The ammonia generating apparatus according to the present invention can be used in connection with a catalytic device of nitrogen oxide (NO _x ), which uses ammonia as a reducing agent to purify the nitrogen product by nitrogen and water vapor, In addition, the ammonia generating apparatus may be used for treating nitrogen oxide discharged from the atmosphere or an industrial complex.

The apparatus for generating ammonia according to the present invention is used for generating ammonia for exhaust gas aftertreatment of a selected one of a vehicle or a ship. The ammonia generating apparatus treats exhaust gas discharged from a vehicle or a ship to produce a harmless gas And can be used in connection with an internal combustion engine using ammonia as a raw material for conversion.

The apparatus for generating ammonia according to the present invention can be used in connection with a hydrogen fuel cell system, and can separate hydrogen from ammonia generated from the ammonia generator. As a result, the separated hydrogen can be used as fuel and used in various transportation means and power plants.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, and that various changes and modifications may be made without departing from the scope of the invention. It will be obvious to those of ordinary skill in the art.

1: Ammonia generator
100: chamber
110:
120: Heat pipe
130:
111: hole
2: Cartridge system
210: pressure control means in the chamber
220: Temperature control means in the chamber
230: Ammonia flow rate control means

Claims (11)

A chamber 100 comprising an ammonia-generating material;
The chamber 100 is a heat transfer member and includes at least one heat plate 110 and at least one heat pipe 120. The at least one heat transfer plate 110 is arranged in the longitudinal direction of the chamber 100 , And the heat transfer tubes (120) are arranged to pass through the heat transfer plate (110). The method according to claim 1,
The heat transfer plate (110) has a porous structure and includes at least one hole (111). The method according to claim 1,
Wherein the material of the chamber (100), the heat transfer plate (110), and the heat transfer pipe (120) is stainless steel or aluminum. The method according to claim 1,
Wherein the ammonia generating material is a metal amine complex. 5. The method of claim 4,
The metal amine complex is SrCl ₂ and 1-8 (NH _3), CaCl ₂ and 1-2 (NH _3), CaCl ₂ and 2-4 (NH _3), CaCl ₂ and 4-8 (NH _3), CaBr ₂ · 2-6 (NH _3), CoCl ₂ · 2-6 (NH _3), FeCl ₂ • 2-6 (NH _3), FeBr ₂ • 2-6 (NH _3), BaCl ₂ • 0-8 ( NH _3), CaI ₂ and 2-6 (NH _3), MgBr ₂ and 2-6 (NH _3), MrBr ₂ and 2-6 (NH _3), MnCl ₂ and 2-6 (NH ₃₎ and MgCl ₂ And 2 to 6 (NH ₃ ). 5. The method of claim 4,
The metal amine complex is an amine containing the CaCl ₂ and 1/2 (NH _3), CaCl ₂ and 2/4 (NH _3), CaCl ₂ and 4/8 (NH ₃₎ or CaCl ₂ in a mixed coordination step Ammonia < / RTI > The method according to claim 1,
Characterized in that a discharge portion (130) for discharging the generated ammonia in the chamber (100) is connected at one end of the chamber (100). 8. The method of claim 7,
Wherein the discharge of the discharge part (130) is controlled by a one-touch valve. The method according to claim 1,
The ammonia generating device
i) a catalytic removal device of nitrogen oxides (NO _x )
ii) a hydrogen fuel cell system; And
and iii) an internal combustion engine using ammonia as a raw material. < Desc / Clms Page number 13 > A cartridge system comprising at least one ammonia generating device according to claim 1,
Characterized in that the cartridge system further comprises pressure control means (210) in the chamber, temperature control means (220) in the chamber and ammonia flow rate regulating means (230). 11. The method of claim 10,
Within the cartridge system, the at least one ammonia generating device is arranged in a single layer and in a multilayer arrangement in parallel with one another.

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