KR102446545B1 - A device for reducing greenhouse gas emissions of ammonia carriers - Google Patents

Abstract

The present invention relates to a device for reducing greenhouse gas emission of an ammonia-carrying vessel, which can remove or minimize an ancillary device, comprising: a liquefied ammonia storage tank (100) for storing liquefied ammonia; a seawater supply unit (110) for supplying seawater; an absorption liquid production unit (120); an absorption tower (130) having a CO_2 removal unit 131 formed therein; an absorption liquid regeneration unit (140); and an absorption liquid circulation unit (150).

Description

Apparatus for reducing greenhouse gas emissions of ammonia carriers

The present invention converts ammonia stored in the cargo hold of an ammonia carrier into a CO ₂ absorption liquid, circulates the remaining unreacted absorption liquid to the absorption tower to maintain the CO ₂ absorption rate, and at least the exhaust gas by the absorption tower according to the load change of the ship engine. It can absorb CO ₂ from only a portion, and a storage tank for storing and supplying a CO ₂ removal unit and an aqueous solution of divalent metal hydroxide for regeneration of the absorbent is configured in the engine casing so that it can be utilized without affecting the space of the existing engine casing area. The installation space problem can be solved, and the storage tank for storing and supplying the divalent metal hydroxide aqueous solution for the regeneration of the absorbent is configured in the form of a silo so that it can be supplied to the mixing tank by its own weight. It relates to a device for reducing greenhouse gas emissions of ammonia carriers, which can eliminate or minimize the device.

Recently, global warming and related environmental disasters have occurred due to the influence of greenhouse gas emissions due to indiscriminate use of fossil fuels.

Accordingly, a series of technologies related to the capture and storage of carbon dioxide, a representative greenhouse gas, without emitting it is called CCS (Carbon dioxide Capture and Storage) technology and has recently received a lot of attention. Among CCS technologies, chemical absorption is It is the most commercialized technology among them in terms of large-scale processing possible.

_In addition, carbon dioxide emission regulation is regulated through the IMO's EEDI, which aims to reduce more than 50% of 2008 emissions in 2050, and 40% of 2008 emissions must be reduced in 2030. , technology to capture the emitted CO ₂ is attracting attention.

For reference, among CCS technologies that directly capture and store carbon dioxide, CO ₂ capture technology can be approached in various ways depending on the CO ₂ generation conditions of the target process. Currently, the representative technologies include absorption, adsorption, and membrane separation, among which The wet absorption method has a high technical maturity in onshore plants and is easy to treat large quantities of CO ₂ , so it can be said to be the closest capture technology to the commercialization of CCS technology. As absorbents, amine series and ammonia are mainly used.

On the other hand, the aforementioned technology for reducing carbon dioxide emission or capturing the generated carbon dioxide has not been commercialized in ships at present, and a method using hydrogen or ammonia as a fuel is currently being developed and is at the stage of commercialization. has not been reached.

In particular, it absorbs CO ₂ , a greenhouse gas, from the exhaust gas emitted from the ship engine of an ammonia carrier into an absorption liquid produced by using ammonia, which is the transport target, and converts it into a substance that does not affect the environment, or converts it to a useful substance and stores it In addition, it is possible to prevent a decrease in absorption liquid due to exhaust gas emission during operation and a decrease in absorption performance due to a change in absorption liquid concentration due to other consumption. A technology that can solve the space problem by not affecting the engine casing area is required.

Korean Patent Publication No. 2031210 (Ship exhaust gas reduction device and pollutant removal method, 2019.10.11) Korean Patent Publication No. 1201426 (Greenhouse Gas Reduction Device for Ships, 2012.11.14)

The technical task to be achieved by the spirit of the present invention is to convert ammonia stored in the cargo hold of an ammonia carrier into a CO ₂ absorption liquid, circulate the remaining unreacted absorption liquid to the absorption tower to maintain the CO ₂ absorption rate, and according to the load change of the ship engine It is possible to absorb CO ₂ from at least a portion of the exhaust gas by the absorption tower, and a storage tank for storing and supplying a CO ₂ removal unit and a divalent metal hydroxide aqueous solution for regeneration of the absorption liquid is configured in the engine casing, so that the existing engine casing area space It is possible to solve the installation space problem by allowing it to be utilized without affecting the An object of the present invention is to provide a device for reducing greenhouse gas emissions of ammonia carriers that can eliminate or minimize ancillary devices required for supply to a tank.

In order to achieve the above object, the present invention, a liquefied ammonia storage tank for storing liquefied ammonia; Seawater supply unit for supplying seawater; an absorption liquid production unit for receiving ammonia from the liquefied ammonia storage tank and manufacturing and supplying a high-concentration CO ₂ absorption liquid; The exhaust gas discharged from the marine engine of the engine room is cooled by reacting with the seawater supplied from the seawater supply unit, and the cooled exhaust gas and the absorption liquid from the absorption liquid production unit are reacted to convert CO ₂ into an aqueous ammonium salt solution to CO ₂ CO ₂ removal unit formed to remove the absorption tower; an absorption liquid regeneration unit for regenerating the absorption liquid and NH ₃ by reacting the aqueous ammonium salt solution discharged from the absorption tower with an aqueous solution of divalent metal hydroxide, circulating and supplying the absorption liquid to the absorption tower to be reused as an absorption liquid; and an absorption liquid circulation unit that circulates a portion of the ammonium salt aqueous solution or unreacted absorption liquid discharged from the lower end of the absorption tower to the upper portion of the absorption tower through an absorption liquid circulation line.

In addition, the absorbent liquid manufacturing unit, a fresh water tank for storing fresh water; a fresh water control valve for supplying fresh water from the fresh water tank; an ammonia water tank for preparing and storing ammonia supplied from the liquefied ammonia storage tank to the fresh water supplied by the fresh water control valve to produce and store high-concentration ammonia water as an absorption liquid; a pH sensor for measuring the ammonia water concentration in the ammonia water tank; and an ammonia water supply pump for supplying ammonia water from the ammonia water tank to the absorption liquid circulation unit.

In addition, the boil-off gas from the liquefied ammonia storage tank may be supplied to the ammonia water tank.

In addition, the liquefied ammonia from the liquefied ammonia storage tank may be vaporized through a vaporizer and supplied to the ammonia water tank.

In addition, the absorbent liquid manufacturing unit further includes an NH ₃ storage for storing NH ₃ (g) of high pressure, and injecting the boil-off gas from the liquefied ammonia storage tank into the NH ₃ storage, and from the NH ₃ storage to the ammonia water tank. As the NH ₃ (g) can be supplied.

In addition, the absorption liquid preparation unit further includes a NH ₃ storage for storing NH ₃ (g) of high pressure, and vaporizes liquefied ammonia from the liquefied ammonia storage tank through a vaporizer and puts it into the NH ₃ storage, and the NH ₃ The NH ₃ (g) may be supplied from the storage to the ammonia water tank.

In addition, it is possible to prevent evaporation loss of NH ₃ by injecting compressed air of a certain pressure into the ammonia water tank.

In addition, the absorption tower branches at least a portion of the exhaust gas discharged from the marine engine of the engine room and reacts with the seawater supplied from the seawater supply unit for cooling, and the cooled exhaust gas and the absorption liquid from the absorption liquid manufacturing unit By reacting CO ₂ to convert CO 2 into an aqueous ammonium salt solution, the CO ₂ removal unit may be formed to remove CO ₂ .

In addition, a blowing means for supplying at least a portion of the branched exhaust gas to the CO ₂ removal unit may be provided.

In addition, the blowing means may be a blower.

In addition, among the exhaust gases discharged from the marine engine, the residual exhaust gas that is not branched to the CO ₂ removal unit is discharged through the main exhaust pipe, and the at least a portion of the exhaust gas branched to the CO ₂ removal unit is CO ₂ removed. After being discharged, it may be discharged by being merged into the main exhaust pipe, or discharged through a separate discharge pipe.

In addition, the CO ₂ removal unit may be installed inside the engine casing above the engine room.

In addition, the absorption liquid regeneration unit includes a storage tank installed in the form of a silo to store and supply an aqueous divalent metal hydroxide solution, and an ammonium salt aqueous solution discharged from the absorption tower and self-weight from the storage tank, which is formed in the lower portion of the storage tank. It may include a mixing tank for generating NH ₃ (g) and carbonate by stirring the divalent metal hydroxide aqueous solution supplied by the stirrer, and a filter for separating carbonate by sucking the solution and precipitate from the mixing tank.

In addition, a storage tank for storing and supplying the divalent metal hydroxide aqueous solution is disposed on an inner side surface of the engine casing adjacent to the absorption tower, and the mixing tank is formed at a lower portion of the storage tank, on the inner side surface of the engine casing can be placed.

In addition, a storage tank for storing and supplying the divalent metal hydroxide aqueous solution may be disposed on an inner side surface of the engine casing adjacent to the absorption tower, and the mixing tank may be disposed in the engine room under the engine casing.

In addition, the storage tank for storing and supplying the divalent metal hydroxide aqueous solution may be disposed on the outer surface of the engine casing adjacent to the absorption tower.

In addition, the absorption liquid circulation unit may include an ammonia water circulation pump for circulating a portion of the ammonium salt aqueous solution or unreacted absorption liquid through the absorption liquid circulation line, and a pH sensor for measuring the concentration of the absorption liquid supplied to the upper end of the absorption tower.

In addition, the absorption liquid regenerating unit, a storage tank for storing the divalent metal hydroxide aqueous solution, and the ammonium salt aqueous solution and the divalent metal hydroxide aqueous solution discharged from the absorption tower are stirred by a stirrer to produce NH ₃ (g) and carbonate. It may include a tank and a filter for separating the carbonate by sucking the solution and the precipitate from the mixing tank.

In addition, NH ₃ (g) generated by the mixing tank may be supplied to the absorption tower, or the absorption liquid separated by the filter may be supplied to the absorption liquid circulation unit.

In addition, the aqueous solution of divalent metal hydroxide stored in the storage tank may be Ca(OH) ₂ or Mg(OH) ₂ generated by reacting fresh water with CaO or MgO.

In addition, the ammonia water or fresh water separated by the filter is supplied to the absorption liquid manufacturing unit, or the surplus fresh water additionally generated by the mixing tank compared to the total circulation fresh water is stored in the fresh water tank to generate a divalent metal hydroxide aqueous solution in the storage tank city can be recycled.

In addition, the absorption tower further includes an SOx absorption unit for dissolving and removing SOx while cooling by reacting the exhaust gas discharged from the marine engine with the seawater supplied from the seawater supply unit, and the CO ₂ removal unit removes the SOx The exhaust gas is cooled by reacting with the seawater supplied from the seawater supply unit, and the cooled exhaust gas and the absorption liquid from the absorption liquid preparation unit are reacted to convert CO ₂ into an aqueous ammonium salt solution to remove CO ₂ .

In addition, the absorption tower further comprises a NOx absorption unit for absorbing and removing NOx of the exhaust gas discharged from the marine engine, and the NOx is removed by reacting the exhaust gas with seawater supplied from the seawater supply unit to cool and By reacting the cooled exhaust gas with the absorption liquid from the absorption liquid preparation unit, CO ₂ may be converted into an aqueous ammonium salt solution to remove CO ₂ .

In addition, the absorption tower, the NO _X absorption unit for absorbing and removing NO _X of the exhaust gas discharged from the marine engine, and the NO _X is removed by reacting the exhaust gas with seawater supplied from the seawater supply unit to cool The SO _X absorption unit for dissolving and removing SO _X , and the CO ₂ removal unit for removing the CO _{2 by converting the CO 2 into} an aqueous ammonium salt solution by reacting the exhaust gas from which the SO _X has been removed and the absorption liquid from the absorption liquid production unit It may be sequentially laminated.

In addition, the NH ₃ regenerated by the absorption liquid regeneration unit may be supplied to the NO _X absorption unit, and the NO _X absorption unit may absorb NO _X as NH ₃ or absorb NO _X using urea water.

In addition, the seawater supply unit, the seawater pump that receives the seawater from the outboard through the sea chest and pumps it to the SO _{X absorption unit, and the amount of exhaust gas to control the injection amount of seawater supplied from the seawater pump to the SO X absorption} unit It may include a seawater control valve.

In addition, the SO _X absorption unit, a multi-stage seawater injection nozzle for spraying the seawater supplied from the seawater supply unit downwardly; and an exhaust gas inlet pipe in the form of a partition wall or an umbrella-shaped blocking plate covering the exhaust gas inlet pipe to prevent the washing water from flowing backward.

In addition, a porous upper plate having a flow path through which the exhaust gas passes is formed in multiple stages under the seawater injection nozzle, respectively, so that seawater and the exhaust gas can contact each other.

In addition, an absorption tower filled with a filler for allowing seawater and exhaust gas to contact is formed under the seawater injection nozzle, so that seawater can dissolve SO _X .

In addition, a neutralizing agent may be added to the seawater supplied to the SO _X absorption unit.

In addition, the CO ₂ removal unit, ammonia water injection nozzle for spraying the absorption liquid downward; A filler for converting CO ₂ into NH ₄ HCO ₃ (aq) by contacting CO ₂ with ammonia water as an absorption liquid; a cooling jacket formed in multiple stages for each section of the absorption tower filled with the filler to cool the heat generated by the CO ₂ removal reaction; Water spray collecting NH ₃ discharged to the outside without reacting with CO ₂ ; Mist removal plate formed in a curved multi-plate shape to return ammonia water in the direction of the filler; barrier ribs formed so that ammonia water does not flow back; and an umbrella-shaped blocking plate covering the exhaust gas inlet hole surrounded by the partition wall.

In addition, the filler is composed of a multi-stage distillation column packing designed to have a large contact area per unit volume, and a solution redistributor may be formed between the distillation column packings.

In addition, the absorption tower may further include an EGE formed between the NO _X absorption unit and the SO _X absorption unit to exchange heat between waste heat of the marine engine and boiler water.

In addition, an auxiliary boiler for receiving a mixture of heat-exchanged steam and saturated water to separate the steam and supplying it to a steam consuming place, a boiler water circulation water pump for circulating and supplying boiler water from the auxiliary boiler to the EGE, and the steam consumption A cascade tank for recovering condensed water from the cascade, and a supply pump and control valve for supplying by controlling the amount of boiler water from the cascade tank to the auxiliary boiler, it may further include a steam generator.

In addition, a washing water tank for storing the washing water discharged from the absorption tower, a filtering unit for adjusting the turbidity to meet the overboard discharge conditions of the washing water transferred to the washing water tank by a transfer pump, and a neutralizer injection for pH control A water treatment device having a unit, and a sludge storage tank for separately storing the solid discharge, may further include a discharge unit.

According to the present invention, the boil-off gas from liquefied ammonia stored in the cargo hold of the ammonia carrier or the vaporized gas vaporized from liquefied ammonia is converted into a CO ₂ absorption liquid, and the absorbed CO ₂ is removed by taking only a portion of the absorption liquid used for collecting CO ₂ It has the effect of keeping the size of the apparatus of the absorption liquid regeneration unit and the absorption liquid circulation unit small by treating it, enabling continuous operation, and flexibly coping with the CO ₂ absorption rate according to the load change of the marine engine.

In addition, by overcoming the back pressure limitation of the absorption tower, it is installed on a ship that cannot be installed in the existing absorption tower, and the size of the absorption tower is optimized to overcome the limitations of the diameter or height in the installation space, and the CO ₂ removal unit and the absorption liquid regeneration By constructing a storage tank in the engine casing that stores and supplies the divalent metal hydroxide aqueous solution for By configuring the storage tank that stores and supplies the silo in the form of a silo so that it can be supplied to the mixing tank by its own weight, there is an effect that can remove or minimize ancillary equipment necessary for supply to the mixing tank.

Furthermore, it is possible to prevent degradation of the greenhouse gas absorption performance by supplying a high-concentration absorbent liquid, and to prevent loss of absorbent liquid due to natural evaporation of the high-concentration absorbent liquid by applying a pressurization system, and to protect the environment to meet IMO greenhouse gas emission regulations. It is converted into a carbonate form in its natural state that does not affect it, separated and discharged or converted into a useful material and stored, and the consumption of relatively expensive NH ₃ by regenerating NH ₃ can be minimized, and the capacity size of the rear end of the filter can be reduced, NH ₃ There is an effect of minimizing the loss of NH ₃ by removing side reactions due to the remaining SO _X during regeneration and preventing impurities from being included in the recovery of ammonia.

1 shows a schematic configuration diagram of an apparatus for reducing greenhouse gas emission of an ammonia carrier according to an embodiment of the present invention.
Figure 2 shows a system circuit diagram implementing the greenhouse gas emission reduction device of the ammonia carrier of Figure 1.
3 is a view showing the separation of the seawater supply unit and the absorption tower of FIG.
FIG. 4 is a view showing the separation of the liquefied ammonia storage tank, the absorbent liquid production unit, the absorbent liquid regeneration unit, and the absorbent liquid circulation unit of FIG. 2 .
FIG. 5 is an exploded view of a part of the absorption tower of FIG. 2 .
FIG. 6 is a view showing the SO _X absorption part of the absorption tower of FIG. 5 separated.
FIG. 7 is a view illustrating the separation of the steam generating unit and the discharging unit of FIG. 2 .
FIG. 8 illustrates the configuration and arrangement of the absorption tower and the absorption liquid regeneration unit of FIG. 2 .
9 illustrates various fillers applied to the greenhouse gas emission reduction device of the ammonia carrier of FIG. 2 .
FIG. 10 illustrates an ammonia water injection nozzle applied to the apparatus for reducing greenhouse gas emissions of the ammonia carrier of FIG. 2 .

Hereinafter, with reference to the accompanying drawings, embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily implement them. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

1, the apparatus for reducing greenhouse gas emission of an ammonia carrier according to an embodiment of the present invention includes a liquefied ammonia storage tank 100 for storing liquefied ammonia, a seawater supply unit 110 for supplying seawater, and a liquefied ammonia storage tank The absorption liquid production unit 120 that receives ammonia supplied from 100 and manufactures and supplies a high-concentration CO ₂ absorption liquid, and the seawater supplied from the seawater supply unit 110 for the exhaust gas discharged from the marine engine 10 of the engine room 20 . The absorption tower 130 is formed with a CO ₂ removal unit 131 for converting CO ₂ into an aqueous ammonium salt solution by reacting the cooled exhaust gas with the absorption liquid from the absorption liquid production unit 120 to remove CO ₂ ), by reacting the aqueous solution of the ammonium salt discharged from the absorption tower 130 with the aqueous solution of divalent metal hydroxide to regenerate the absorption liquid and NH ₃ and circulately supply it to the absorption tower 130 for reuse as the absorption liquid, the absorption liquid regeneration unit 140, and Including an absorption liquid circulation unit 150 that circulates a portion of the ammonium salt aqueous solution or unreacted absorption liquid discharged from the bottom of the absorption tower 130 to the top of the absorption tower 130 through the absorption liquid circulation line (A), storing liquefied ammonia of the ammonia carrier The ammonia stored in the tank 100 is converted into a CO ₂ absorption liquid, the remaining unreacted absorption liquid is circulated to the absorption tower 130 to maintain the CO ₂ absorption rate, and the absorption tower 130 according to the load change of the marine engine 10. The gist is to absorb CO ₂ from at least a portion of the exhaust gas by the

Here, the type and specification of the marine engine used as the main engine for propulsion or the engine for power generation (low-pressure engine or high-pressure engine), and the type of fuel supplied to the marine engine (HFO, MDO, LNG, MGO, LSMGO, ammonia, etc.) Accordingly, the absorption tower 130 may be configured to include, in addition to the CO ₂ removal unit, a NOx absorption unit for removing nitrogen oxides or a SOx absorption unit for removing sulfur oxides, or to include all of them.

In particular, when low-sulfur oil (LSMGO) is used as a fuel for a marine engine, an SOx absorption unit capable of simultaneously performing both cooling of exhaust gas and absorption and removal by dissolution of SOx may be additionally provided.

Hereinafter, an embodiment in which the NOx absorption unit, the SOx absorption unit and the CO ₂ removal unit are sequentially stacked on the absorption tower 130 will be described, but the present invention is not limited thereto. Depending on the engine specifications and the type of fuel, it is possible to selectively decide whether to have the device or not.

Hereinafter, with reference to FIGS. 1 to 10 , the configuration of the apparatus for reducing greenhouse gas emission of the above-described ammonia carrier will be described in detail as follows.

First, the liquefied ammonia storage tank 100 may be an example of a cargo containment system of an ammonia carrier that stores and transports liquefied ammonia, and the ammonia carrier lowers the liquefied ammonia to a temperature below the boiling point to liquefy and transport, Ammonia storage tank 100 may be made of an insulating tank made of a barrier made of nickel steel or stainless steel resistant to low temperature to maintain a pressure of 1 bar and a temperature of -33 ℃.

On the other hand, the liquefied ammonia storage tank 100 may be a membrane type tank having a heat dissipation structure integrated with the hull, or may be an independent tank, and in the case of an independent tank, Type A prescribed by the International Maritime Organization (IMO). , it may be a Type B or Type C storage tank, but is not limited thereto.

Specifically, the liquefied ammonia storage tank 100 supplies boil-off gas (BOG) generated by naturally evaporating liquefied ammonia in the liquefied ammonia tank 100 to the absorption liquid manufacturing unit 120, or evaporates. When the amount of ammonia gas required for the production of the absorbent liquid by gas alone is insufficient, the ammonia gas in which liquid ammonia is forcibly vaporized may be supplied to the absorbent liquid production unit 120 through the vaporizer 102 .

Here, the liquefied ammonia is discharged through a feed pump (not shown) disposed in the liquefied ammonia tank 100 and supplied to the vaporizer 102 , and the ammonia gas forcedly vaporized through the vaporizer 102 is produced as an absorption liquid It may be additionally supplied to the unit 120 .

Next, the seawater supply unit 110 supplies seawater to the absorption tower 130 to lower the temperature of the high-temperature and high-pressure exhaust gas to facilitate the absorption of CO ₂ by the absorption liquid.

Specifically, the seawater supply unit 110, as shown in FIGS. 2 and 3, sucks and supplies seawater from the outboard through a sea chest (not shown) and absorbs SO _X of the absorption tower 130 . It may be composed of a seawater pump 111 for pumping to the unit 132 and a seawater control valve 112 for controlling the injection amount of seawater supplied to the SO _X absorption unit 132 according to the amount of exhaust gas. Here, the seawater pump 111 may be separated into a suction pump for sucking seawater from the outboard and a seawater transfer pump for pumping and transferring seawater to the SO _X absorption unit 132 .

For reference, depending on the berthing or sailing time of the ship, depending on the depth of the water, the high sea chest that sucks the sea water at the top or the low sea chest that sucks the sea water at the bottom can selectively use the sea water pump 111 . can supply That is, when the ship is berthing, the high sea chest is used because the sea water above is cleaner than the sea water at the bottom, and when the ship is sailing, the low sea chest can be used because the sea water at the bottom is cleaner than the sea water at the top.

Here, the seawater control valve 112 may be a manually operated diaphragm valve or a solenoid valve for controlling the flow rate of _seawater , but is not limited thereto. Any type of valve may be applied as long as the amount of seawater injected through the seawater injection nozzle 132a of the absorption unit 132 can be adjusted.

Next, the absorbent liquid manufacturing unit 120 reacts with fresh water and ammonia supplied from the liquefied ammonia storage tank 100 as shown in the following [Formula 1] to supply a high-concentration absorbent liquid to maintain the concentration of the absorbent liquid. to prepare a high-concentration ammonia water (NH ₄ OH(aq)), which is a high-concentration CO ₂ absorption liquid, and supply it to the CO ₂ removal unit 131 formed at the upper end of the absorption tower 130 through the absorption liquid circulation unit 150 .

Specifically, as shown in FIGS. 2 and 4, the absorption liquid manufacturing unit 120 includes a fresh water tank (not shown) for storing fresh water, and a fresh water control valve for supplying fresh water from the fresh water tank to the ammonia water tank 123 ( 121), NH ₃ storage 122 for storing high-pressure NH ₃ , and NH ₃ supplied from the NH ₃ storage 122 to the fresh water supplied by the fresh water control valve 121 to produce and store high-concentration ammonia water An ammonia water tank 123, a pH sensor 124 for measuring the ammonia water concentration in the ammonia water tank 123, and an ammonia water supply pump 125 for supplying a high concentration ammonia water from the ammonia water tank 123 to the absorption liquid circulation unit 150. can be

On the other hand, the boil-off gas from the liquefied ammonia storage tank 100 is directly introduced into the ammonia water tank 123 and supplied, or the liquefied ammonia from the liquefied ammonia storage tank 100 is forcibly vaporized through the vaporizer 102 to the ammonia water tank. It can be supplied by directly inputting into (123).

Alternatively, the boil-off gas from the liquefied ammonia storage tank 100 is introduced into the NH ₃ storage 122, and ammonia is introduced from the NH ₃ storage 122 to the ammonia water tank 123, or from the liquefied ammonia storage tank 100. of liquefied ammonia is forcibly vaporized through the vaporizer 102 and put into the NH ₃ storage 122, and ammonia is introduced from the NH ₃ storage 122 into the ammonia water tank 123, thereby selectively opening and closing the switching valve 103 Accordingly, the boil-off gas from the liquid ammonia storage tank 100 or the vaporized gas forcibly vaporizing liquid ammonia may be directly supplied to the ammonia water tank 123, but boil off gas or liquid ammonia from the liquid ammonia storage tank 100 The forced vaporized gas may be separately stored in the NH ₃ storage 122 and supplied to the ammonia water tank 123 by opening the switching valve 103 when necessary.

Ammonia water, which is an absorption liquid that circulates through the absorption tower 130 and the absorption liquid regeneration unit 140 along the absorption liquid circulation line (A), changes in concentration while repeating operation. For example, NH ₃ is supplied to the NO _X absorption unit 133 . is used for absorption and removal of NO _X , or NH ₃ is discharged into the atmosphere as exhaust gas through the absorption tower 130, so that the concentration of ammonia water is lowered. 120) by supplying a high concentration of ammonia water to the absorption liquid circulation line (A) of the absorption liquid circulation unit 150, compensating for the lowered ammonia water concentration can be kept constant at the designed ammonia water concentration.

On the other hand, high-concentration ammonia water has a higher partial pressure of NH ₃ (g) compared to low-concentration ammonia water at the same temperature, so that NH ₃ evaporates more easily at atmospheric pressure, thereby increasing loss. Therefore, in order to store the high concentration ammonia water, the solubility is high and the temperature is lowered so that the vapor pressure of NH ₃ (g) is lowered, and it must be operated under a pressurized system.

That is, in order to prevent NH ₃ (g) from being evaporated and lost into the atmosphere, compressed air of a certain pressure is injected into the ammonia water tank 123, and the pressure in the ammonia water tank 123 is maintained at a high state to evaporate NH ₃ loss can be effectively prevented.

For example, NH ₃ can be stored in a liquid state at -34 ° C. and 8.5 bar, so by using 7 bar compressed air available in the ship, the inside of the ammonia water tank 123 is maintained at a constant pressure, and 50% concentration of ammonia water is obtained. It can be stored in the ammonia water tank (123).

In addition, a safety valve 123a for preventing overpressure of the ammonia water tank 123 may be installed.

Next, the absorption tower 130 has an exhaust gas discharged from the marine engine 10 of the engine room 20, preferably by branching at least a portion of the exhaust gas and reacting with the seawater supplied from the seawater supply unit 110 to cool it. And, by reacting the cooled exhaust gas CO ₂ and the ammonia water from the absorption liquid production unit 120 or the ammonia water circulating the absorption liquid circulation line (A), as in the following [Formula 2], CO ₂ is converted into a high-concentration ammonium salt aqueous solution ( NH ₄ HCO ₃ (aq)) is converted to CO ₂ to remove CO ₂ The removal unit 131 is formed.

That is, even by absorbing only some CO ₂ from the exhaust gas discharged from the marine engine 10, in most cases, the greenhouse gas emission standard can be satisfied, so branch from the main exhaust pipe 135 connected to the marine engine 10 ( branched) or by injecting at least a portion of the exhaust gas into the absorption tower 130 according to the load change of the marine engine 10 through the branched first bypass pipe 136 to absorb CO ₂ , the marine engine 10 The CO ₂ absorption rate can be flexibly changed according to the load change.

Meanwhile, referring to FIG. 8 , the CO ₂ removal unit 131 (CO ₂ scrubber) may be disposed in combination with the main exhaust pipe 135 inside the engine casing 30 above the engine room 20 . Alternatively, the entire absorption tower 130 including the CO ₂ removal unit 131 may be disposed in combination with the main exhaust pipe 135 inside the engine casing 30 above the engine room 20 .

Specifically, the CO ₂ removal unit 131, as shown in FIG. 3, the ammonia water injection nozzle 131a for spraying the ammonia water supplied from the absorption liquid circulation unit 150 downward, and the first bypass pipe 136. The filler (131b) that converts CO ₂ into high-concentration NH ₄ HCO ₃ (aq) by contacting the CO ₂ and ammonia water of the exhaust gas injected through it, is formed in multiple stages for each section of the absorption tower filled with the filler (131b) to absorb CO ₂ A cooling jacket (not shown) that cools the heat generated by the reaction, a water spray (131c) that collects NH ₃ that is discharged into the atmosphere without reacting with CO ₂ , is formed in the form of a curved multi-plate, and is formed in the form of an ammonia water spray nozzle ( 131a) a mist removing plate 131d for returning the ammonia water scattered during injection in the direction of the filler 131b, and a partition wall 131e formed so that the ammonia water that has passed through the filler 131b does not flow back to the SO _X absorption unit 132. , and an umbrella-shaped blocking plate 131f covering the exhaust gas inlet hole surrounded by the partition wall 131e.

Here, the cooling jacket is cooled to 30° C. to 50° C. where material shearing is the most smooth, and while maintaining the CO ₂ absorption rate at a constant level, NH ₃ can be prevented from being vaporized and lost.

On the other hand, the CO ₂ removal unit 131 can be considered in various forms to operate within the allowable pressure drop of the exhaust pipe required by the engine specification while increasing the contact area between the exhaust gas and NH ₃ , for example, the filler (131b) is composed of a multi-stage distillation column packing designed to have a large contact area per unit volume, and a distillation column packing suitable for the absorption process as illustrated in FIG. 9 in consideration of the contact area per unit area, pressure drop and overflow rate of gas can be selected, and as illustrated in FIG. 10 , the ammonia water injection nozzle 131a may be configured in a ladder pipe type (a) or a spray type (b).

In addition, ammonia water passes downward through the filler 131b and the exhaust gas passes upward through the filler 131b and comes into contact, so that a solution redistributor (not shown) may be formed between the distillation column packings to prevent channeling.

In addition, the mist removing plate (131d) is to be discharged (drain) in the direction of the filler (131b) by its own weight so that the scattered ammonia water is adhered to the curved multi-plate so that the droplets (droplets) become large.

On the other hand, when using LNG as a fuel, there may be no amount of SOx generated, but when the marine engine 10 uses low-sulfur oil as a fuel, the absorption tower 130 may additionally include an SOx absorption unit 132 . may be

That is, the SOx absorption unit 132 reacts the exhaust gas discharged from the marine engine 10 with the seawater supplied from the seawater supply unit 110 to dissolve and remove SOx while cooling, and the CO ₂ removal unit 131 is the SOx is cooled by reacting the removed exhaust gas with seawater supplied from the seawater supply unit 110, and by reacting the cooled exhaust gas with the absorption liquid from the absorption liquid production unit 120 to convert CO ₂ into an aqueous ammonium salt solution to absorb CO ₂ can be removed

Specifically, the SOx absorption unit 132 is a section in primary contact with seawater, and as shown in FIGS. 3 and 6 , by spraying the seawater supplied from the seawater supply unit 110 downward to dissolve _SOx and chute A multi-stage seawater injection nozzle 132a for removing dust (soot), and an umbrella-type blocking that covers the bulkhead-type exhaust gas inlet pipe 132b or the exhaust gas inlet pipe 132b to prevent backflow of washing water It may include a plate 132c.

On the other hand, through the seawater injection nozzle (132a) or a separate cooling jacket (not shown), the temperature of the exhaust gas can be cooled to 27°C to 33°C, preferably around 30°C, required by the CO ₂ removal unit 131. There, as shown in (a) of FIG. 6 , the porous upper plate 132d in which the flow path through which the exhaust gas is formed is formed in the lower part of the seawater injection nozzle 132a is formed in multiple stages, so that seawater and exhaust gas smoothly As shown in (b) of FIG. 6 , an absorption tower 132e filled with a filler for contacting seawater and exhaust gas is formed under the seawater injection nozzle 132a, respectively, so that seawater is SO _X It can also be made to dissolve.

On the other hand, in order to further increase the solubility of SO _X , a compound that forms alkali ions, for example, a basic chemical of NaOH or MgO is introduced into the seawater supplied to the SOx absorption unit 132. It can be configured as a closed loop system. .

For reference, the closed-loop system entails additional basic chemical consumption, but has the advantage that the amount of circulating seawater is small, and the open-loop system that discharges dissolved _SOx by spraying only seawater to the outboard consumes additional basic chemical Since there are no and simple advantages, in order to maximize these advantages, a hybrid system that combines an open circuit and a closed circuit may be configured.

Accordingly, SO _X is first removed through the SO _X absorbing unit 132 and then CO ₂ is subsequently removed through the CO ₂ removing unit 131 , so that the solubility of SO _X is large, so that it is first used as a compound such as Na ₂ SO ₃ It is possible to improve the solubility of CO ₂ and the removal efficiency of CO ₂ by solving the problem that it is difficult to remove CO ₂ until all the dissolution of SO _X is completed.

Here, the washing water that absorbs SO _X by the SO _X absorption unit 132 and drains to the discharge unit 170 includes SO ₃ ⁻ , SO ₄ ²⁻ , chute, NaSO ₃ , NaSO ₄ , MgCO ₃ , MgSO ₄ and Other ionic compounds are also included.

On the other hand, as mentioned above, the absorption tower 130 further includes a NOx absorption unit 133 that absorbs and removes NOx of the exhaust gas discharged from the marine engine 10, and removes the NOx from the exhaust gas. It is cooled by reacting with the seawater supplied from the seawater supply unit 110 and the cooled exhaust gas and the absorption liquid from the absorption liquid preparation unit 120 are reacted to convert CO ₂ into an aqueous ammonium salt solution to remove CO ₂ .

That is, the absorption tower 130 is a NO _X absorption unit 133 that absorbs and removes NO _X of the exhaust gas discharged from the marine engine 10, and the NO _X is removed by reacting the exhaust gas with seawater to cool the SO The SO _X absorption unit 132 for dissolving and removing _X reacts with the exhaust gas from which SO _X has been removed and the ammonia water supplied from the absorption liquid production unit 120 to convert CO ₂ into NH ₄ HCO ₃ (aq) to CO The CO ₂ removal unit 131 for removing ₂ is stacked, and sequentially absorbs and removes NO _X and SO _X and CO ₂ .

Accordingly, the CO ₂ removal unit 131 reacts the exhaust gas from which NO _X and SO _X have been previously removed with ammonia water to first remove NO _X and SO _X , and side reactions due to NO _X and SO _X during the CO ₂ removal process Since this does not occur, the generation of impurities can be minimized, so that NH ₄ HCO ₃ with less impurities can be obtained in the subsequent process.

Here, the absorption tower 130 is configured to include a CO ₂ removal unit 131 , a SO _X absorption unit 132 , an NO _X absorption unit 133 , and an EGE 134 to be described later, each of which is configured as an individual module. It may be modularized and combined configuration, may be configured to be integrated in the form of a single tower, and the absorption tower 130 itself may be configured to be grouped into a single tower or a plurality of towers.

Specifically, the NO _X absorption unit 133 is a Selective Catalyst Reactor (SCR), and as shown in FIG. 5 , the absorption liquid regeneration unit 140 through the blower 133a or the first NH ₃ injection nozzle 133b ) to directly supply NH ₃ or, when NH ₃ is insufficient, the urea water (UREA) of the urea water storage tank 133c is supplied to the second NH ₃ injection nozzle 133e through the urea water supply pump 133d. It can also be substituted to compensate for the shortfall.

On the other hand, when urea water is decomposed, NH ₃ and CO ₂ are generated, so it may be preferable to directly supply NH ₃ to reduce the amount of CO ₂ generated.

In addition, the absorption tower 130 is formed between the NO _X absorption unit 133 and the SO _X absorption unit 132 to exchange heat with the waste heat of the marine engine 10 and boiler water (EGE (Exhaust Gas Economizer) 134 ) may further include.

On the other hand, as shown in FIG. 3, the piping system between the marine engine 10 and the absorption tower 130 is connected to the exhaust pipe of the marine engine 10 to directly discharge CO ₂ to the atmosphere without removing the main exhaust pipe ( 135), and a first bypass pipe 136 branched from the main exhaust pipe 135 and connected to the lower end of the absorption tower 130 so that at least a portion of the exhaust gas is introduced, and the absorption tower 130 passing through the CO ₂ The second bypass pipe 137 for directly discharging the exhaust gas from which has been removed, and the second bypass pipe 137 branched from the second bypass pipe 137 and connected to the main exhaust pipe 135 to remove CO ₂ through the main exhaust pipe 135. It may be composed of a third bypass pipe 138 that joins the exhaust gas and discharges it to the atmosphere.

Through such a piping system, after removing CO ₂ from some exhaust gas from the marine engine 10, it joins the main exhaust pipe 135 and discharges it to the atmosphere, or separately to the atmosphere through the second bypass pipe 137. Thus, by optimizing the greenhouse gas processing capacity, it is possible to minimize the size of the absorption tower 130 to overcome the limitations on the installation space.

In addition, referring to FIGS. 2 and 3 , the blowing means 139 branching from the main exhaust pipe 135 and supplying at least a portion of the exhaust gas to the CO ₂ removal unit 131 is installed in the middle of the first bypass pipe 136 . provided, the CO ₂ removal unit 131 and the SO _X absorption unit 132 of the absorption tower 130, the NO _X absorption unit 133 and the EGE 134, and the back pressure generated due to the configuration of the piping system pressure), the diameter of the absorption tower 130 is minimized and the height is designed to be high to overcome the limitations of the installation space.

Here, the blowing means 139 may be configured as a blower, and the blower blows or pressurizes the exhaust gas at 40° C. to 50° C. when the scrubber, that is, the SOx absorption unit 132 is installed. If the SOx absorption unit 132 is not installed, it is preferably designed to blow or pressurize the exhaust gas around 300°C.

In addition, the blower can variably adjust the amount of air blown according to the load of the ship engine 10 , and the operating point can be determined through the step of determining the amount of exhaust gas to be blown to the absorption tower 130 .

For reference, the marine engine 10 drives a turbine of a turbocharger using exhaust gas, compresses air required for combustion through a compressor connected to the turbine shaft, and the amount of compressed air flows into the turbocharger It is affected by the temperature, pressure, and flow rate of exhaust gas, and the amount of change in enthalpy by the temperature, pressure, and flow rate discharged from the turbocharger.

In particular, the back pressure on the piping system is a factor directly related to the performance of the turbocharger, and the total back pressure is limited to 450 mmAq to 600 mmAq. When the EGE 134 and the SOx absorption unit 132 are installed, the CO ₂ removal unit Due to the additional back pressure generated by the installation, there is a limitation on the installation, or there is a difficulty in manufacturing the absorption tower to minimize the back pressure.

For example, when the CO ₂ removal unit 131 is limited by the back pressure, the back pressure can be reduced by expanding the diameter through which the exhaust gas flows, but the size of the device increases and installation is restricted, so by installing a blower, the CO ₂ The diameter of the removal part 131 may be small and the height may be large to provide a significant advantage in installation.

In addition, as mentioned above, after removing CO ₂ from some exhaust gas from the marine engine 10, when it joins the main exhaust pipe 135 and discharges to the atmosphere, only one CO ₂ sensor is provided in the main exhaust pipe 135. may be configured, and each CO ₂ sensor may be configured when the main exhaust pipe 135 and the second bypass pipe 137 each discharge to the atmosphere.

Next, the absorption liquid regeneration unit 140 regenerates NH ₃ from the ammonium salt aqueous solution and returns it to the CO ₂ removal unit 131 of the absorption tower 130 through the absorption liquid circulation unit 150 to be reused as a CO ₂ absorption liquid, CO ₂ may be stored in the form of CaCO ₃ (s) or MgCO ₃ (s) or discharged overboard, or NH ₃ may be supplied to the NO _X absorption unit 133 to absorb NO _X.

On the other hand, the absorption liquid regeneration unit 140, as shown in FIGS. 4 and 8 (b) and (c), is installed in the form of a silo (silo) to store the divalent metal hydroxide aqueous solution storage tank (141) , the aqueous solution of ammonium salt formed in the lower part of the storage tank 141 and discharged from the absorption tower 130 and the aqueous solution of divalent metal hydroxide supplied by its own weight from the storage tank 141 are stirred with a stirrer to obtain the following [Formula 3] As such, it may be composed of a mixing tank 142 for generating NH ₃ (g) and carbonate, and a filter 143 for separating carbonate by sucking the solution and precipitate from the mixing tank 142 .

Referring to Figure 8 (b), the storage tank 141 is configured in the form of a silo by the self-load of the divalent metal hydroxide aqueous solution from the bottom to the mixing tank 142, an auxiliary device necessary for supply By removing or minimizing the divalent metal hydroxide aqueous solution can be easily supplied.

Here, the storage tank 141 is adjacent to the absorption tower 130, for example, adjacent to both sides of the absorption tower 130, disposed on the inner side of the engine casing 30, the mixing tank 142 is It may be configured to be disposed on the inner side surface of the engine casing 30 while being formed in the lower portion of the storage tank 141 .

Alternatively, the storage tank 141 is adjacent to the absorption tower 130, for example, adjacent to both sides of the absorption tower 130, disposed on the inner side of the engine casing 30, the mixing tank 142 is It may be separately disposed in the engine room 20 under the engine casing 30 while being formed in the lower portion of the storage tank 141 .

On the other hand, in the case of a modified ship, the storage tank 141 may be additionally disposed on the outer surface of the existing engine casing 30 , or the existing engine casing 30 may be expanded and disposed on the inner side as described above.

Through the arrangement of the above-described storage tank 141, the installation space problem can be solved by utilizing it without affecting the space of the existing engine casing area. By enabling the supply to the 142), it is possible to eliminate or minimize ancillary devices necessary for supply to the mixing tank 142.

In addition, the aqueous solution of divalent metal hydroxide stored in the storage tank 141 may be Ca(OH) ₂ or Mg(OH) ₂ generated by reacting fresh water with CaO or MgO.

In addition, when the concentration of ammonia water circulating in the absorption liquid circulation line (A) is low, the generation of (NH ₄ ) ₂ CO ₃ of the previous [Formula 2] is reduced to increase CO ₂ emission, and when the concentration is high, excessive CO ₂ Because the carbonate production increases more than necessary due to absorption, the concentration of ammonia water must be kept constant so that the CO ₂ absorption performance of the absorption tower 130 can be continued. In order to implement this, it can be designed to adjust the concentration of ammonia water to 12% by mass, but is not limited thereto and may be changed according to the conditions of use.

In addition, the carbonate (CaCO ₃ (s), MgCO ₃ (s)) separated by the filter 143 is transferred to a slurry state, or a dryer (not shown) and transferred to a solid state, which is stored separately. It may be provided with a storage tank (not shown) of the, or may be discharged overboard without storage. Here, as an example of the filter 143, a membrane filter suitable for sediment separation by high-pressure fluid transport may be applied.

On the other hand, the ammonia water or fresh water separated by the filter 143 is supplied to the absorption liquid circulation unit 150, or the surplus fresh water additionally generated by the mixing tank 142 compared to the total circulation fresh water is stored in a fresh water tank (not shown). When the divalent metal hydroxide aqueous solution is generated in the storage tank 141, fresh water can be saved by recycling it.

Through this, only relatively inexpensive metal oxide (CaO or MgO) or divalent metal hydroxide aqueous solution (Ca(OH) ₂ or Mg(OH) ₂ ) is added, so that additional input of water is not required, there is no decrease in the concentration of ammonia water, and the filter ( 143), it is possible to reduce the capacity size, and it is possible to reduce the cost of NH ₃ regeneration. That is, in theory, only metal oxide is consumed, and NH ₃ and fresh water are reused, thereby significantly reducing the cost of CO ₂ removal.

In addition, ammonia gas generated in the mixing tank 142 may be supplied to the CO ₂ removal unit 131 of the absorption tower 130 or may be supplied to the NOx absorption unit 133 .

Next, the absorption liquid circulation unit 150 continuously circulates the absorption liquid to the absorption tower 130 to maximize CO ₂ absorption, and the high concentration ammonium salt aqueous solution discharged from the CO ₂ removal unit 131 of the absorption tower 130 and , a portion of the non-reacted absorption liquid that did not react with CO ₂ is circulated to the ammonia water injection nozzle 131a of the CO ₂ removal unit 131, so that only a portion of the ammonium salt aqueous solution is converted into carbonate by the absorption liquid regeneration unit 140, and the remaining The reaction absorption liquid is circulated to the absorption tower 130 to maintain the CO ₂ absorption rate.

Specifically, as shown in FIG. 4, the absorption liquid circulation unit 150 includes a centrifugal pump type ammonia water circulation pump 151 that circulates a portion of the ammonium salt aqueous solution and the unreacted absorption liquid through the absorption liquid circulation line A, and CO ₂ It may include a pH sensor 152 for measuring the concentration of the absorbent solution supplied to the upper end of the removal unit 131 .

Here, when the concentration of HCO ₃ ⁻ in the absorption liquid is high, the amount of CO ₂ absorption decreases and the CO ₂ emission increases, and when the concentration of HCO ₃ ⁻ is low, the carbonate production increases more than necessary due to excessive CO ₂ absorption, so the pH By continuously monitoring the concentration of the absorption liquid through the sensor 152 , the concentration of HCO ₃ ⁻ or OH ⁻ in the absorption liquid, that is, the pH may be maintained at an appropriate level.

Through this, a portion of the ammonium salt aqueous solution flowing through the absorption liquid circulation line (A) is transferred to the mixing tank 142 of the absorption liquid regeneration unit 140, converted into carbonate, and only a portion of CO ₂ is removed and regenerated by the filter 143. By supplying the ammonia water to the absorption liquid circulation line (A), the absorption liquid having a high OH ⁻ concentration and a low HCO ₃ ⁻ concentration may be supplied to maintain the CO ₂ absorption rate.

Accordingly, by taking only a portion of the absorbent liquid used for collecting CO ₂ and removing the absorbed CO ₂ , the size of the apparatus of the absorbent regeneration unit 140 and the absorbent liquid circulation unit 150 is kept small and continuous operation is possible, and the marine engine It is possible to flexibly cope with the CO ₂ absorption rate according to the load change in (10).

Next, as shown in FIG. 7 , the steam generating unit 160 receives a mixture of steam and saturated water heat-exchanged through the EGE 134 to receive a steam drum (not shown). The auxiliary boiler 161 for separating steam and supplying it to the steam consuming place, the boiler water circulating water pump 162 for circulating and supplying boiler water from the auxiliary boiler 161 to the EGE 134, and consumption from the steam consuming place A cascade tank 163 for recovering condensed water that is condensed after being condensed and a phase changed condensate, and a supply pump 164 and a control valve for controlling and supplying the amount of boiler water from the cascade tank 163 to the auxiliary boiler 161 Consist of (165), it generates and supplies the necessary steam to the heating equipment in the ship.

Here, when the load of the ship engine 10 is large, the amount of heat that can be provided from the exhaust gas is high, so that the amount of steam required in the ship can be sufficiently produced through the EGE 134, but if not, the auxiliary boiler 161 itself The fuel can be burned to produce the required steam.

Next, the discharge unit 170, as shown in Figure 7, the washing water tank 171 for storing the washing water discharged from the absorption tower 130, from the washing water tank 171 to the transfer pump 172 A water treatment device 173 having a filtering unit for controlling turbidity to meet the conditions for outboard discharge of the washing water transported by the vehicle and a neutralizing agent injection unit for pH adjustment, and a sludge storage tank for separating and storing solid discharges such as chute ( 174), the washing water passing the water treatment device 173 and meeting the overboard discharge condition is discharged overboard, and the solid discharge such as a chute that does not meet the overboard discharge condition is separately stored in the sludge storage tank 174 can be kept

On the other hand, NaOH may be exemplified as a neutralizing agent for satisfying the overboard discharge condition, but it is possible to neutralize these acidic or basic properties, respectively, as needed, assuming that the material discharged from the absorption tower 130 is acidic or basic. A neutralizing agent may be selected and used.

Therefore, in the ammonia carrier that transports liquefied ammonia by sea, liquefied ammonia is used to manufacture and supply the greenhouse gas absorbent, and NOx contained in ship exhaust gas according to IMO's Convention on the Prevention of Marine Pollution (Marpol 73/78) Annex VI and 80% or more of NOx emission reduction, which is the standard IMO Tier III with stricter SOx emission restrictions.

Therefore, by the configuration of the greenhouse gas emission reduction device of the ammonia carrier as described above, the boil-off gas from the liquefied ammonia stored in the cargo hold of the ammonia carrier or the vaporized gas obtained by vaporizing the liquefied ammonia is converted into a CO ₂ absorption liquid, and CO ₂ is collected By taking only a portion of the absorption liquid used at the time of operation to remove the absorbed CO ₂ , the size of the apparatus of the absorption liquid regeneration part and the absorption liquid circulation part is kept small, continuous operation is possible, and it is designed to flexibly cope with the CO ₂ absorption rate according to the load change of the ship engine. can, and overcome the back pressure limitation of the absorption tower to install it on a ship that cannot install the existing absorption tower, to optimize the size of the absorption tower to overcome the limitations _of the diameter or height of the installation space, and to By constructing a storage tank for storing and supplying an aqueous solution of divalent metal hydroxide for the regeneration of the absorbent in the engine casing, it can be used without affecting the space of the existing engine casing area, thereby solving the installation space problem. By configuring the storage tank that stores and supplies the aqueous hydroxide solution in the form of a silo so that it can be supplied to the mixing tank by its own weight, it is possible to eliminate or minimize ancillary equipment necessary for supply to the mixing tank, and to supply a high-concentration absorption liquid to the greenhouse It can prevent the deterioration of gas absorption performance, and apply a pressurization system to prevent absorption liquid loss due to natural evaporation of high-concentration absorbent liquid, and natural carbonate form that does not affect the environment to meet IMO greenhouse gas emission regulations It is converted to and discharged separately or converted into useful substances and stored, and by regenerating NH ₃ , consumption of relatively expensive NH ₃ can be minimized, the capacity size of the rear end of the filter can be reduced, and the remaining SO _X during NH ₃ regeneration By removing the side reaction, it is possible to minimize the loss of NH ₃ and to prevent impurities from being included in the recovery of ammonia.

The embodiments described in this specification and the configurations shown in the drawings are only the most preferred embodiment of the present invention, and do not represent all of the technical spirit of the present invention, so various equivalents that can replace them at the time of the present application It should be understood that there may be water and variations.

100: liquefied ammonia storage tank 102: vaporizer
103: switching valve 110: seawater supply part
111: sea water pump 112: sea water control valve
120: absorbent liquid production unit 121: fresh water control valve
122: NH ₃ storage 123: ammonia water tank
124: pH sensor 125: ammonia water supply pump
130: absorption tower 131: CO ₂ removal unit
132: SOx absorption part 133: NOx absorption part
134: EGE 135: main exhaust engine
136: Bypass Hall 1 137: Bypass Hall 2
138: 3rd bypass hall 139: ventilation means
140: absorption liquid regeneration unit 141: storage tank
142: mixing tank 143: filter
150: absorption liquid circulation unit 151: ammonia water circulation pump
152: pH sensor 160: steam generator
161: auxiliary boiler 162: boiler water circulating water pump
163: cascade tank 164: supply pump
165: control valve 170: discharge part
171: washing water tank 172: transfer pump
173: water treatment device 174: sludge storage tank

Claims (35)

A liquefied ammonia storage tank for storing liquefied ammonia;
Seawater supply unit for supplying seawater;
an absorption liquid production unit for receiving ammonia from the liquefied ammonia storage tank and manufacturing and supplying a high-concentration CO ₂ absorption liquid;
The exhaust gas discharged from the marine engine of the engine room is cooled by reacting with the seawater supplied from the seawater supply unit, and the cooled exhaust gas and the absorption liquid from the absorption liquid production unit are reacted to convert CO ₂ into an aqueous ammonium salt solution to CO ₂ CO ₂ removal unit formed to remove the absorption tower;
an absorption liquid regeneration unit for regenerating the absorption liquid and NH ₃ by reacting the aqueous ammonium salt solution discharged from the absorption tower with an aqueous solution of divalent metal hydroxide, circulating and supplying the absorption liquid to the absorption tower to be reused as an absorption liquid; and
An absorption liquid circulation unit circulating a portion of the ammonium salt aqueous solution or unreacted absorption liquid discharged from the lower end of the absorption tower to the upper portion of the absorption tower through an absorption liquid circulation line; Containing,
A device for reducing greenhouse gas emissions of ammonia carriers. The method of claim 1,
The absorbent liquid production unit,
Fresh water tank for storing fresh water;
a fresh water control valve for supplying fresh water from the fresh water tank;
an ammonia water tank for preparing and storing ammonia supplied from the liquefied ammonia storage tank to the fresh water supplied by the fresh water control valve to produce and store high-concentration ammonia water as an absorption liquid;
a pH sensor for measuring the ammonia water concentration in the ammonia water tank; and
An ammonia water supply pump for supplying ammonia water from the ammonia water tank to the absorption liquid circulation part; characterized in that it comprises,
A device for reducing greenhouse gas emissions of ammonia carriers. 3. The method of claim 2,
characterized in that the boil-off gas from the liquefied ammonia storage tank is supplied to the ammonia water tank,
A device for reducing greenhouse gas emissions of ammonia carriers. 3. The method of claim 2,
Characterized in that the liquefied ammonia from the liquefied ammonia storage tank is vaporized through a vaporizer and supplied to the ammonia water tank,
A device for reducing greenhouse gas emissions of ammonia carriers. 3. The method of claim 2,
The absorbent liquid production unit further includes an NH ₃ storage for storing NH ₃ (g) of high pressure, and injects the boil-off gas from the liquefied ammonia storage tank into the NH ₃ storage, and from the NH ₃ storage to the ammonia water tank. Characterized in supplying NH ₃ (g),
A device for reducing greenhouse gas emissions of ammonia carriers. 3. The method of claim 2,
The absorbent liquid preparation unit further includes an NH ₃ storage for storing NH ₃ (g) of high pressure, and vaporizes liquefied ammonia from the liquefied ammonia storage tank through a vaporizer to put it into the NH ₃ storage, and from the NH ₃ storage Characterized in supplying the NH ₃ (g) to the ammonia water tank,
A device for reducing greenhouse gas emissions of ammonia carriers. 3. The method of claim 2,
It is characterized in that by injecting compressed air of a certain pressure into the ammonia water tank to prevent evaporation loss of NH ₃ ,
A device for reducing greenhouse gas emissions of ammonia carriers. The method of claim 1,
The absorption tower is
At least a part of the exhaust gas discharged from the marine engine of the engine room is branched to react with the seawater supplied from the seawater supply unit to cool, and the cooled exhaust gas and the absorption liquid from the absorption liquid production unit react to react to convert CO ₂ to an ammonium salt It is characterized in that the CO ₂ removal unit is formed to remove the CO ₂ by converting to an aqueous solution,
A device for reducing greenhouse gas emissions of ammonia carriers. 9. The method of claim 8,
It characterized in that it comprises a blowing means for supplying at least a portion of the branched exhaust gas to the CO ₂ removal unit,
A device for reducing greenhouse gas emissions of ammonia carriers. 10. The method of claim 9,
The blowing means is characterized in that the blower,
A device for reducing greenhouse gas emissions of ammonia carriers. 9. The method of claim 8,
Of the exhaust gas discharged from the marine engine, the residual exhaust gas that is not branched to the CO ₂ removal unit is discharged through the main exhaust pipe,
The at least a portion of the exhaust gas branched to the CO ₂ removal unit is discharged by being joined to the main exhaust pipe after the CO ₂ is removed, or characterized in that it is discharged through a separate discharge pipe,
A device for reducing greenhouse gas emissions of ammonia carriers. The method of claim 1,
The CO ₂ removal unit is characterized in that it is installed inside the engine casing above the engine room,
A device for reducing greenhouse gas emissions of ammonia carriers. 13. The method of claim 12,
The absorbent liquid regeneration unit,
A storage tank installed in the form of a silo to store and supply an aqueous solution of divalent metal hydroxide;
A mixing tank formed in the lower part of the storage tank and stirred with an agitator for an aqueous solution of ammonium salt discharged from the absorption tower and an aqueous solution of divalent metal hydroxide supplied by its own weight from the storage tank to produce NH ₃ (g) and carbonate Wow,
Characterized in that it comprises a filter for separating the carbonate by sucking the solution and the precipitate from the mixing tank,
A device for reducing greenhouse gas emissions of ammonia carriers. 14. The method of claim 13,
A storage tank for storing and supplying the divalent metal hydroxide aqueous solution is disposed on the inner side of the engine casing,
The mixing tank is formed in the lower part of the storage tank, characterized in that it is disposed on the inner side of the engine casing,
A device for reducing greenhouse gas emissions of ammonia carriers. 14. The method of claim 13,
A storage tank for storing and supplying the divalent metal hydroxide aqueous solution is disposed on the inner side of the engine casing,
The mixing tank is characterized in that it is disposed in the engine room under the engine casing,
A device for reducing greenhouse gas emissions of ammonia carriers. 14. The method of claim 13,
The storage tank for storing and supplying the divalent metal hydroxide aqueous solution is characterized in that it is disposed on the outer surface of the engine casing,
A device for reducing greenhouse gas emissions of ammonia carriers. The method of claim 1,
The absorption liquid circulation unit comprises an ammonia water circulation pump that circulates a portion of the ammonium salt aqueous solution or unreacted absorption liquid through the absorption liquid circulation line, and a pH sensor for measuring the concentration of the absorption liquid supplied to the upper end of the absorption tower,
A device for reducing greenhouse gas emissions of ammonia carriers. The method of claim 1,
The absorption liquid regeneration unit includes a storage tank for storing an aqueous solution of divalent metal hydroxide, and a mixing tank for generating NH ₃ (g) and carbonate by stirring the aqueous solution of ammonium salt and aqueous solution of divalent metal hydroxide discharged from the absorption tower with a stirrer; , characterized in that it comprises a filter for separating the carbonate by sucking the solution and the precipitate from the mixing tank,
A device for reducing greenhouse gas emissions of ammonia carriers. 19. The method of claim 18,
NH ₃ (g) generated by the mixing tank is supplied to the absorption tower, or the absorption liquid separated by the filter is supplied to the absorption liquid circulation unit,
A device for reducing greenhouse gas emissions of ammonia carriers. 19. The method of claim 18,
The divalent metal hydroxide aqueous solution stored in the storage tank is Ca(OH) ₂ or Mg(OH) ₂ generated by reacting fresh water with CaO or MgO, characterized in that
A device for reducing greenhouse gas emissions of ammonia carriers. 19. The method of claim 18,
The ammonia water or fresh water separated by the filter is supplied to the absorption liquid manufacturing unit, or the surplus fresh water additionally generated by the mixing tank compared to the total circulation fresh water is stored in the fresh water tank and recycled when the divalent metal hydroxide aqueous solution is generated in the storage tank. characterized in that
A device for reducing greenhouse gas emissions of ammonia carriers. The method of claim 1,
The absorption tower further comprises an SOx absorption unit for dissolving and removing SOx while cooling by reacting the exhaust gas discharged from the marine engine with the seawater supplied from the seawater supply unit,
The CO ₂ removal unit reacts with the exhaust gas from which the SOx is removed and the seawater supplied from the seawater supply unit to cool, and by reacting the cooled exhaust gas with the absorption liquid from the absorption liquid preparation unit to convert CO ₂ into an aqueous ammonium salt solution. Characterized in removing CO ₂ ,
A device for reducing greenhouse gas emissions of ammonia carriers. The method of claim 1,
The absorption tower further includes a NOx absorption unit for absorbing and removing NOx of the exhaust gas discharged from the marine engine, and the exhaust gas from which the NOx is removed is cooled by reacting with seawater supplied from the seawater supply unit, and the cooled Characterized in that by reacting the exhaust gas and the absorption liquid from the absorption liquid production unit to convert CO ₂ into an aqueous ammonium salt solution to remove CO ₂ ,
A device for reducing greenhouse gas emissions of ammonia carriers. The method of claim 1,
The absorption tower includes a NO _X absorbing part that absorbs and removes NO _X of the exhaust gas discharged from the marine engine, and the exhaust gas from which the NO _X is removed reacts with seawater supplied from the seawater supply unit to cool the SO _X The SO _X absorption unit for dissolving and removing the SO X and the CO ₂ removal unit for removing the CO _{2 by converting the CO 2 into} an aqueous ammonium salt solution by reacting the exhaust gas from which the SO _X has been removed and the absorption liquid from the absorption liquid preparation unit are sequentially removed characterized in that it is laminated,
A device for reducing greenhouse gas emissions of ammonia carriers. 25. The method of claim 23 or 24,
NH ₃ regenerated by the absorption liquid regeneration unit is supplied to the NO _X absorption unit,
The NO _X absorbing part absorbs NO _X as NH ₃ or absorbs NO _X by using urea water,
A device for reducing greenhouse gas emissions of ammonia carriers. 25. The method of claim 22 or 24,
The seawater supply unit,
A seawater pump that receives seawater from the outboard through the sea chest and pumps it to the SO _{X absorption unit, and a seawater control valve that controls the injection amount of seawater supplied from the seawater pump to the SO X absorption} unit according to the amount of exhaust gas. characterized in that
A device for reducing greenhouse gas emissions of ammonia carriers. 25. The method of claim 22 or 24,
The SO _X absorption unit,
a multi-stage seawater spray nozzle for spraying the seawater supplied from the seawater supply unit downwardly; and
It characterized in that it comprises a; bulkhead-shaped exhaust gas inlet pipe or an umbrella-shaped blocking plate that covers the exhaust gas inlet pipe to prevent the washing water from flowing backward.
A device for reducing greenhouse gas emissions of ammonia carriers. 28. The method of claim 27,
In the lower part of the seawater injection nozzle, a porous upper plate having a flow path through which the exhaust gas passes is formed in multiple stages, characterized in that the seawater and the exhaust gas are in contact with each other,
A device for reducing greenhouse gas emissions of ammonia carriers. 28. The method of claim 27,
An absorption tower filled with a filler to allow seawater and exhaust gas to contact is formed under the seawater injection nozzle, characterized in that the seawater dissolves SO _X ,
A device for reducing greenhouse gas emissions of ammonia carriers. 28. The method of claim 27,
Characterized in that the neutralizing agent is added to the seawater supplied to the SO _X absorption unit,
A device for reducing greenhouse gas emissions of ammonia carriers. The method of claim 1,
The CO ₂ removal unit,
an ammonia water spray nozzle for spraying the absorbent liquid downward;
A filler for converting CO ₂ into NH ₄ HCO ₃ (aq) by contacting CO ₂ with ammonia water as an absorption liquid;
a cooling jacket formed in multiple stages for each section of the absorption tower filled with the filler to cool the heat generated by the CO ₂ removal reaction;
Water spray collecting NH ₃ discharged to the outside without reacting with CO ₂ ;
Mist removal plate formed in a curved multi-plate shape to return ammonia water in the direction of the filler;
barrier ribs formed so that ammonia water does not flow back; and
It characterized in that it comprises a; umbrella-shaped blocking plate covering the exhaust gas inlet hole surrounded by the partition wall.
A device for reducing greenhouse gas emissions of ammonia carriers. 32. The method of claim 31,
The filler is composed of a multi-stage distillation column packing designed to have a large contact area per unit volume,
characterized in that a solution redistributor is formed between the distillation column packings,
A device for reducing greenhouse gas emissions of ammonia carriers. 25. The method of claim 24,
The absorption tower is
It is formed between the NO _X absorbing part and the SO _x absorbing part, characterized in that it further comprises an EGE for exchanging the waste heat of the marine engine with the boiler water,
A device for reducing greenhouse gas emissions of ammonia carriers. 34. The method of claim 33,
An auxiliary boiler for receiving a mixture of heat-exchanged steam and saturated water, separating the steam and supplying it to a steam consuming place, a boiler water circulation water pump circulating and supplying boiler water from the auxiliary boiler to the EGE, and from the steam consuming place A cascade tank for recovering the condensed condensate, and a steam generator including a supply pump and a control valve for controlling and supplying the amount of boiler water from the cascade tank to the auxiliary boiler, characterized in that it further comprises a steam generator,
A device for reducing greenhouse gas emissions of ammonia carriers. The method of claim 1,
A washing water tank for storing the washing water discharged from the absorption tower, a filtering unit for adjusting turbidity to meet the overboard discharge condition of the washing water transferred to the washing water tank by a transfer pump, and a neutralizing agent injection unit for pH control A water treatment device having a water treatment device, and a sludge storage tank for separately storing the solid waste, characterized in that it further comprises a discharge unit,
A device for reducing greenhouse gas emissions of ammonia carriers.

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