WO2014092510A1

WO2014092510A1 - Temperature and pressure swing moving bed adsorption process system using novel heat exchange system

Info

Publication number: WO2014092510A1
Application number: PCT/KR2013/011614
Authority: WO
Inventors: 이광순; 손용호; 김기웅
Original assignee: 서강대학교 산학협력단
Priority date: 2012-12-14
Filing date: 2013-12-13
Publication date: 2014-06-19
Also published as: KR20140077465A; KR101442673B1

Abstract

The present invention relates to an adsorption system for selective gas isolation, which uses a phased desorption and a novel heat exchange system. The adsorption system comprises: an adsorption bed; a blower for injecting a mixture gas; a transfer device for transferring an adsorbent; a high-temperature desorption bed which desorbs adsorbates a first time and which is arranged above the adsorption bed; a desorption bed for desorbing adsorbates a second time; a reflux pipe for moving adsorbent powder to the adsorption bed; and a heat exchange system for raising the temperature of the high-temperature desorption bed, wherein the temperature of the high-temperature desorption bed is the same as the pressure (PA) of the adsorption bed, the pressure (PD) of the desorption bed is maintained lower than that of the adsorption bed and the temperature (TD) of the desorption bed is maintained higher than that of the adsorption bed, and backflow of a portion of the gas caused by the pressure difference in the reflux pipe is prevented by adjusting the size of the particle of the adsorbent and/or the diameter and length of the reflex pipe.

Description

【Specification】

[Name of invention]

Temperature Pressure Fluctuation Mobile Phase Adsorption Process System Using New Heat Exchanger System

Technical Field

The present invention relates to a specific gas adsorption process system, and more particularly, to the adsorption and stepwise high temperature-low pressure desorption in a different temperature and pressure environment, and a heat exchange system that can improve the adsorption performance and economic optimization, The invention relates to a mobile bed temperature pressure ^ copper adsorption process system for the separation and circulation of adsorbents into a mobile bed for selective gas separation.

Background Art

The adsorption step is a step of separating the gas or liquid by equilibrium adsorption to the adsorbent for each component, and has been particularly applied to separation and purification of gas. Typical examples include separation and concentration of air vaporization oxygen, high-purity hydrogen separation in petrochemical plants, separation of normal paraffins and isoguaraffins, separation of methane in anaerobic fermentation gases, and removal or separation of volatile organic compounds in industrial environments. Belongs. In particular, the adsorption process has recently been studied for the purpose of recovering carbon dioxide, which is a major cause of global warming, from the combustion exhaust fl of large industrial processes such as power plants and steel mills.

Adsorbents used for gas separation include zeolite, molecular sieve, activated carbon, ^' carbon molecular sieve, silica gel, activated alumina, etc., and the adsorption process is due to the many pores. (Van der Waals) Most of them use physical adsorption to attach force as a binding force. This is because physical adsorption may have a smaller amount of adsorption than chemical adsorption, but the bonding force is relatively low, so that desorption is easy.

1 is a graph showing the relationship between the amount of gas adsorbed on an adsorbent and a partial pressure of one component of a general mixed gas by adsorption isotherm. As shown in Fig. 1, the physical adsorption amount of a gas component increases as the partial pressure of the gas component increases. The lower the temperature increases, the adsorptive separation process is constructed using this principle.

Gas separation using adsorption has traditionally been the most commonly used pressure swing adsorption (PSA) method. Basically, this process is to separate and purify the pressurization, high pressure adsorption, depressurization discharge, decompression washing, or modified operation in a single cycle in a single cycle. On the other hand, TSA (Temperature Swing Adsorption) method, which is used to balance the adsorption of equilibrium adsorption, is often used, and the combined Pressure Temperature Swing Adsorption (PTSA) method is used. They are all operated in such a way that the adsorption and desorption steps are repeated periodically, and the desorbed components and components are recovered and commercialized as necessary.

In the recovery of V0C, a lot of temperature swing adsorption process (TSA) using a mobile phase is used (see FIG. 2). It is similar to the mobile bed temperature pressure fluctuation adsorption process of the present invention in the concept of a mobile phase, but the pressure of the adsorption unit and the desorption unit is the same by using one bed, which has the disadvantage of receiving the efficiency of adsorption and desorption.

Looking at the temperature swing adsorption (TSA) process, as shown in Figure 1, the adsorption at the temperature (T _L , q _ads ) at a constant pressure, heating the bed to (T _H , q _des ) The method of desorption by means of temperature variation absorption. In the variable temperature adsorption process, the most convenient way to increase the temperature is to purify the adsorbent with preheated gas or to increase or decrease the temperature of the adsorbent in a short time. This method is also employed in the removal of volatile organic components using carbon.

And, the silver fluctuation adsorption process takes ί beds and repeats the adsorption (glass at low temperature) and desorption (glass at high temperature) within one minute and at short intervals. It is very difficult to change the temperature in cycles. In addition, heating and cooling the temperature of a bed with a large thermal mass in a short time is expensive.

Looking at the pressure swing adsorption (PSA) process, as shown in Figure 1, as shown in Figure 1, the pressure is applied at low pressure (P _H , q _ads ) without applying heat, The method of desorption by depressurizing to (PL qdes) is pressure fluctuation adhesion. Compared to temperature swing adsorption, the cycle time of pressure swing adsorption is usually short, up to a few minutes or seconds because of the rapid pressure reduction, and the basic steps constituting the pressure swing adsorption process are raw material pressurization, adsorption, decompression and washing (see FIG. 2). ) To increase the efficiency of the process, new steps such as product pressurization, cocurrent depressurization, pressure equalization, vacuum desorption, and strong adsorbate purification steps were added, and most pressure swing adsorption processes now consist of a combination of these steps. However, the pressure swing adsorption is in a constant dynamic state because several modes of operation are switched in series, resulting in severe gas flow changes. As a result, the operating points of gas pumps such as blowers, compressors and vacuum pumps cannot be fixed in the high-efficiency area and move between low-efficiency and high-efficiency areas. In the case of a process, it can be a big burden on the operating cost.

In the conventional pressure swing adsorption process, the flow rate flowing into the bed is proportional to the difference between the pressure at the bed inlet and the pressure inside the bed. When the gas is pressurized by blowing gas into the bed for adsorption, the gas flows at a high flow rate because the pressure of the bed is low at first, but as the pressure of the bed increases over time, the flow of gas into the bed becomes smaller and smaller. You lose. This causes the operating conditions of the pump to be changed over time.

When degassing the gas from the bed through the Jingu pump for desorption, there is a lot of gas. The amount of gas flowing out of the bed decreases as time passes and the pressure of the bed decreases. ^Therefore, due to: the pump becomes the driving conditions depending on the time driving. In addition, the efficiency of the pump varies depending on the operating conditions. Therefore, when the operating conditions are changed as in the adsorption and desorption process described above, it is difficult to always operate the pump at maximum efficiency, which consumes a lot of operating costs.

In the operating cost of the process, the pump power required for the joining (or depressurization) takes up the majority, so the disadvantages described above result in high operating costs. 3 is a process flow diagram of a conventional seven-component fluidized bed adsorption system. The apparatus is composed of a chest part, a detachable part, an activated carbon conveyance part, a solvent separation part, and the like. The adsorption part is a multi-stage porous plate, which is composed of a flow part and a bottom part of activated carbon. Activated carbon forms a fluidized bed on the porous plate by the solvent-containing gas rising from the bottom to adsorb the solvent. And activated carbon is removed from the lower part to the lower perforated plate in an amount equal to the circulation amount. The detachable part mainly uses a multi-tube heat exchange system.

The activated carbon flowing down from the adsorption unit contacts the desorption gas underneath the tube being heated in the heat exchange system. Desorption gas is discharged from the upper part of the desorption part containing the desorbed solvent to the solvent separation part. On the other hand, the activated carbon from which the solvent has been desorbed is conveyed to the porous plate at the uppermost end of the adsorption unit through the air flow conveying pipe at the lower part of the desorbing unit. Through the same process, activated carbon undergoes continuous circulation and repeats adsorption and desorption.

The most feature of this device is that the adsorption unit and the desorption unit are separated in one bed, and because the indirect heating desorption method allows the selection of desorption gas such as water vapor, air, nitrogen, etc. There is a disadvantage of operating under the same pressure.

In addition, the conventional adsorption process system is required to increase the flow rate of the water flow into the adsorption bed is required to increase the flow rate, but to increase the flow rate, but in order to increase the economic efficiency or optimization, Since the temperature must be high, there is a problem in that the flow rate of the coolant flowing into the suction seed must be reduced.

[Detailed Description of the Invention]

[Ki: artistic problem]

The problem of the present invention for solving and solving the above problems is first, the adsorption process is a continuous ^' process, it is possible to operate continuously in a fixed condition of the gas pumps, each pump ^ to the operating conditions to the maximum efficiency It is possible to operate, and to achieve the operation and energy savings through this, secondly, to achieve higher productivity in the same size device, and thirdly, to the pressure fluctuation, temperature to the desired conditions Fourth, to increase the operating efficiency of the system and pump, to reduce operating costs, and to improve the separation and recovery of the mixed gas. It is to achieve the adsorption performance and economic optimization at the same time by enabling saving and low cost operation.

In addition, it is intended to be used for the separation of various kinds of gas mixtures, and to provide a process system that is particularly useful for one-stage concentration processes for separating gases in large quantities, such as carbon dioxide recovery from combustion exhaust gases. .

Technical Solution

The first feature of the present invention for solving the above problems is an adsorption bed for selectively adsorbing the mixed gas introduced; A blower mounted at a lower portion of the adsorptive bed to pressurize a mixed gas mixture; A transporting device for transporting the adsorbent that has come out from the lower portion of the adsorption bed; Heating the adsorbent and flows are transported in the transport ^device, and to desorb the adsorbate primarily, a high temperature desorption ssedeu positioned upper than the adsorption bed; A desorption bed to which the adsorbent powder desorbed from the high temperature desorption bed is moved to desorb the adsorbate secondly; A reflux tube for moving the adsorbent powder desorbed from the desorption bed to the hopsick bed; And injecting and removing water from the lower end of the adsorption bed, separating the water from the outlet, and separating the separated water from the lower part of the suction bed. It includes a heat exchange system for heating the angle of exit from the lower ^ ^ to flow into the high temperature desorption bed to increase the temperature of the silver desorption bed, the high temperature desorption bed is equal to the pressure (P _A ) of the adsorption bed, The desorption bed maintains a lower pressure (P _D ) and a higher temperature (T _D ) than the adsorption bed, and the size of the adsorbent particles, the size of the reflux tube. And by adjusting at least one of the lengths, to prevent backflow of some of the gases generated by the pressure difference in the reflux tube.

Here, the heat exchange system, the cooling water is hydraulically heated to the lower portion of the lower end of the adsorption bed, and the first fin angle which separates a portion of the outlet angle is separated into the upper portion of the lower end of the adsorption bed to remove the fourth fin. Angle A first heat exchanger that heats and flows into the high temperature desorption bed to raise the temperature of the desorption bed; It is preferable that the second heat exchanger is configured to increase the temperature of the removable bed by introducing the removable bed.

In addition, preferably, the third cooling water and the fourth cooling water exiting from the adsorption bed and introduced into the high temperature desorption bed may be heated by at least one steam heater installed in each flow path, and heat the third cooling water. The steam heater may include a steam heater using waste gas discharged on the upper end of the adsorption bed. And a second feature of the present invention is a compressor (compressor) is mounted to the lower portion of the adsorption bed to compress and inject the mixed gas; A transfer device for transferring the adsorbent flowing out from the lower portion of the adsorption bed; A high temperature desorption bed disposed on the upper side of the adsorptive bed to desorb the adsorbate first by heating the adsorbent adsorbed by the transfer device; An adsorbent powder desorbed from the high temperature desorption bed to desorb the adsorbent secondary, and a desorption bed positioned above the adsorption bed; The degreaser; a reflux tube for moving the adsorbent powder desorbed from the bed to the adsorption bed; And removing the coolant from the lower part of the adsorption bed by removing the coolant from the lower part of the adsorption bed and removing the cooling water from the lower part of the adsorption bed. by heating the gaksu and entering the ^"high temperature desorption bed comprising: a heat exchange system to increase the temperature of the high temperature desorption bed, the high temperature desorption bed is equal to the pressure (P _a) of the adsorption bed and the desorption beds are the Maintain a low pressure (P _D ) and a high temperature (T _D ) relative to the adsorptive bed, which is caused by the pressure difference in the reflux tube through the adjustment of at least one of the size of the adsorbent particles, the diameter and the length of the reflux tube. Backflow of some of the gas being prevented.

Here, the heat exchange system, the first 넁 angle water is introduced into the upper portion of the lower end of the adsorption bed to remove the cooling water flows into the lower portion of the lower end of the adsorption bed and separated from the cooling water, the fourth heat exchanger Angle The first heat exchanger for heating and desorbing the high temperature desorption bed to increase the temperature of the desorption bed, and the low 12 cooling water which is partially separated from the water discharged from the lower end of the adsorption bed are discharged. It is preferable that the second heat exchanger is configured to increase the temperature of the removable bed by introducing the removable bed.

In addition, preferably, the third cooling water and the fourth cooling water exiting from the adsorption bed and flowing into the high temperature desorption bed may be heated by at least one steam heater installed in each flow path, and heat the third cooling water. The steam heater may include a steam heater using waste gas discharged from the upper end of the adsorption bed.

Advantageous Effects

In this manner, by providing the invention, it is possible to increase the operating efficiency of the system by using the stepwise desorption and to improve the separation and recovery efficiency of the gas mixture. And, since it is possible to operate under the fixed fixed condition and continuous operation, it is possible to obtain higher productivity than other size separators of the same size, and it is possible to operate the pressure fluctuation and temperature fluctuation with the desired operation. By using heat exchange system, energy saving in each stage is possible and low cost operation is possible so that efficient operation is possible to achieve energy saving and improve adsorption performance and economic efficiency.

In addition, it can be used for the separation of various kinds of gas mixtures, and is particularly useful in the one-stage concentration process for separating gases in large quantities such as, for example, recovering carbon oxides from a flue gas.

In addition, the process of the present invention can replace and supplement the pressure swing adsorption process, which is currently widely used gas adhesion separation process, drying of gas, recovery of hydrogen from steam reforming gas, oxygen from air Separation of Nitrogen: in the separation of various gas mixtures such as recovery of argon from ammonia scrubbing gas, recovery of CO from steel mill exhaust gas, recovery of CH ₄ and CO ₂ from landfill gas, It is possible to operate and continuous operation, so that higher productivity and higher than other gas separators of the same standard Quality products can be obtained and pressure fluctuations and temperature fluctuations can be achieved under the desired conditions.

In particular, in the conventional two-stage pressure fluctuation deposition process used to separate and recover carbon dioxide from a flue gas having a low partial pressure of carbon dioxide, it can be said to be particularly useful for the one-stage diffusion carbon enrichment process, which accounts for 70% of the energy consumption. . As such, the present invention provides an opportunity for research into a wide variety of studies, such as absorption technology, adsorption bed, membrane separation technology, etc., in the present study, which is mainly focused on absorption technology in relation to carbon dioxide reduction, separation, and recovery. Ultimately, this will be an opportunity to further develop the current ^ suction separation technology.

[Brief Description of Drawings]

1 shows an adsorption isotherm showing the relationship between the partial pressure of a gas component and the amount adsorbed.

2 is a conventional pressure _; Process flow chart of variable adsorption process,

3 is a process flow diagram of a conventional improved fluidized bed adsorption device,

4 is a view illustrating a configuration of a temperature pressure mobile phase swing adsorption process system according to an embodiment of the present invention,

Figure 5 is a schematic diagram of the cooling water flow of the new heat exchange method of the temperature pressure mobile phase fluctuation process system according to an embodiment of the present invention,

6 is a view showing a temperature gradient of the heat exchange system structure of the temperature pressure mobile phase variable adsorption process system according to the present invention and an embodiment,

7 is a view showing the temperature change of the cooling water through the heat exchange system design of the temperature pressure mobile phase fluctuation adsorption process system according to an embodiment of the present invention obtained through a computer simulation simulator, and the 넁 angular temperature change of the conventional heat exchange system design,

8 is a graph showing a curve of adsorption amount according to temperature and pressure fluctuations, and FIG. 9 is a graph showing heat required for process angle / heating during heat exchange of a system according to the present invention.

10 is a view illustrating a configuration of a temperature pressure mobile phase swing adsorption process system according to another embodiment of the present invention. FIG. 11 is a flowchart of a gas mixture and an adsorbent in a mobile phase temperature pressure swing adsorption process in operation of the adsorption and desorption process system using the staged desorption illustrated in FIGS. 4 and 10.

[Best form for implementation of the invention]

4 and 10 are views illustrating a configuration of a temperature pressure mobile phase variable adsorption process system according to an exemplary embodiment of the present invention, and FIG. 4 illustrates an example of a process system for adsorbing at atmospheric pressure and desorption at low pressure. 10 illustrates a process system for adsorbing at high pressure and desorption at normal pressure. In the case of a heat exchange system. It is an example of a system having a heat exchange system in the same manner as in FIG. 4 and FIG. 10, but having internal water circulating in itself and supplying only necessary heat from the outside. In order to separate the material with high purity, adsorption and desorption have to be made smoothly, and for this purpose, it has been conceived that the pressure during adsorption must be higher than the pressure during desorption.

As shown in Fig. 4, the temperature pressure mobile phase variable adsorption process system according to the embodiment of the present invention comprises: an adsorption bed 4 for selectively adsorbing the mixed gas introduced therein; A blower (BlowerXlO) mounted below the adsorption bed 4 to inject the mixed gas; A transporting device (6) for transporting the adsorbent that has been removed from the lower portion of the adsorption bed (4); A high silver desorption bed (30) which desorbs adsorbate primarily by heating the adsorbent transferred and introduced from the conveying device (6), and positioned above the adsorbent bed; Desorption bed (5) to move the adsorbent powder desorbed in the high temperature desorption bed (30) to desorb the adsorbate secondary; A reflux tube (7) for moving the adsorbent powder desorbed from the desorption bed (5) to the adsorption bed (4); And after the cooling water flows into the lower portion of the lower end of the adsorption bed (4), and after separating the pentagonal water discharged, the separated part of the pentagonal water is introduced into the lower upper portion of the adsorption bed, and the upper and lower A heat exchange system (40a, 40b) for heating the pentagonal water exiting from the lower portion and heating it to the high temperature desorption bed to raise the temperature of the high temperature desorption bed, wherein the high temperature desorption bed (30) is the adsorption bed (4). Is equal to the pressure P _A , and the detachable bed 5 has a lower pressure P _D and a higher pressure than the adsorptive bed 4. Maintaining the temperature T _D and preventing the backflow of some gas generated by the pressure difference in the reflux tube 7 by adjusting at least one of the diameter and the length of the reflux tube 7 of the adsorbent particles. It is characterized by.

[Form for implementation of invention]

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.

4 and 10 is a temperature pressure mobile phase swing adsorption process according to an embodiment of the present invention. Figure 4 illustrates the configuration of the system, Figure 4 illustrates a process system for adsorbing all at normal pressure and desorption at low pressure and Figure 10 illustrates a process system for adsorbing at high pressure and desorption at normal pressure. Heat ^! In the case of a ring system, it has a heat exchange system as shown in Figs. 4 and 10, but the cooling water itself is internal. _{In addition,} only the necessary heat is supplied from the outside and the water is circulated _. This is an example of a system for minimizing effluent. It is conceived that adsorption and desorption must be smoothly performed in order to separate materials with high purity, and for this purpose, the pressure at adsorption must be higher than the pressure at desorption.

As shown in Figure 4, the temperature pressure mobile phase fluctuation process system according to an embodiment of the present invention comprises an adsorption bed (4) for selectively adsorbing the incoming mixed gas; A blower (BlowerXlQ) mounted under the adsorption bed (4) to inject the mixed gas; (6) a device for conveying the adsorbent that has come out of the lower part of the adsorption bed (4); A high temperature desorption bed (30) which heats the adsorbent conveyed from the transfer device (6) and desorbs hop adhesion ^ primarily and is located above the adsorption bed; Desorption bed (5) to move the adsorbent powder desorbed in the high temperature desorption bed (30) to desorb the adsorbate secondary; A reflux tube (7) for moving the adsorbent powder desorbed from the desorption bed (5) to the adsorption bed (4); And removing the pentagonal water from the bottom of the adsorption bed (4) and separating the exiting angular water. Heat exchange systems 40a and 40b for heating the angled water exiting the upper and lower portions and heating the negative-temperature beds to increase the temperature of the ^ -desorbable bed It includes, but the high temperature desorption bed (30) is the same as the pressure (P _A ) of the adsorption bed (4), the desorption bed (5) is a lower pressure (P _D ) and higher than the adsorption bed (4) Maintaining a temperature T _D , and through the adjustment of at least one of the size of the adsorbent particles, the diameter and the length of the reflux tube 7, the reverse flow of some gas generated by the pressure difference in the reflux tube 7 It is characterized in that it is prevented.

Here, when the flow rate of the gas mixture, such as the flue gas of the factory, it is very difficult to pressurize all of them and inject it into the adsorption bed (4), as shown in Figure 4 through the blower (blowerXlO) at atmospheric pressure gas mixture Is injected into the adsorption bed, the first recovery in the high temperature desorption bed 30 of the same pressure, and the operation method of recovering the strong adsorbate gas from the desorption bed (5) which is relatively low pressure with the adsorption seed (4) should be selected. .

If the flow rate of the gas mixture to be treated is not large, the gas mixture is pressurized using a compressor (compressorXlO ') as well as the process by the process system illustrated in FIG. 10 as well as the process by the air system illustrated in FIG. _vermiculite: by injecting the bed, it is possible to construct a process in a high-pressure state.

Referring to FIG. 4, the gas mixture 1 is first supplied to the adsorption bed 4 through a blower BlowerXlO, passes through the adsorption bed 4, and a large amount of strong adsorbent is adsorbed on the adsorbent, and then the cyclone ( 11) and the bag filter 12 to remove the dust, it is discharged to the weak adsorbate gas (2).

At this time, the flow rate of the gas in the adsorption bed (4) is good to maintain the initial rate of fluidization, so that the adsorbent flows well under the adsorption bed (4), at the same time so that the adsorbent powder is not mixed too much. The adsorbent that flowed out of the adsorption bed 4 in the state of adsorbing a lot of strongly adsorbents is transferred to the high temperature desorption bed 30 by using the sealed powder transfer device 6 and injected.

Here, the high temperature desorption bed 30 is a device for desorption by applying heat to the adhesive, which is located between the adsorption bed 4 and the desorption bed 5, the cost of maintaining the desorption bed 5 in a vacuum or low pressure, It is a device for staged removal for a feeling of redness. The pressure of the silver desorption bed 30 is equal to the pressure P _A of the adsorption bed 4, and degassing: maintains the same or higher than the temperature T _D of the bed 5. Through this high temperature desorption bed (30) through the primary desorption process, it is possible to reduce the cost of pumping and operation for low pressure or vacuum in the conventional desorption bed, it is possible to increase the C0 ₂ recovery rate through the step-by-step desorption Will be.

That is, as a device for performing a process of recovering the gas such as C02 in the desorption bed (5) after the first recovery through the temperature fluctuation desorption in the high temperature desorption bed (30), all the power of the low pressure pump through the external energy Whereas the heat source required in the high temperature desorption bed 30 can be obtained through the heat exchange system 40 itself in the process, it is possible to provide an efficient system for supplying additional heat source as needed. ^■

Hereinafter, more specifically, as a configuration of the adhesion bonding process system for gas separation according to an embodiment of the present invention, the configuration and operation of the heat exchange system will be described with reference to FIGS. 4 and 10.

In order to simultaneously satisfy the ① adsorption performance and ② economic optimization of the adsorption process of the present invention: In the embodiment of the present invention, the heat exchange of the angles in the adsorption bed (4) is proposed as follows.

(1) Adsorption performance: The adsorption performance is maximized when the desorption of the desorption through the angular water in the adsorption bed (4) is greatly affected by the desorption of the desorption from the adsorption seed (4). (Because the equilibrium adsorption amount is high at low temperature by adsorption isotherm. On the contrary, if the adsorption bed is operated at high temperature without being de-heated by 넁, angle, water, adsorption and performance is not good.)

② Economic optimization: Since the cooling water in the adsorption bed 4 must be heated to the highest temperature in order to maximize the 'heating angle: heat H ring efficiency through water' obtained at the outlet of the adsorption bed 4 described above. ， Make sure the outlet water temperature is maximum. do. (At this time, unlike the assumptions above, the angle of water used for heat exchange is assumed to be in a liquid state, not evaporated at 100 ° C, by mixing materials with high boiling points.) the ^ is nyaeng gaksu be so introduced into the adsorption bed (4) it requires the flow rate is so large and to chumjjok the condition ② is the outlet temperature of the wihaeseongneun nyaeng gaksu higher flows into the adsorption bed ⁽⁴⁾ must use less nyaeng gaksu flow rate . Therefore, the existing heat exchange method Conditions ① and ② at the same time can not be cheungjok and appropriately between the two conditions to determine the ^cooling, can flow.

That is, in order to fundamentally control two conditions, in the present invention, it occurs as a structural problem in which only one variable of the angular water flow rate to be sucked into the adsorption bed is generated. We propose a new heat exchange system and method that can stir two conditions at the same time by introducing a new process design that can add.

However, in the embodiment of the present invention reflects the structure that can control the cooling water flow flowing in the adsorption bed (4) as well as the 넁 Kang existing oil variable to be held in the lower end of the adsorption bed (4).

That is, the heat exchange system, which is one of the configurations of the present invention, is a part in which adsorption occurs intensively by using killing that the adsorption occurs mostly in the lower part of the adsorption bed (4) due to the countercurrent characteristics of gases and solids in the adsorption bed (4). The bottom of the bed) flows a lot of angles: water is used to make a delicate heat removal, and only a part of the heat exchanged water flows from the bottom of the adsorption bed (4) to the top of the suction bed (4). Adjust the temperature to maximize the temperature. (At the same time to optimize adsorption performance and economic efficiency)

Thus, the present invention can realize the adsorption performance and economic volume through the heat exchange system configured to separate the cooling water from the adsorption bed (4) to the two heat ventilation (40a, 40b) (first heat exchanger (40W: bottom lower, 2nd heat exchanger (40a): lower end _< upper part), without separating the angled water, and using the angled water flow control device in the middle of the I. Of course, it is possible to use the giving method.

And, as shown in Figure 4 and 10, in the manner of heat-exchanging the heated cooling water used before entering the high-temperature desorption bed 30, g. Since the heated cooling water must have a temperature corresponding to the operating range for the satisfactory thermal desorption, the angle of heat exchanged in the adsorption bed cannot be thermodynamically matched to the operating temperature. Realize the operating temperature. That is, as the second heat exchanger ('40b), the suction: the angle of inflow into the lower portion of the bottom of the bed (4) is separated into two cooling water streams, and the third angle of water (CWR3) is the top of the adsorption bed (4). After heat exchange by hot waste gas that has been heat-exchanged by the cyclone U and the bag filter 12, it is heated to an operating temperature using the first steam heater HE1, and the second cooling water CRW2, which is the other flow. Is discharged without use for internal heat exchange.

As the first heat bridge 40a, the flow rate of the fourth cooling water CRW4, which is discharged to the upper portion of the lower end of the adsorption bed 4 and exits again, reaches the operating temperature using the second steam heater HE2 (heated 넁) and the third 넁 K (CRW3) of the first heat exchanger heat exchanged to the same temperature is supplied to the high temperature desorption bed (30).

4 and 10. As shown in the figure, the heat exchanger in the previously determined angle water flow rate is exchanged in the adsorption bed sieve section, so that both conditions of the adsorption performance and economic optimization cannot be stratified at the same time. The determined water flow rate (CW) is responsible only for the heat exchange at the bottom of the adsorption bed, and then the heat exchange from the bottom to the top of the adsorption bed is made through the adjusted channel angle flow rate, that is, the first cooling water (CWR1). . In other words, the amount of the maximum power angle (CW) is a variable that controls the adsorption performance condition, and the first angle angle (CWR1) is a variable that causes maximum heat exchange by controlling the temperature of the angle outlet.

Here, as the heat H ventilation 40b, the angle flow flowing into the lower part of the lower end of the adsorption bed 4 and exiting thereafter, followed by 5 minutes, and flowing into the high temperature desorption bed 30 is regarded as approximately 3 angles CWR3. And the residual angle remaining flow is represented by the second angle (CWR2). In addition, as the second heat exchanger 40a, the angle flow flowing into the upper portion of the lower end of the adsorption bed 4 and exiting ¹ represents a crab angle 4 CWR4, and the third cooling water CWR3 and the fourth cooling water ( CWR4) combines and flows into and out of the high temperature desorption bed 30 at 15 ° C ^ (CWR ⁵ ). FIG. 5 is a novel heat exchange method of a temperature pressure mobile phase variable adsorption process system according to an embodiment of the present invention. It is a schematic diagram of the power angle flow of. As shown in FIG. Likewise, the third coolant (CRW3) of the second heat exchanger is heat exchanged by the waste gas heat exchanger system U steam heater (HE1) and then heat exchanged with steam through the third steam heater (HE3) to enter the silver-removable bed. The heated water cooling fourth cooling water CWR4 is exchanged with only the second steam heater HE2 and flows into the high temperature desorption bed. 6 is a view showing a temperature gradient of the heat exchange system structure of the temperature pressure mobile phase change adsorption process system according to an embodiment of the present invention. As shown in FIG. 6, the blue line is a higher temperature change in the adsorption bed (ADBX4) when compared with the existing heat exchange structure (black line) as the temperature change preheated when the heat exchange system proposed in the embodiment of the present invention is used. It can be predicted that the angle of temperature is obtained, thereby confirming that the amount of steam heating required before applying to the high temperature desorption bed (A-DEB) 30 is less than that of conventional heat; The temperature change of the third power angle CWR3 is shown. 7 is a view showing the temperature H, the change in temperature H of the angle through the heat exchange system design of the mobile phase fluctuation adsorption process system according to an embodiment of the present invention obtained through a computer simulation simulator and the temperature of the angle of change of the conventional heat exchange system design to be. Bar "shown in Fig. 7 and the like, the horizontal axis indicates the height of the adsorbent bed (4) and the vertical axis heuphwat represents the temperature of the heat exchanger cooling water in the bed _(4), the first adsorption bed 4 of nyaeng gaksu flow Chu left in the lower The rest of the conditions, including the change of heat exchange system structure was kept constant and the results were obtained. Until the length of the adsorption bed (4) is about 50 cm H, the two design structures have similar temperatures, but afterwards, the proposed design of the thermal bridge / ring system reduces the angle flow rate so that the adsorption bed (4) exits. In the case of the proposed process, the temperature is obtained at 40 ~ 50 ^° C higher than the conventional process. 8 is a graph showing the adsorption amount curve of all on / off pressure change. Degree

As shown in Fig. 8, Η0 represents the temperature and pressure at the outlet of the adsorption bed (4), and in the conventional process, the pressure is reduced from Ρ _Η to P _L using a low pressure pump in the desorption bed (5). Low to obtain the desired desorption amount (H0-> H1 of FIG. 5), in the case of the process of adding the high silver desorption bed 30 according to the present invention by supplying a heat source in the high temperature desorption bed 30 to the temperature T After removing a certain amount by increasing from _L to T _H , use the low pressure pump in the detachable bed (5) to change the operating condition to low pressure and perform the final detachment. In this case, the low pressure required to achieve the desired recovery rate is between P _L and, which in turn can reduce the cost of the low pressure pump itself compared to conventional processes. (Η0->ΗΓ> Η2 in FIG. 5) Also, as shown in FIG. 4, the adsorption bed, the high temperature desorption bed 30 and the desorption bed are newly proposed; By exchanging _{, it is} possible to optimize the process economically by minimizing the supply heat source.

Table 1 shows in-process _. This table shows the required heat ¾ according to the heat capacity and the inlet temperature of each flow.

(AXmin = 15 ^° C, adsorbent specific heat: 0.924J / gK, 120 ^° C exhaust gas ((Χ> 2: Ν ₂ = 0.13: 0.87), specific heat (： 1.0299J / gK, 26 ^° C exhaust gas (C0 ₂ : N Specific heat of ₂ O.13: 0.87): 1.0112J / gK, mass flow of exhaust gas: 167.79ton / hr (120 ^° C 101.3kPa, CO ₂ : N ₂ = 0.13: 0.87), Hop IT mass flow: 360ton / hr) HI corresponds to the adsorbent entering the adsorption bed (4.) from the desorption bed (5), H2 is introduced into the adhesion bed (4) ^ exhaust gas, and C1 is the high temperature desorption bed (30) from the adsorption bed (4) Corresponds to each adsorbent flowing into the. Without heat exchange, the total amount of heat required for cooling and heating corresponds to 85,282,000 kJ / hr, and as shown in FIG. 5, the amount of heat required for each flow or heating can be effectively exchanged through the heat exchanger 20. . Heat required for cooling / heating of the process during heat exchange is shown in FIG. 9. FIG. 9 shows the heat required for the ire angle to be 100 ^° C. The maximum temperature of the angle is approx. to ioo ° c angle; Even considering the amount of heat required, the final heat required for cooling or heating

It can be seen numerically that 62,098,000 kJ / hr is reduced compared to 85,282,000 kJ / hr without heat exchange.

Although there is a difficulty in the heat exchange between the solids, when the heat exchange between the adsorbents is effective: the heat required for cooling / heating is calculated to be 26,077,000 kJ / hr, and as shown in FIG. Through the heat exchange as shown in Figure 4 for minimizing the required coolant flow rate is also possible, in this case, only heating or cooling is required at the local point, the other point can be supplied or removed by circulating inside the water.

This heat exchange method controls the temperature of the adsorption bed 4, the high temperature desorption bed 30 and the desorption bed 5, as shown in Figures 4 and 10, 6) or through a transfer pipe and the adsorbent is introduced into the high temperature desorption bed 30 by raising the silver by the steam heater (s _. Team heater) of the heat exchange system.

Here, the high temperature desorption bed (30), unlike the desorption bed (5), is not a rule through the temperature and pressure ^, but a device that desorbs primarily by applying heat to the adsorbent, the pressure is the same pressure ( P _A ) and the temperature is at least above the detachable bed temperature (T _D ). After desorbing the strong adsorbate such as C0 ₂ primarily from the high temperature desorption bed (30), the resorbent is transferred to the desorption bed (5) through the reflux tube (7). Since the pressure of the high temperature desorption bed 30 is higher than the pressure of the desorption bed, it is possible to induce a natural movement according to the pressure difference, so that the position of the high silver desorption bed 30 is within the range of the pressure difference. You can adjust the height difference. That is, it is possible to selectively position the detachable bed 5 so as to overcome the force due to the gravity difference according to the height difference to move the adsorbent through the reflux pipe (7) with a pressure difference.

The desorption bed 5 maintains a relatively low pressure (P _D ) and a high temperature (T _D ) relative to the adsorption bed (4) so that a significant amount of strongly adsorbents (such as CO ₂ ) in the adsorbent are desorbed. The desorbed gas is removed through the cyclone 14 and the bag filter 15, and then discharged through the gas pump 13, and the desorbed adsorbent powder is gravity-adsorbed along the adsorbent reflux tube 7. Return to (4). FIG. 11 is a flow chart of a gas mixture and an adsorbent in a mobile phase temperature pressure swing adsorption process during operation of the adsorption and desorption process system using the staged desorption illustrated in FIGS. 4 and 10. As shown in FIG. 8, the gas mixture is continuously supplied to the adsorption bed (atmospheric pressure or high pressure, low temperature) 4 through the blower 10 or the compressor 10 '(S100), and in the adsorption bed 4. The gaseous mixture is selectively adsorbed to the adsorbent and the concentrated weak adsorbate gas is recovered (S110), and the adsorbent to which the selected gas is adsorbed is moved to the high temperature desorption bed 30 through the transfer device (S120), In the desorption bed (30) (high pressure or high pressure ᅳ high temperature) (5), the primary adsorbent is desorbed at a high temperature (S130), and the adsorbent of the desorption bed (30) is desorbed by the pressure difference. (S140), the adsorbent is regenerated by separating the adsorbed secondary gas from the desorption bed (low pressure, high temperature) (5), and the concentrated strongly adsorbate gas (C0 _2, etc.) is recovered (S150), The regenerated adsorbent is moved to the adsorption bed 4 through the adsorbent down pipe 7 and circulated. (S160)

In the adsorption process system shown in FIG. 10, the basic operating situation is very similar to the case of the uptake: adsorption-vacuum desorption of FIG. 4. However, when the gas mixture is injected into the desorption bed, it is supplied at a high pressure through a compressor. Is different. Also, the kinetic energy of the concentrated weak adsorbate is recovered through the expander 16 and the generator 17.

Meanwhile, mobile phase temperature pressure fluctuations according to the present invention as shown in FIGS. 4 and 10. Since the pressure of the adsorption bed 4 is higher than the pressure of the desorption bed 5 in the process by the adsorption process system, some gaseous mixture flows from the adsorption bed to the desorption bed and leaks along the adsorbent reflux tube 7. Symptoms may occur. This leak occurs due to the pressure difference between the adsorption bed 4 and the desorption bed 5, and the flow rate thereof is proportional to the pressure difference between the adsorption bed 4 and the desorption bed 5.

At this time, by controlling at least one of the size of the adsorbent particles, the diameter and the length of the reflux tube 7, it is possible to prevent the backflow of some gas generated by the pressure difference in the reflux tube (7), Pressure drop through tube (7) can be adjusted, leaking enough to not cause problems ^; Can be reduced.

At this time, the size of the particles is approximately 0.1mm ~ 10mm. In addition, the general flue gas is discharged to about 16C C, the temperature required for efficient desorption in the desorption bed (5) is about 50 ~ 70 ^° C. Therefore, before injecting the flue gas into the adsorption bed 4, by heating the desorption bed 5 using the exhaust gas, energy required for maintaining the temperature of the desorption bed 5 can be saved. Hereinafter, effects through the process conditions of the process system illustrated in FIGS. 4 and 11 will be described.

The operating conditions of the process are classified into atmospheric adsorption-vacuum desorption operation, high pressure adsorption-atmospheric desorption operation, and high pressure adsorption-vacuum desorption according to the characteristics of the target gas mixture and the target adsorbent. Conventionally, the pressure adsorption-progression / desorption operation was performed in a system composed of only an adsorption bed and a desorption bed, but the high temperature desorption bed 30 in the embodiment of the present invention to overcome the disadvantage that the operation cost of the low pressure pump for vacuum is high. In addition, the high pressure adsorption-low pressure desorption operation can be performed by using the stepwise desorption, which can significantly reduce the pump operation cost.

Atmospheric pressure gas mixture (1) is supplied to the adsorption bed, the hobbed bed (4) is operated at atmospheric pressure (P _A ), desorbs the strong adsorbate from the high temperature desorption bed (30) first, and recovers the strongly adsorbate second. Desorption bend 5 is operated at low pressure (P _D <P _A ). From the detachable bed (5) Strong adsorbate enriched gas is recovered using a gas pump.

As shown in FIG. 9, in the case of the high pressure adsorption-atmospheric desorption operation, the gas mixture 1 of high pressure is supplied to the adsorption bed 4 so that the adsorption bed is operated at a high pressure P _A , The desorption bed 5 is operated at atmospheric pressure ((P _D <P _A ). The weak adsorbate enriched gas from the adsorption bed 4 is recovered through the diffuser 13 and the generator 16, so that the pressure difference across the diffuser is increased. The resulting mechanical energy is also recovered.

Adsorption heat generated during the adsorption is recovered through the adsorption bed (4) heat exchange system and supplied to the desorption bed to be used as heat energy required for desorption. When the raw material gas mixture (1) has a high temperature, the temperature of the gas mixture is reduced to the temperature (T _A ) of the adsorptive bed through a heat exchange system before raw material supply to recover thermal energy from the raw material, and the recovered thermal energy is a high temperature desorption bed through a heat exchange system. (30) and the desorption bed (5) to maintain the desorption temperature (T _D ).

Here, the lower the temperature, the better the gas is adsorbed to the adsorbent. When the gas mixture is adsorbed on the adsorbent in the adsorbent bed (4), the heat of the hopping occurs and the bed temperature rises. It will lower the temperature of 4).

The higher the temperature, the better the gas desorbs from the adsorbent. When the gas desorbs from the adsorbent, the temperature of the adsorption bed (4) is increased through a heater (8) because the bed temperature drops due to desorption. It will increase. Powder transfer

The adsorbent regenerated in the desorption bed (5) is transferred to the adsorption seed (4) by gravity along the adsorbent reflux tube (7). The adsorbent brought out into the lower part of the adsorption bed 4 is transferred to the high temperature desorption bed 30X5 by using a closed powder transport device 6, and the powder is transported to a bucket elevator or a bucket elevator. Bucket conveyor is used. Then, the adsorbent of the high temperature desorption bed 30 is moved back to the desorption bed through the reflux tube (7), the high temperature desorption bed (30) is the pressure of the suction bed and Since it is the same, it is higher than the detachable bed 5 so that a natural movement can be induced by the pressure difference. As such, the normal flue gas applied to the adsorption process system according to the present invention is composed of 10% carbon dioxide (C0 ₂ ) and 90% nitrogen (N ₂ ), and in the case of carbon dioxide (C02), high purity of about 99% after separation. Since it is not possible to recover all of them in one step, the carbon dioxide is separated and recovered by operating the PSA process in at least two steps. Among these, the first stage PSA process accounts for a large part of the total operating cost. The mobile phase pressure fluctuation adsorption process of the present invention can replace the first stage PSA process, and the staged desorption compared to the first stage PSA process. As it is possible to separate to higher purity by using the process, as a result, when the carbon dioxide produced through the one-stage mobile phase pressure fluctuation adsorption process is injected into the two-stage separation f process to increase the purity, the burden on the purity of the two-stage separation process is increased. This reduces the overall operating cost.

In addition, the system of the present invention uses heat and steam in the utility to maintain the temperature change occurring in the adsorption bed and the desorption bed at the optimum operating point temperature in the mobile bed pressure fluctuation adsorption hole which enables the continuous process. Be. The utility cost is a big expense in the overall operating cost, so the system according to the invention, which makes it possible to minimize this cost, is of great industrial significance. While the invention has been shown and described in connection with specific embodiments thereof, it is well known in the art that various modifications and changes can be made without departing from the spirit and scope of the invention as indicated by the claims. Anyone who has a can easily know.

[Description of the code]

4: adsorption bed, 5: desorption bed, 6: adsorber feeder, 7: hops reflux tube

8a, 8b: Each, 9: Heater 10: Blower, 10 ': Compressor, 11,14: cyclone, 12,15: bag filter, 16: expander, 17: generator, 30: high

Industrial Applicability

The present invention relates to a specific gas adsorption process system, and ≤Γ in detail from the adsorbent by applying a heat exchange system that can increase the adsorption and stepwise high temperature-low pressure desorption and optimization of the adsorption performance and economics in different temperature and pressure environment There is industrial applicability as it relates to a mobile bed temperature pressure swing adsorption process system for separating gases and circulating adsorbents into a mobile bed and for selective gas separation.

Claims

[Range of request]

[Claim 1]

An adsorption bed for selectively adsorbing the introduced mixed gas;

A blower mounted under the adsorption bed to inject the mixed gas;

A transporting device for transporting the adsorbent that has come out from the lower portion of the adsorption bed;

A high temperature desorption bed for heating and adsorbing the adsorbent transferred from the transfer device to desorb adsorbate first and positioned above the adsorption bed;

A desorption bedo for desorbing adsorbents by moving the adsorbent powder desorbed from the high temperature desorption bed;

A reflux tube for moving the adsorbent powder desorbed from the desorption bed to the adsorption bed; And

After removing the pentagonal water from the bottom of the adsorption bed and separating the exiting pentagonal water, the separated partial angular water is introduced into the upper and lower ends of the adsorption bed, and the heat is removed. It includes a heat exchange system for heating the cooling water to be introduced into the high temperature desorption bed to increase the temperature of the high temperature desorption bed,

The high silver desorption bed is equal to the pressure of the adsorption bed (P _A ), the desorption seed is maintained at a low pressure (P _D ) and high temperature (T _D ) compared to the adsorption bed, the size of the adsorbent particles, By controlling at least one of the diameter and the length of the reflux tube to prevent backflow of some gases generated by the pressure difference in the reflux tube;

.

【Old Port 2】

In U,

The heat exchange system,

The first angled water separated from the lower portion of the adsorption bed is heated by inflowing and removing the angled water into the lower portion of the lower end of the adsorption bed. Afterwards, the first heat interchanger which heats the outlet fourth discharge water and inflows into the silver desorbing bed to increase the temperature of the desorbing bed; And a second heat exchanger configured to increase the temperature of the desorption bed by heating the remaining third exponent water after introducing the high temperature desorption bed.

[Claim 3]

The method of claim 2,

The third and fourth angles, which are discharged from the adsorption bed and closed to the high temperature desorption bed, are heated by at least one steam heater installed in each flow path. .

【Old Port 4】

According to claim 13,

The third pressure # steam-heated steam heater is a temperature and pressure fluctuations two-phase adsorption process system, characterized in that it comprises a steam heater using the waste gas discharged from the upper end of the adsorption bed.

[¾ port 5]

An adsorption bed for selectively adsorbing the introduced mixed gas;

A compressor installed under the adsorption bed to compress and inject the mixed gas;

Adsorbent powder desorbed from the high temperature desorption bed is moved to desorb the adsorbate secondary: a desorption bed positioned above the adsorption bed;

A reflux tube for moving the adsorbent powder desorbed from the desorption vessel ^ to the adsorption bed; And The water is introduced into the lower portion of the lower end of the adsorption bed, and the water is separated, and the separated water angle is separated. A heat exchange system for heating the angled water and introducing the high temperature desorption bed to increase the temperature of the high temperature desorption bed,

The high temperature desorption bed is equal to the pressure P _A of the hopping bed, and the desorption bed maintains a lower pressure (P _D ) and a higher temperature (T _D ) than the adsorption bed, and the size of the adsorbent particles; A temperature pressure fluctuation mobile bed adsorption process system, characterized in that by controlling at least one of the diameter and the length of the reflux tube back flow of some gas generated by the pressure difference in the reflux tube.

[Claim 6]

The method of claim 5,

The heat exchange system,

The first angle of the water is introduced into the lower portion of the adsorptive bed, and the first angle is separated from the lower portion of the adsorption bed. In order to increase the temperature of the desorption bed by flowing into the desorption bed, the heat exchanger is discharged from the lower end of the adsorption bed, and the second condensate is partially discharged from the lower end of the adsorption bed. A temperature pressure fluctuation mobile bed adsorption process system, characterized in that consisting of a second heat exchanger to increase the temperature of the desorption bed by flowing.

[Claim 7]

The method of claim 6,

And said third angle and the fourth angle, which are discharged from said adsorption bed and introduced into said high temperature desorption bed, are heated by at least one steam heater installed in each flow path. [Claim 8]

The method of claim 7,

The steam heater for heating the third water is characterized in that it comprises a steam heater using the waste gas at the upper end of the adsorption bed

Mobile phase adsorption process system.