CN1956768A - Method and system for treating exhaust gas, and method and apparatus for separating carbon dioxide - Google Patents

Method and system for treating exhaust gas, and method and apparatus for separating carbon dioxide Download PDF

Info

Publication number
CN1956768A
CN1956768A CNA2005800111997A CN200580011199A CN1956768A CN 1956768 A CN1956768 A CN 1956768A CN A2005800111997 A CNA2005800111997 A CN A2005800111997A CN 200580011199 A CN200580011199 A CN 200580011199A CN 1956768 A CN1956768 A CN 1956768A
Authority
CN
China
Prior art keywords
waste gas
carbon dioxide
gas
cooling agent
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2005800111997A
Other languages
Chinese (zh)
Inventor
平野义男
引野健治
角谷贡
清木义夫
常冈晋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chugoku Electric Power Co Inc
Mitsubishi Heavy Industries Ltd
Original Assignee
Chugoku Electric Power Co Inc
Mitsubishi Heavy Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chugoku Electric Power Co Inc, Mitsubishi Heavy Industries Ltd filed Critical Chugoku Electric Power Co Inc
Publication of CN1956768A publication Critical patent/CN1956768A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Landscapes

  • Treating Waste Gases (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

A method for treating an exhaust gas, which comprises passing an exhaust gas discharged from a boiler using coal or LNG as a fuel through a cooling medium, to cool the exhaust gas to a first temperature at which carbon dioxide is not solidified and a nitrogen oxide or a sulfur oxide is liquefied or solidified, to thereby liquefy or solidify a nitrogen oxide or a sulfur oxide contained in the above exhaust gas as a harmful gas component and separate it from the exhaust gas and simultaneously remove the moisture contained in the exhaust gas, and then cool the resultant exhaust gas to a second temperature at which carbon dioxide is solidified, to thereby solidify the carbon dioxide contained in the exhaust gas and separate the carbon dioxide from the exhaust gas.

Description

Handle the method and system of waste gas and the method and apparatus of separating carbon dioxide
Technical field
The present invention relates to handle the method and system of waste gas.
Background technology
Contained harmful gas component such as oxysulfide and nitrogen oxide are by using for example wet desulfurizer or using the nitrogen rejection facility that adopts denitrification catalyst to separate and remove in exhaust gas discharged from the blast furnace of the coal-burning boiler of power plant, chemical plant installations or the like and iron-smelter, coke oven, converter or the like.In addition, the so-called physical absorption process of use active carbon is known is the more effective ways that separate and remove harmful gas component.
Simultaneously, in recent years, amount of carbon dioxide continues to increase in the atmosphere, thus itself and atmospheric temperature to raise be that the relation of so-called greenhouse effects is becoming focal issue.The increase of carbon dioxide generating amount mainly is to be caused by fossil-fuel-fired institute.Therefore, consider, require that power plant, chemical plant installations etc. will carbon dioxide be limited in the least possible amount in the waste gas of atmosphere with being discharged into from the environment viewpoint.(list of references 1: Japanese Patent Application Publication publication No.2000-317302.)
In such environment, just handle exhaust gas discharged blast furnace from for example coal-burning boiler and iron-smelter, coke oven, converter or the like, carbon dioxide need be reclaimed effectively simultaneously harmful gas component such as nitrogen oxide and oxysulfide are removed effectively.Therefore, need one can be effectively and remove harmful gas component continuously successively and reclaim the exhaust treatment system of carbon dioxide.
In addition, with regard to handling harmful gas component such as nitrogen oxide are removed effectively from for example firing exhaust gas discharged such as LNG boiler, carbon dioxide need being reclaimed simultaneously effectively.Therefore, need a technological process of can be effectively and removing harmful gas component continuously successively and reclaiming carbon dioxide.
As for these treatment of waste gas, need reclaim carbon dioxide effectively, need to remove effectively harmful gas component such as nitrogen oxide and oxysulfide simultaneously.Therefore, need one can be effectively and remove harmful gas component continuously successively and reclaim the exhaust treatment system of carbon dioxide.
Here, for the technology of institute's carbonated in reclaiming waste gas, the technology of isolating carbon dioxide from waste gas is important basic fundamental.For example, list of references 1 discloses this type of technology, in this technology the carbon dioxide in the waste gas is frozen into dry ice and is also separated, and heats then and add to be pressed into liquid carbon dioxide.The disclosed method of this list of references can be by for example shown in Figure 11 enforcement.In the method shown in this figure, the gas 1103 mobile cooling agent 1100 in the hot carrier pipe 1102 of heat exchanger that makes desire therefrom isolate carbon dioxide then flows outside carrier pipe, thus institute's carbonated in the gas is frozen into dry ice and collects it with collection container 1104.Be transported to collection container 1104 contained dry ice 1105 in the liquefaction device 1106 and be liquefied as liquid carbon dioxide 1107, recovery is got up.It is to be noted that the reason that collected dry ice 1105 is liquefied is to be convenient to store and transportation.
Method shown in Figure 11 can have the dry ice precipitation in the inside of hot carrier pipe 1102.Therefore, the dry ice that is precipitated can stop up the passage of hot carrier pipe 1102, and this device is difficult to continuously or operation automatically.In addition, because the collection container 1104 of the section of solidifying and the liquefaction device 1106 of liquefaction stages are respectively independent equipment, therefore needs one respectively can be transported to carbon dioxide the mechanism of liquefaction device 1106 from collection container 1104.That is to say that for method shown in Figure 11, the process of separating carbon dioxide can not be carried out continuously and effectively from gas, and if especially be applied to produce source such as the thermo-power station and the iron-smelter of large quantity of exhaust gas, this method may be not enough at aspect of performance.
The present invention finishes in view of above background, the purpose of this invention is to provide a kind of waste gas processing method and system that can effectively remove harmful gas component and reclaim carbon dioxide from waste gas.
The mode of dealing with problems
According to claim 1 of the present invention, a kind of waste gas processing method is provided, it comprises that allowing waste gas flow through cooling agent makes it to be cooled to make nitrogen oxide liquefaction or solidify but first temperature that carbon dioxide can not solidify, thereby thus with harmful gas component nitrogen oxide liquefaction contained in the waste gas or solidify first process that they are separated from waste gas; With second temperature that waste gas is cooled to carbon dioxide is solidified, thereby thus carbon dioxide contained in the waste gas is solidified second process that it is separated from waste gas.
Here, first temperature is that carbon dioxide can not liquefy or solidify but temperature that moisture and nitrogen oxide can liquefy or solidify.Second temperature is the temperature that carbon dioxide is solidified.
The waste gas that this method will contain harmful gas component is cooled to liquefy or solidifies nitrogen oxide but first temperature that can not solidify carbon dioxide, thereby thus nitrogen oxide contained in the waste gas is liquefied or solidifies it is separated (first process) from waste gas, then this waste gas is cooled to solidify second temperature of carbon dioxide, it is separated (second process) from waste gas thereby carbon dioxide contained in the waste gas is solidified.In first process, carbon dioxide is stayed in the waste gas and is not separated from waste gas, in second process subsequently, will reclaim carbon dioxide beyond doubt.Like this, as the waste gas of harmful gas component, can effectively reclaim carbon dioxide after removing harmful gas component concerning nitrogen-containing oxide.
According to claim 2 of the present invention, waste gas processing method by claim 1 is provided, comprise that allowing waste gas flow through cooling agent makes it to be cooled to make nitrogen oxide and oxysulfide liquefaction or solidify but first temperature that can not solidify carbon dioxide, thus with in the waste gas contained as harmful gas component nitrogen oxide and oxysulfide liquefaction or solidify and first process that they are separated from waste gas; With second temperature that waste gas is cooled to solidify carbon dioxide, thereby thus carbon dioxide contained in the waste gas is solidified second process that it is separated from waste gas.
Here, first temperature is that carbon dioxide can not liquefy or solidify but temperature that moisture, nitrogen oxide and oxysulfide can liquefy or solidify.Second temperature is the temperature that carbon dioxide is solidified.
The waste gas that this method will contain harmful gas component is cooled to liquefy or to solidify nitrogen oxide and oxysulfide but first temperature that can not solidify carbon dioxide, thereby thus with the liquefaction of nitrogen oxide contained in the waste gas and oxysulfide or solidify they are separated (first process) from waste gas, then this waste gas can be solidified second temperature of carbon dioxide to cooling, it be separated (second process) from waste gas thereby carbon dioxide contained in the waste gas is solidified.In first process, carbon dioxide is stayed in the waste gas and is not separated from waste gas, in second process subsequently, will reclaim carbon dioxide beyond doubt.Like this, as the waste gas of harmful gas component, can effectively reclaim carbon dioxide after removing harmful gas component concerning nitrogen-containing oxide and oxysulfide.
According to claim 3 of the present invention, waste gas processing method by claim 2 is provided, it comprises that one is elevated to the evaporative cooling agent but the temperature of not evaporating harmful gas component from the temperature of the isolated harmful gas component of waste gas, the process of separating harmful gas component and cooling agent thus with first process.
According to the present invention, thereby cooling agent can separate with the poisonous gas component and reclaim reliably and be effectively used.
According to claim 4 of the present invention, the waste gas processing method by claim 3 is provided, it comprises that a cooling agent that will separate with harmful gas component is as a kind of process that waste gas is circulated through its cooling agent that flows through.
Because cooling agent recycles by this way, this cooling agent is able to efficient utilization.
According to claim 5 of the present invention, any one the waste gas processing method by claim 2-4 is provided, it comprises one first process temperature of isolated harmful gas component from waste gas being brought up to can evaporate oxysulfide but the temperature of non-vaporized nitrogen oxide, thus that harmful gas component is contained oxysulfide and nitrogen oxide separating process.
Like this, can isolate the contained nitrogen oxide of harmful gas component from waste gas, oxysulfide that can harmful gas component is contained separates with nitrogen oxide like this.
According to claim 6 of the present invention, any one the waste gas processing method by claim 2-5 is provided, wherein cooling agent comprises any in dimethyl ether, methyl alcohol, ethanol, toluene and the ethylbenzene.
Require cooling agent can harmful gas component be liquefied or the temperature of solidifying under can not solidify so that can be in first process cooling agent and liquefaction or the harmful gas component that solidifies be separated.In addition, in order to liquefy effectively with cooling agent or to solidify harmful gas component, require cooling agent to have the characteristic of easy absorption harmful gas component.Also have,, require this cooling agent to have the characteristic of absorbing carbon dioxide hardly in order in second process, from waste gas, to reclaim carbon dioxide effectively.Any in dimethyl ether, methyl alcohol, ethanol, toluene and the ethylbenzene all satisfies this requirement.
According to claim 7 of the present invention, any one the waste gas processing method by claim 2-6 is provided, wherein first process comprises a process of isolating the waste gas contained humidity from waste gas.
In first process with waste gas in contained humidity separate, can in second process, reclaim carbon dioxide effectively like this.
According to claim 8 of the present invention, any one the waste gas processing method by claim 2-7 is provided, wherein second process comprises a process that drikold (dry ice) is liquefied.
Like this, by with drikold (dry ice) liquefaction, improved the storability of carbon dioxide and conveying property and improved the property disposed.
According to claim 9 of the present invention, any one the waste gas processing method by claim 2-8 is provided, wherein before first process, will carries out one and will be cooled to waste gas after about room temperature by carrying out the preprocessing process that heat exchange removes contained humidity in the waste gas, harmful gas component and dust with water.
By carrying out this preprocessing process, moisture, harmful gas component and dust can remove from waste gas reliably.
According to claim 10 of the present invention, a kind of exhaust treatment system is provided, it comprises first device, this device is used for implementing one to be allowed waste gas flow through cooling agent to make it to be cooled to make nitrogen oxide liquefaction or solidify but first temperature that can not solidify carbon dioxide, thus with harmful gas component nitrogen oxide liquefaction contained in the waste gas or solidify and process that they are separated from waste gas; With second device, this device is used for implementing one waste gas is cooled to solidify second temperature of carbon dioxide, and institute's carbonated solidifies the process that it is separated in the waste gas from waste gas thereby make thus.
According to claim 11 of the present invention, exhaust treatment system by claim 10 is provided, it comprises first device, this device is used for implementing one to be allowed waste gas flow through cooling agent to make it to be cooled to make nitrogen oxide and oxysulfide liquefaction or solidify but first temperature that can not solidify carbon dioxide, thereby with contained harmful gas component nitrogen oxide and oxysulfide liquefaction in the waste gas or solidify and process that they are separated from waste gas; With second device, this device is used for implementing one waste gas is cooled to solidify second temperature of carbon dioxide, thereby makes carbon dioxide contained in the waste gas solidify the process that it is separated thus from waste gas.
According to claim 12 of the present invention, exhaust treatment system by claim 11 is provided, it comprises will bringing up to first device isolated harmful gas component temperature from waste gas for one makes the refrigerant evaporates of mixing with harmful gas component but the temperature that harmful gas component can not evaporate, and separates the device of harmful gas component and cooling agent thus.
According to claim 13 of the present invention, the exhaust treatment system by claim 11 is provided, it comprises that a cooling agent that will separate with harmful gas component is as a kind of device that waste gas is circulated through its cooling agent that flows through.
According to claim 14 of the present invention, any one the exhaust treatment system by claim 11-13 is provided, it comprises that one will be brought up to the evaporation oxysulfide but the temperature of non-vaporized nitrogen oxide, the device that thus that harmful gas component is contained oxysulfide separates with nitrogen oxide with first device temperature of isolated harmful gas component from waste gas.
According to claim 15 of the present invention, any one the exhaust treatment system by claim 11-14 is provided, wherein cooling agent comprises any in dimethyl ether, methyl alcohol, ethanol, toluene and the ethylbenzene.
According to claim 16 of the present invention, any one the exhaust treatment system by claim 11-15 is provided, wherein first device comprises that an energy isolates the device of waste gas contained humidity from waste gas.
According to claim 17 of the present invention, any one the exhaust treatment system by claim 11-16 is provided, wherein second device comprise one can be with the device of drikold (dry ice) liquefaction.
According to claim 18 of the present invention, any one the exhaust treatment system by claim 11-17 is provided, and it comprises that one will be implemented the waste gas after will being cooled to about room temperature by carrying out the device that heat exchange removes the preprocessing process of contained humidity in the waste gas, harmful gas component and dust with water before the process of implementing first device.
According to claim 19 of the present invention, a kind of waste gas processing method is provided, it is characterized in that it comprises that allowing the waste gas of combustion LNG boiler emission flow through cooling agent makes it to be cooled to make nitrogen oxide liquefaction or solidify but first temperature that carbon dioxide can not solidify, thereby thus with harmful gas component nitrogen oxide liquefaction contained in the waste gas or solidify first process that it is separated from waste gas; With second temperature that waste gas is cooled to carbon dioxide is solidified, thereby thus carbon dioxide contained in the waste gas is solidified second process that it is separated from waste gas.
The waste gas that this method will be fired the LNG boiler emission is cooled to liquefy or solidifies nitrogen oxide but first temperature that can not solidify carbon dioxide, thereby thus nitrogen oxide contained in the waste gas is liquefied or solidifies it is separated (first process) from waste gas, then this waste gas is cooled to solidify second temperature of carbon dioxide, it is separated (second process) from waste gas thereby carbon dioxide contained in the waste gas is solidified.In first process, carbon dioxide is stayed in the waste gas and is not separated from waste gas, in second process subsequently, will reclaim carbon dioxide beyond doubt.Like this, as the waste gas of harmful gas component, can effectively reclaim carbon dioxide after removing harmful gas component concerning nitrogen-containing oxide.
According to claim 20 of the present invention, the waste gas processing method by claim 19 is provided, it comprises that a nitrogen oxide that first process is solidified is incorporated into solid-liquid separator, thus the process of separating nitrogen oxide and cooling agent.
Like this, just harmful gas component and the cooling agent that mixes with it can be separated.
According to claim 21 of the present invention, the waste gas processing method by claim 20 is provided, it comprises the temperature the fluid temperature that solid-liquid separator separated being brought up to the evaporative cooling agent but do not evaporate harmful gas component, isolates the process of cooling agent thus.
According to the present invention, because cooling agent can reclaim effectively, this cooling agent is able to efficient utilization.
According to claim 22 of the present invention, the waste gas processing method by claim 21 is provided, it comprises that will be from a liquid isolated cooling agent is as the process that allows waste gas circulate through its cooling agent that flows through.
Because cooling agent in this way uses circularly, cooling agent is able to efficient utilization.
According to claim 23 of the present invention, any one the waste gas processing method by claim 19-22 is provided, wherein cooling agent comprises any in dimethyl ether, methyl alcohol, ethanol, toluene and the ethylbenzene.
Require cooling agent can harmful gas component be liquefied or the temperature of solidifying under can not solidify so that can be in first process cooling agent and liquefaction or the harmful gas component that solidifies be separated.In addition, in order to liquefy effectively with cooling agent or to solidify harmful gas component, require cooling agent to have the characteristic of easy absorption harmful gas component.Also have,, require this cooling agent to have the characteristic of absorbing carbon dioxide hardly in order in second process, from waste gas, to reclaim carbon dioxide effectively.Any in dimethyl ether, methyl alcohol, ethanol, toluene and the ethylbenzene all satisfies this requirement.
According to claim 24 of the present invention, any one the waste gas processing method by claim 19-23 is provided, wherein first process comprises a process of isolating the waste gas contained humidity from waste gas.
Like this, in first process, contained humidity in the waste gas is separated, so just can in second process, be reclaimed carbon dioxide effectively.
According to claim 25 of the present invention, any one the waste gas processing method by claim 19-24 is provided, wherein second process comprises a process that drikold (dry ice) is liquefied.
Like this, by with drikold (dry ice) liquefaction, improved the storability of carbon dioxide and conveying property and improved the property disposed.
According to claim 26 of the present invention, any one the waste gas processing method by claim 19-25 is provided, wherein before first process, will carries out one and will be cooled to waste gas after about room temperature by carrying out the preprocessing process that heat exchange removes contained humidity and harmful gas component in the waste gas with water.
By carrying out this preprocessing process, moisture and harmful gas component can remove from waste gas reliably.
According to claim 27 of the present invention, any one the waste gas processing method by claim 19-26 is provided, wherein at least one waste gas or the heat of evaporation that produced during as gaseous fuel because of LNG of cooling agent of first and second processes is cooled.
Like this, the heat of evaporation that is produced when utilizing LNG to be used as gaseous fuel is cooled off the waste gas or the cooling agent of one of at least the first and second processes, and cooling is saved with energy.
According to claim 28 of the present invention, a kind of exhaust treatment system is provided, it comprises first device, this device is used for implementing a waste gas that allows combustion LNG boiler emission and flows through cooling agent and make it to be cooled to make nitrogen oxide liquefaction or solidify but first temperature that can not solidify carbon dioxide, thus with harmful gas component nitrogen oxide liquefaction contained in the waste gas or solidify and process that they are separated from waste gas; With second device, this device is used for implementing one waste gas is cooled to solidify second temperature of carbon dioxide, and institute's carbonated solidifies the process that it is separated in the waste gas from waste gas thereby make thus.
According to claim 29 of the present invention, the exhaust treatment system by claim 28 is provided, it comprises that a nitrogen oxide that first device is solidified is incorporated into solid-liquid separator, thus the device of separating nitrogen oxide and cooling agent.
According to claim 30 of the present invention, the exhaust treatment system by claim 29 is provided, it comprises that the fluid temperature that solid-liquid separator is separated brings up to the temperature of can the evaporative cooling agent but not evaporating harmful gas component, isolates the device of cooling agent thus.
According to claim 31 of the present invention, the exhaust treatment system by claim 30 is provided, it comprises that will be from a liquid isolated cooling agent is as the device that waste gas is circulated through its cooling agent that flows through.
According to claim 32 of the present invention, any one the exhaust treatment system by claim 28-31 is provided, wherein cooling agent comprises any in dimethyl ether, methyl alcohol, ethanol, toluene and the ethylbenzene.
According to claim 33 of the present invention, any one the exhaust treatment system by claim 28-32 is provided, wherein first device comprises the device of isolating the waste gas contained humidity from waste gas.
According to claim 34 of the present invention, any one the exhaust treatment system by claim 28-33 is provided, be characterised in that second device comprise one can be with the device of drikold (dry ice) liquefaction.
According to claim 35 of the present invention, any one the exhaust treatment system by claim 28-34 is provided, and it comprises that one will be implemented the waste gas after will being cooled to about room temperature by carrying out the device that heat exchange removes the preprocessing process of contained humidity and harmful gas component in the waste gas with water before the process of implementing first device.
According to claim 36 of the present invention, any one the exhaust treatment system by claim 28-35 is provided, wherein be cooled in the waste gas or the heat of evaporation that produced during as gaseous fuel because of LNG of cooling agent of first and second devices at least one.
According to claim 37 of the present invention, a kind of exhaust treatment system is provided, it comprises first device, this device flows through cooling agent with waste gas to be made it to be cooled to make nitrogen oxide and oxysulfide liquefaction or solidifies but the temperature that can not solidify carbon dioxide, thereby with contained harmful gas component nitrogen oxide and oxysulfide liquefaction in the waste gas or solidify and process that they are separated from waste gas; With second device, this device makes the waste gas that removes nitrogen oxide and oxysulfide flow through a pressure vessel to cool off and solidify carbon dioxide, this pressure vessel of bubble-tight shut-off, the temperature of rising drikold is evaporated, owing to evaporating the carbon dioxide that makes the pressure rising make co 2 liquefaction and will liquefy in pressure vessel, carbon dioxide is discharged to outside the pressure vessel.
Like this, in this system, the gas cooled that first device will contain harmful gas component is to liquefiable or solidify nitrogen oxide and oxysulfide but the temperature of not solidifying carbon dioxide, thereby thus contained nitrogen oxide and oxysulfide as harmful gas component in the waste gas is liquefied or solidify they are separated from waste gas.Therefore, in first device, carbon dioxide is stayed in the waste gas and is not separated from waste gas, in second device, will reclaim carbon dioxide beyond doubt subsequently.Adopt second device, carbon dioxide can solidify in same pressure vessel and liquefy.According to exhaust treatment system of the present invention, can be by simply installing separating carbon dioxide from waste gas, realized thus under low cost effectively and the technological process of recovery carbon dioxide from waste gas reliably.And under the situation of not using special liquefying plant, carbon dioxide can be discharged with the liquid form that can store and carry.Therefore, exhaust treatment system of the present invention can be effectively, reclaim carbon dioxide reliably from the waste gas that contains harmful gas component such as nitrogen oxide and oxysulfide, removes this harmful gas component simultaneously.
According to claim 38 of the present invention, exhaust treatment system by claim 37 is provided, it comprises will bringing up to first device isolated harmful gas component temperature from waste gas for one makes the refrigerant evaporates of mixing with harmful gas component but the unvaporized temperature of harmful gas component, separates the device of harmful gas component and cooling agent thus.
In this way, cooling agent can be separated from harmful gas component reliably and reclaim reliably, be effectively used thus.
According to claim 39 of the present invention, exhaust treatment system by claim 37 or 38 is provided, it comprises that one will be brought up to the evaporation oxysulfide but the temperature of non-vaporized nitrogen oxide, the device that thus that harmful gas component is contained oxysulfide separates with nitrogen oxide with first device temperature of isolated harmful gas component from waste gas.
In this way, can from waste gas, isolate nitrogen oxide contained in the harmful gas component, oxysulfide contained in the harmful gas component can be separated with nitrogen oxide thus.
According to claim 40 of the present invention, exhaust treatment system is provided, it comprises first device, this installs this device and is used for implementing a waste gas that allows combustion LNG boiler emission and flows through cooling agent and make it to be cooled to make nitrogen oxide liquefaction or solidify but first temperature that can not solidify carbon dioxide, thus with harmful gas component nitrogen oxide liquefaction contained in the waste gas or solidify and process that they are separated from waste gas; With second device, the waste gas that this device will remove nitrogen oxide flows through a pressure vessel and cools off and solidify carbon dioxide, this pressure vessel of bubble-tight shut-off, the temperature of rising drikold is evaporated, owing to evaporating the carbon dioxide that makes the pressure rising make co 2 liquefaction and will liquefy in pressure vessel, carbon dioxide is discharged to outside the pressure vessel.
In this system, the gas cooled that first device will fire the LNG boiler emission is to liquefiable or solidify nitrogen oxide but first temperature of not solidifying carbon dioxide, thereby thus contained nitrogen oxide liquefaction or solidify as harmful gas component in the waste gas is separated them from waste gas.Therefore, in first device, carbon dioxide is stayed in the waste gas and is not separated from waste gas, in second device, will reclaim carbon dioxide beyond doubt subsequently.Adopt second device, carbon dioxide can solidify in same pressure vessel and liquefy.According to exhaust treatment system of the present invention, can be by simply installing separating carbon dioxide from waste gas, realized thus under low cost effectively and the technological process of recovery carbon dioxide from waste gas reliably.And under the situation of not using special liquefying plant, carbon dioxide can be discharged with the liquid form that can store and carry.Therefore, exhaust treatment system of the present invention can be effectively, reclaim carbon dioxide reliably from the waste gas that contains harmful gas component such as nitrogen oxide, removes this harmful gas component simultaneously.
According to claim 41 of the present invention, the exhaust treatment system by claim 40 is provided, it comprises that a nitrogen oxide that first device is solidified is incorporated into solid-liquid separator, thus the device of separating nitrogen oxide and cooling agent.
In this way, the poisonous gas component with the cooling agent of its mixing can be effectively, separate reliably.
According to claim 42 of the present invention, the exhaust treatment system by claim 41 is provided, it comprises the temperature the fluid temperature that solid-liquid separator separated being brought up to the evaporative cooling agent but do not evaporate harmful gas component, isolates the device of cooling agent thus.
In this way, can reclaim cooling agent effectively, therefore be effectively used.
According to claim 43 of the present invention, any one the exhaust treatment system by claim 37-42 is provided, be characterised in that cooling agent comprises any in dimethyl ether, methyl alcohol, ethanol, toluene and the ethylbenzene.
Require cooling agent can harmful gas component be liquefied or the temperature of solidifying under can not solidify so that can be in first process cooling agent and liquefaction or the harmful gas component that solidifies be separated.In addition, in order to liquefy effectively with cooling agent or to solidify harmful gas component, require cooling agent to have the characteristic of easy absorption harmful gas component.Also have,, require this cooling agent to have the characteristic of absorbing carbon dioxide hardly in order in second process, from waste gas, to reclaim carbon dioxide effectively.Any in dimethyl ether, methyl alcohol, ethanol, toluene and the ethylbenzene all satisfies this requirement.
According to claim 44 of the present invention, any one the exhaust treatment system by claim 37-43 is provided, and wherein the carbon dioxide cooling of carrying out with second device is to be undertaken by the coolant flow tubes outside that has cooling agent to flow through that allows carbonated gas contact pressure vessel to provide with solidifying.
Like this, dry ice is deposited on the outside of coolant flow tubes, and the internal path of heat-transfer pipe can not blocked.Therefore, be easy to carry out operate continuously or automatically.
According to claim 45 of the present invention, any one the exhaust treatment system by claim 37-44 is provided, wherein coolant flow tubes is back-shaped arranging.
Like this, back-shaped the arranging of coolant flow tubes can be guaranteed that enough contacts area are arranged between gas and the coolant flow tubes, thereby can solidify carbon dioxide effectively.
According to claim 46 of the present invention, a kind of method of separating carbon dioxide is provided, this method comprises that allowing the gas that contains carbon dioxide flow through a pressure vessel cools off and solidify carbon dioxide, this pressure vessel of bubble-tight shut-off, the temperature of rising drikold is evaporated, owing to evaporating the carbon dioxide that makes the pressure rising make co 2 liquefaction and will liquefy in pressure vessel, carbon dioxide is discharged to outside the pressure vessel.
According to the present invention, carbon dioxide can solidify in same pressure vessel and liquefy.Above method can be implemented by simple mechanism, and can be with low-cost high-efficiency and isolate carbon dioxide reliably from gas.In addition, under the situation of not using special liquefying plant, carbon dioxide can be discharged with the liquid form that can store and can carry.
According to claim 47 of the present invention, method by the separating carbon dioxide of claim 46 is provided, wherein cools off and solidify that operation is to be undertaken by the coolant flow tubes outside that has cooling agent to flow through that allows carbonated gas contact pressure vessel to provide.
According to the present invention, dry ice is deposited on the outside of coolant flow tubes, and the internal path of heat-transfer pipe can not blocked.Therefore, be easy to carry out operate continuously or automatically.
According to claim 48 of the present invention, the method by the separating carbon dioxide of claim 47 is provided, wherein coolant flow tubes is back-shaped arranging.
Like this, back-shaped the arranging of coolant flow tubes can be guaranteed that enough contacts area are arranged between gas and the coolant flow tubes, thereby can solidify carbon dioxide effectively.
According to claim 49 of the present invention, the method by the separating carbon dioxide of claim 46 is provided, wherein raise and solidify the temperature of carbon dioxide by the heat-transfer pipe that disposes in the pressure vessel or electric heater.
According to claim 50 of the present invention, method by the separating carbon dioxide of claim 46 is provided, and wherein pressure vessel has one to allow the gas that contains carbon dioxide flow into the gas feed in the pressure vessel, an outer gas vent and the liquid outlet that makes outside the liquefied carbon dioxide discharge pressure vessel of gas discharge pressure vessel that makes in the pressure vessel.
According to claim 51 of the present invention, the method by the separating carbon dioxide of claim 46 or 47 is provided, wherein gas comprises nitrogen oxide or oxysulfide.
According to claim 52 of the present invention, a kind of method of separating carbon dioxide is provided, this method has used one to have the gas feed that allows gas flow into wherein, make the gas vent that gas wherein discharges and make the pressure vessel of the liquid outlet that liquid wherein discharges, a cooler and a heat-transfer equipment that is used to improve the pressure vessel internal temperature that is installed in the pressure vessel; Described method comprises allows the gas that contains carbon dioxide flow into pressure vessel through gas feed; Make gas contact cooler, thereby cool off and solidify carbon dioxide; Close gas feed and gas vent, thereby make the pressure vessel bubble-tight shut-off; Temperature with heat-transfer equipment rising drikold is evaporated; Owing to evaporating in pressure vessel, carbon dioxide make the pressure rising make co 2 liquefaction; With through gas vent liquefied carbon dioxide is discharged to outside the pressure vessel.
According to claim 53 of the present invention, a kind of device of separating carbon dioxide is provided, comprise one have the gas feed that allows gas flow into wherein, make gas vent that gas wherein discharges, make liquid outlet that liquid wherein discharges, the pressure vessel of the control valve of amount of liquid that the control valve of gas flow that the control valve of the gas flow of control gas coming through import, control are discharged via gas vent and control are discharged via liquid outlet; A cooler and a heat-transfer equipment that is used to improve the pressure vessel internal temperature that is installed in the pressure vessel.
The accompanying drawing summary
Fig. 1 illustrates the layout of exhaust treatment system according to an embodiment of the invention;
Fig. 2 A shows when the analog gas that with sulfur dioxide concentration is 80ppm flows through according to embodiments of the present invention DME, the measurement result that sulfur dioxide concentration changes in the analog gas;
Fig. 2 B shows an installation drawing that is used for measuring sulfur dioxide and nitric oxide at the cooling agent meltage according to embodiments of the present invention;
Fig. 2 C shows the composition of simulated exhaust according to embodiments of the present invention;
Fig. 2 D shows the result who measures sulfur dioxide and nitric oxide meltage in cooling agent according to an embodiment of the present invention;
Fig. 2 E shows a layout that is used to measure the dry ice sublimation device 24 of recovery rate of CO 2 and analog gas temperature relation relation according to an embodiment of the present invention;
Fig. 2 F is the side view of dry ice sublimation device 24 when observing on the arrow A direction indication among Fig. 2 E according to an embodiment of the present invention;
Fig. 2 G shows the result who measures recovery rate of CO 2 and analog gas temperature relation according to embodiment of the present invention;
Fig. 3 illustrates the layout of exhaust treatment system according to an embodiment of the invention;
Fig. 4 A shows when the analog gas that with sulfur dioxide concentration is 80ppm flows through according to embodiments of the present invention DME, the measurement result that sulfur dioxide concentration changes in the analog gas;
Fig. 4 B shows an installation drawing that is used for measuring sulfur dioxide and nitric oxide at the cooling agent meltage according to embodiments of the present invention;
Fig. 4 C shows the composition of simulated exhaust according to embodiments of the present invention;
Fig. 4 D shows the result who measures sulfur dioxide and nitric oxide meltage in cooling agent according to an embodiment of the present invention;
Fig. 4 E shows a layout that is used to measure the dry ice sublimation device 24 of recovery rate of CO 2 and analog gas temperature relation according to an embodiment of the present invention;
Fig. 4 F is the side view of dry ice sublimation device 24 when observing on the arrow A direction indication among Fig. 2 E according to an embodiment of the present invention;
Fig. 4 G shows the result who measures recovery rate of CO 2 and analog gas temperature relation according to embodiment of the present invention;
Fig. 5 illustrates the layout of exhaust treatment system according to an embodiment of the invention;
Fig. 6 shows when the analog gas that with sulfur dioxide concentration is 80ppm flows through according to embodiments of the present invention DME, the measurement result that sulfur dioxide concentration changes in the analog gas;
Fig. 7 illustrates the layout according to the carbon dioxide separator 30 of one embodiment of the invention;
Fig. 8 illustrates according to one embodiment of the invention and separates the technological process of institute's carbonated method in the waste gas with carbon dioxide separator 30;
Fig. 9 is T-P (temperature and pressure) figure of carbon dioxide;
Figure 10 illustrates the layout according to the exhaust treatment system of one embodiment of the invention; With
Figure 11 is the technology of a kind of separating carbon dioxide of diagram.
The explanation of＜reference number 〉
10 exhaust gas source, 11 heat exchangers,
13 condensers, 14 discharging basins,
17 dehydrating towers, the 18DME cooling tower,
The 20DME knockout tower, 22 component knockout towers,
23 reversible heat exchanger, 24 dry ice sublimation devices,
25 cyclone separators, 26 dry ice melting units,
27 liquefaction carbonic acid storage tanks, 28 solid-liquid separators,
30 carbon dioxide separators, 40 refrigerators,
50 go out material processing device, 51 chimneys.
Implement best mode of the present invention
Describe preferred embodiment below with reference to the accompanying drawings in detail according to exhaust treatment system of the present invention.
=the first embodiment=
Fig. 1 shows the schematic diagram according to the exhaust treatment system of first embodiment of the invention.The exhaust treatment system of the present embodiment provides an energy effectively to reclaim the technological process that institute's carbonated can effectively remove contained humidity and harmful gas component in the waste gas simultaneously from the waste gas that comprises harmful gas component such as nitrogen oxide and oxysulfide of exhaust gas source 10 as dischargings such as the blast furnace of the coal-burning boiler of power plant, chemical plant installations etc. or burning heavy oil boiler and iron-smelter, coke oven, converters.
In the exhaust treatment system of this programme, in its preprocessing process, to be incorporated into from the waste gas that comprises harmful gas component such as nitrogen oxide and oxysulfide of exhaust gas source 10 discharging the heat exchanger 11 contained water for industrial use and condenser 13, thereby about cool to room temperature.Then, in first process, in dehydrating tower 17, be cooled to first temperature that carbon dioxide is solidified, thereby make in the waste gas contained humidity and nitrogen oxide and oxysulfide liquefaction or solidify and from waste gas, separate being cooled to waste gas about room temperature.Then, in second process, the waste gas of isolating moisture, nitrogen oxide and oxysulfide is cooled to second temperature lower than first temperature in dry ice sublimation device 24, thereby carbon dioxide contained in the waste gas is solidified and from waste gas, separates.
Although isolated harmful gas component and cooling agent mix in first process.But preferably cooling agent is circulated and is effectively used, so that can operate exhaust treatment system efficiently.Therefore, in the present embodiment, utilize the evaporating temperature between cooling agent and the harmful gas component poor, the employing method of evaporating makes cooling agent separate with harmful gas component and is recovered, and the cooling agent that reclaims is used as cooling agent once more.Need heat energy although it is pointed out that method of evaporating, can reduce this heat energy by adopting the low boiling cooling agent.
In order to reclaim carbon dioxide contained in the waste gas effectively in second process, carbon dioxide must be able to not liquefy or solidify when liquefying or solidifying moisture and harmful gas component.Carbon dioxide in the thermo-power station waste gas can be frozen into dry ice when being lower than predetermined temperature.Therefore, in order not allow carbon dioxide solidify, the gas temperature in dehydrating tower 17 exits must be higher than this predetermined temperature.
In first process, require cooling agent harmful gas component be liquefied or the temperature of solidifying under itself do not solidify so that from liquefaction or the harmful gas component that solidifies, isolate cooling agent.In addition, in order to liquefy effectively or to solidify harmful gas component, require cooling agent to have the characteristic of easy absorption harmful gas component.And,, require cooling agent to have carbon dioxide and be difficult for dissolving performance wherein in order in second process, from waste gas, to reclaim carbon dioxide effectively.
The specific cooling agent that satisfies these requirements is dimethyl ether (below be called DME).Can use except that dimethyl ether other material as cooling agent, as long as they satisfy the requirement of cooling agent.For example, can satisfy the inorganic salts (sodium chloride of these requirements, potassium chloride etc.), bromine compounds (lithium bromide, bromo bromide (bromo bromide), or the like), ether (dimethyl ether, methyl ether etc.), alcohol (methyl alcohol, ethanol etc.), silicone oil, paraffin hydrocarbon (propane, butane etc.), olefin(e) etc. can be used as cooling agent.For the harmful gas component that will liquefy or solidify separates with cooling agent, there is very big boiling-point difference more favourable between cooling agent and harmful gas component.Consider that from this type of viewpoint ether and alcohol are preferably as cooling agent.
It is 10% the analog gas measurement result that gas concentration lwevel changes in the analog gas when flowing through DME according to embodiments of the present invention that Fig. 2 A shows when making gas concentration lwevel.As shown in this Fig, when analog gas began to flow through DME, concentration of carbon dioxide temporarily descended in the analog gas because analog gas is dissolved among the DME, after a period of time, became the concentration (10%) when cycling through before the DME gradually.This be because carbon dioxide in DME saturated after, almost no longer include carbon dioxide and be dissolved in DME.In order to confirm that DME easily absorbs harmful gas component such as nitrogen oxide and oxysulfide, the inventor has done one and has allowed and comprise harmful gas component (ammonia: analog gas 10ppm) cycles through the experiment of DME for nitrogen dioxide: 60ppm, sulfur dioxide: 80ppm.The result has confirmed in after analog gas begins to flow through DME about 1 hour that all harmful gas component concentration become 1ppm or lower in the analog gas.
Then, describe the idiographic flow of the exhaust treatment system of the present embodiment in detail.At first, in preliminary treatment, be introduced in the heat exchanger 11 from the waste gas that comprises harmful gas component such as nitrogen oxide and oxysulfide of exhaust gas source 10 dischargings, in heat exchanger 11, introduced by the seawater (for example, 25 ℃) of sea water pump 12 supplies and cooling agent such as the ethylene glycol that comes from refrigerator 40 circulations.The waste gas of introducing from exhaust gas source 10 (for example 55 ℃) pass heat exchanger 11 therefore and by seawater and coolant cools to the room temperature.
The waste gas that will be cooled in heat exchanger 11 about room temperature is incorporated in the condenser 13 subsequently, and the waste gas that will introduce condenser 13 imports in the contained water for industrial use of condenser 13.Thus, moisture contained in the waste gas, harmful gas component, dust and analog are removed.The liquefaction water that comprises moisture, harmful gas component, dust and analog that shifts out from waste gas temporarily is stored in the discharging storage tank 14, is incorporated into out in the material processing device 50 with discharging pump 15 subsequently.The waste gas that will pass condenser 13 at last is incorporated in the dehydrating tower 17 with exhaust gas blower 16.It is pointed out that in condenser 13 heat exchange with water for industrial use makes waste gas be cooled to for example 5 ℃ from about room temperature.
In dehydrating tower 17, waste gas is further dehydrated and removes harmful gas component.By removing moisture contained in waste gas, carbon dioxide contained in the waste gas can reclaim subsequently effectively.
Waste gas is to be introduced in the dehydrating tower 17 in the lower end of dehydrating tower 17.The waste gas (for example, 5 ℃) of introducing dehydrating tower 17 is flow through by pack into the cooling agent DME that is used for cooling exhaust of dehydrating tower 17 of bubbling method.The waste gas that is incorporated into dehydrating tower 17 is by being cooled to chilling temperature with the DME heat exchange, and contained moisture and harmful gas component such as nitrogen oxide and oxysulfide are liquefied or solidify in waste gas under this temperature, and carbon dioxide does not solidify.By waste gas being cooled to this temperature, harmful gas component is liquefied or solidifies and therefore separate with waste gas, and carbon dioxide remains gas in waste gas.
In order to confirm that dehydrating tower 17 has the function that removes harmful gas component from waste gas, measure the sulfur dioxide (SO that is dissolved in cooling agent 2) and nitric oxide (NO) amount.Fig. 2 B shows the installation drawing that is used for this measurement.As shown in this Fig, the cooling simulated exhaust that this device 210 has a blender that can produce simulated exhaust 211, a simulation dehydrating tower 17 with cooled containers 212 (for example, test tube or beaker), one simulated exhaust be incorporated into the air inlet pipe 213 of cooled containers 212 and gas that will be accumulated in cooled containers 212 tops be discharged into blast pipe 214 beyond the cooled containers, they connect like that according to shown in the figure.
Cooled containers 212 contains toluene (0 to 5 ℃, the amount of 100cc) as cooling agent.Air inlet pipe is set at below the liquid level that its opening is positioned at toluene.In addition, by carbon dioxide (CO that blender mixed 2), sulfur dioxide (SO 2), nitric oxide (NO) and nitrogen (N 2) mixture as simulated exhaust.Fig. 2 C shows the composition of simulated exhaust.Under the condition that simulated exhaust is introduced with the constant speed of 1l/h, measure.
Fig. 2 D shows measurement result.In the figure, with cooling agent (toluene) temperature and sulfur dioxide (SO 2) and nitric oxide (NO) meltage (ppm) between the relation curve map measurement result is shown.Two curves drawing in this curve map are represented the sulfur dioxide (SO that calculated according to SRK (Soave-Redlich-Kwong) respectively 2) and the theoretical value of nitric oxide (NO) meltage (ppm).The circle of mark is represented the measured value obtained by measuring, sulfur dioxide (SO on curve map 2) measured value of meltage is that the measured value of 48 (ppm) and nitric oxide (NO) meltage is 0.1 (ppm).Here, under the temperature corresponding with the mark circle, sulfur dioxide (SO 2) theoretical value of meltage is that the theoretical value of 36 (ppm) and nitric oxide (NO) meltage is 0.07 (ppm).As can be seen, any one among the measured value almost conforms to its theoretical value.
Measure confirmation from above, can obtain sulfur dioxide (SO theoretically according to coolant temperature 2) and nitric oxide (NO) meltage, and can in dehydrating tower 17, harmful gas component be separated from waste gas effectively.
With DME in DME cooling tower 18, cool off and circulation-supplied in dehydrating tower 17.Circulate through DME cooling tower 18 with the cooling agent (liquid nitrogen) of circulating pump 19 40 coolings of refrigerator/heat exchanger.DME is by being cooled with the cooling agent heat exchange.
By making waste gas flow through dehydrating tower 17, DME and then contain moisture and liquefaction or the harmful gas component that solidifies is introduced in the solid-liquid separation column 20 afterwards for re-using.Be introduced in the DME knockout tower 20 DME by with the seawater indirect heat exchange temperature (for example, being elevated to-20 ℃) that raises.Under this temperature, moisture and harmful gas component are liquid or solids, and DME is a gas.Therefore, DME rises to the top of DME knockout tower 20, separates with other component thus.The DME that rises to DME knockout tower 20 tops is reclaimed and is incorporated in the DME cooling tower 18 from this place, and introduce dehydrating tower 17 again.In this way, recycle DME.Like this, by recycling cooling agent DME, the exhaust treatment system integral body of the present embodiment is operated and is efficiently utilized cooling agent.
Liquid or solid moisture and the harmful gas component from dehydrating tower 17 stayed in the DME knockout tower 20 are incorporated in the component knockout tower 22 with delivery pump 21.Introduce the moisture of component knockout tower 22 and harmful gas component by in component knockout tower 22 with the seawater indirect heat exchange temperature (for example bringing up to 5 ℃) that raises.Under this temperature, moisture and nitrogen dioxide are liquid and sulfur dioxide is gas.Sulfur dioxide gas is discharged and is incorporated into the heat exchanger 11 from component knockout tower 22 tops, thus serve as cooling agent and cool off waste gas (for example being 5 ℃) from exhaust gas source 10.By in this way sulfur dioxide being used as cooling agent, the cooling of whole system is reduced with energy consumption, realizes efficient the processing thus.
Will be as the waste gas after the cooling agent by the heat exchange temperature (being increased to for example 45 ℃) that raises, and be discharged to outside the system through chimney 51.Simultaneously, will stay liquefaction water in the component knockout tower 22 and harmful gas component such as nitrogen dioxide except that sulfur dioxide is incorporated into out in the material processing device 50.
The waste gas that comprises carbon dioxide that rises to dehydrating tower 17 tops is incorporated in the reversible heat exchanger 23.The waste gas of introducing reversible heat exchanger 23 is cooled by carry out heat exchange with waste gas from cyclone separator 25 (hereinafter description) in reversible heat exchanger 23, is introduced into then in the dry ice sublimation device 24.The waste gas of introducing in the dry ice sublimation device 24 is cooled by carry out indirect heat exchange with the cooling agent that cycles through by refrigerator/heat exchanger 40 (liquid nitrogen) in dry ice sublimation device 24.
In order to confirm the carbon dioxide (CO in the dry ice sublimation device 24 2) rate of recovery, measure carbon dioxide (CO 2) relation of the rate of recovery and analog gas temperature.Fig. 2 E, 2F show the layout of the dry ice sublimation device 24 that is used for this measurement.Fig. 2 E is that the side view of dry ice sublimation device 24 and Fig. 2 F are the side views of the dry ice sublimation device 24 seen by arrow A direction indication among Fig. 2 E.As shown in the figure, dry ice sublimation device 24 comprises two upright first cylinders of arranging 241 (for example being made by SUS304), horizontally disposed under first cylinder 241 (that is) second cylinder 242, perpendicular to first cylinder 241, the inside UNICOM of it and first cylinder 241.In first cylinder 241, be furnished with the coolant flow tubes 244 (material: copper that cooling agent (for example liquid nitrogen) cycles through; Long 900mm, 20 circles, external area 7.1m 2).Forming helical form fin (not shown) on coolant flow tubes 244 outer surfaces increases and carbon dioxide (CO 2) contact area.Each personal stopper 246 sealing of the two ends end of first cylinder 241 and second cylinder 242.
15% carbon dioxide (CO 2) and 85% nitrogen (N 2) mixture as analog gas.The outlet 249 that the inlet 248 that sets from the pre-position of one of first cylinder 241 with 670 liters/minute flow velocity when analog gas is introduced and set from the pre-position of another first cylinder 241 is discharged and is measured when making it flow through equipment.The analog gas of introducing dry ice sublimation device 24 inner spaces 247 contacts to be cooled to by the outside with coolant flow tubes 244 and can make carbon dioxide (CO 2) solidify but nitrogen (N 2) temperature that can not solidify.Like this, the carbon dioxide in the analog gas just becomes dry ice, is deposited in second cylinder 242.Simultaneously, the nitrogen component in the analog gas is discharged from exporting 249.
Fig. 2 G shows measurement result.In the figure, use carbon dioxide (CO 2) concentration is 15% analog gas, with graphical representation from exporting the temperature and the carbon dioxide (CO of 249 analog gas of discharging 2) relation between the rate of recovery.Shown in this measurement result, confirmed to reclaim carbon dioxide (CO effectively with dry ice sublimation device 24 2).
The dry ice that produces in the dry ice sublimation device 24 is introduced cyclone separator 25, separate dry ice and waste gas.Wherein, waste gas is introduced in the reversible heat exchanger 23 and plays the cooling agent effect as previously mentioned.Because institute's waste gas cooled is as the cooling agent in the reversible heat exchanger 23 in the dry ice sublimation device 24, the cooling energy consumption of whole system is reduced, and has therefore realized efficient processing.The waste gas that is used as cooling agent in the reversible heat exchanger 23 is introduced heat exchanger 11 and in heat exchanger 11, be used as cooling agent once more.Then, by chimney 51 it is discharged into beyond the system.Discharge the exhaust in the atmosphere be for a part of toxic emission beyond the system to reduce waste gas gathering in system.Therefore, it is very low to be discharged in the waste gas of atmosphere concentration of carbon dioxide.
25 isolated dry ice of cyclone separator are introduced in the dry ice melting unit 26, made dry ice pressurization and liquefaction.By with dry ice liquefaction, carbon dioxide is being improved aspect storability and the conveying property, and become and be easy to disposal.For a large amount of dry ice that produce that liquefy efficiently, a kind of in Japanese Patent Application Publication publication No.2000-317302 etc. the equipment or the similar devices of disclosed employing screw type ejecting mechanism can be used as dry ice melting unit 26.Carbon dioxide after the liquefaction is stored in the liquefaction carbonic acid storage tank 27 and can be used as liquefaction carbonic acid and is used for various purposes.
If the layout that comprises dry ice sublimation device 24, cyclone separator 25 and dry ice melting unit 26 that need not be shown in Figure 1, can change the layout of the dry ice sublimation device 24 that adopts Fig. 2 E, in this case, can use first cylinder 241 more than three or three, be not limited to they two.
Here, refrigerator 40 is by utilizing energy such as electric energy and compress repeatedly and expansion nitrogen making nitrogen be cooled to cooling agent.The liquid nitrogen that cooling down operation produced be used to cool off via the ethylene glycol of heat exchanger 11 circulations with cooling agent is for example cooled off through the liquid nitrogen of the different passages in the office of liquid nitrogen therewith of circulations such as DME cooling tower 18, dry ice sublimation device 24.The refrigeration plant 43 that refrigerator 40 comprises turbocompressor 41 (nitrogen supercharging equipment), circulating nitrogen gas compressor 42, the cooling agent that is used to expand obtains low temperature, carry out heat exchanger 44 of exchange heat or the like as cooling agent and ethylene glycol with by the liquid nitrogen of other channel cycle with liquid nitrogen.
As mentioned above, effectively remove moisture and harmful gas component the waste gas that comprises harmful gas component such as nitrogen oxide and oxysulfide that the exhaust treatment system of the present embodiment can discharge from blast furnace, coke oven or the converter of coal-burning boiler, heavy oil combustion boiler or iron-smelter, and can when effectively removing moisture and harmful gas component, from waste gas, reclaim carbon dioxide effectively.
Here, the pernicious gas that need remove from waste gas for example comprises carbon monoxide, nitrogen oxide (NO x) as nitric oxide, oxysulfide (SO x) as sulfur monoxide and halogen compounds such as hydrogen fluoride.The setting temperature by suitable setting carbon dioxide and the liquefaction or the setting temperature of harmful gas component are also selected suitable cooling agent, can remove harmful gas component effectively.That is to say, make it to be cooled to first temperature by allowing the waste gas that comprises another type pernicious gas flow through cooling agent, contained pernicious gas is liquefied or solidifies and separate from waste gas in this waste gas, and by waste gas being cooled to second temperature that is lower than first temperature, make carbon dioxide contained in the waste gas be solidified and from waste gas, separate, be achieved this exhaust treatment system like this.
=the second embodiment=
Fig. 3 shows the schematic diagram according to the exhaust treatment system of second embodiment of the invention.The exhaust treatment system of the present embodiment provides an energy can effectively remove the technological process of contained humidity and harmful gas component in the waste gas from exhaust gas source 10 simultaneously as effectively reclaiming institute's carbonated the waste gas that comprises harmful gas component such as nitrogen oxide of combustion LNG boiler emissions such as power plant, chemical plant installations.
In the exhaust treatment system of this programme, in its preprocessing process, will be incorporated into from the waste gas that comprises harmful gas component such as nitrogen oxide of exhaust gas source 10 discharging the heat exchanger 11 contained water for industrial use and condenser 13, thereby about cool to room temperature.Then, in first process, in dehydrating tower 17, be cooled to first temperature that carbon dioxide is solidified, thereby make in the waste gas contained humidity and nitrogen oxide liquefaction or solidify and from waste gas, separate being cooled to waste gas about room temperature.Then, in second process, the waste gas of isolating moisture and nitrogen oxide is cooled to second temperature lower than first temperature in dry ice sublimation device 24, thereby carbon dioxide contained in the waste gas is solidified and from waste gas, separates.
Isolated harmful gas component and cooling agent mix in first process.Preferably cooling agent is circulated and is effectively used, so that can operate exhaust treatment system efficiently.Therefore, in this embodiment, utilize the evaporating temperature between cooling agent and the harmful gas component poor, the employing method of evaporating makes cooling agent separate with harmful gas component and is recovered, and the cooling agent that reclaims is used as cooling agent once more.Need heat energy although it is pointed out that method of evaporating, can reduce this heat energy by adopting the low boiling cooling agent.
In order to reclaim carbon dioxide contained in the waste gas effectively in second process, carbon dioxide must be able to not liquefy or solidify when liquefying or solidifying moisture and harmful gas component.Carbon dioxide in the combustion LNG boiler waste gas can be frozen into dry ice when being lower than predetermined temperature.Therefore, in order not allow carbon dioxide solidify, the gas temperature in dehydrating tower 17 exits must be higher than this predetermined temperature.
In first process, require cooling agent harmful gas component be liquefied or the temperature of solidifying under itself do not solidify so that from liquefaction or the harmful gas component that solidifies, isolate cooling agent.In addition, in order to liquefy effectively or to solidify harmful gas component, require cooling agent to have the characteristic of easy absorption harmful gas component.And,, require cooling agent to have carbon dioxide and be difficult for dissolving performance wherein in order in second process, from waste gas, to reclaim carbon dioxide effectively.
The specific cooling agent that satisfies these requirements be dimethyl ether (below be called DME, cold point :-141.5 ℃, boiling point :-24.9 ℃).Can use except that dimethyl ether other material as cooling agent, as long as they satisfy the requirement of cooling agent.For example, can satisfy the inorganic salts (sodium chloride of these requirements, potassium chloride etc.), bromine compounds (lithium bromide, bromo bromide (bromobromide), or the like), ether (dimethyl ether, methyl ether etc.), alcohol (methyl alcohol, ethanol etc.), silicone oil, paraffin hydrocarbon (propane, butane etc.), olefin(e) etc. can be used as cooling agent.For the harmful gas component that will liquefy or solidify separates with cooling agent, there is very big boiling-point difference more favourable between cooling agent and harmful gas component.Consider that from this type of viewpoint ether and alcohol are preferably as cooling agent.
It is 10% the analog gas measurement result that gas concentration lwevel changes in the analog gas when flowing through DME according to embodiments of the present invention that Fig. 4 A shows when making gas concentration lwevel.As shown in this Fig, when analog gas began to flow through DME, concentration of carbon dioxide temporarily descended in the analog gas because analog gas is dissolved among the DME, after a period of time, became the concentration (10%) when cycling through before the DME gradually.This be because carbon dioxide in DME saturated after, almost no longer include carbon dioxide and be dissolved in DME.In order to confirm that DME easily absorbs harmful gas component such as nitrogen oxide, the inventor has done one and has allowed and comprise harmful gas component (ammonia: analog gas 10ppm) cycles through the experiment of DME for nitrogen dioxide: 60ppm, sulfur dioxide: 80ppm.The result has confirmed in after analog gas begins to flow through DME about 1 hour that all harmful gas component concentration become 1ppm or lower in the analog gas.
Then, describe the idiographic flow of the exhaust treatment system of the present embodiment in detail.At first, in preliminary treatment, be introduced in the heat exchanger 11 from the waste gas that comprises harmful gas component such as nitrogen oxide of exhaust gas source 10 as combustion LNG boiler emission, in heat exchanger 11, introduced by the seawater (for example, 25 ℃) of sea water pump 12 supplies and cooling agent such as the ethylene glycol that comes from refrigerator 40 circulations.The waste gas of introducing from exhaust gas source 10 (for example 55 ℃) pass heat exchanger 11 therefore and by seawater and coolant cools to the room temperature.
The waste gas that will be cooled in heat exchanger 11 about room temperature is incorporated in the condenser 13 subsequently, and the waste gas that will introduce condenser 13 imports in the contained water for industrial use of condenser 13.Thus, moisture contained in the waste gas, harmful gas component, dust and analog are removed.The liquefaction water that comprises moisture, harmful gas component, dust and analog that shifts out from waste gas temporarily is stored in the discharging storage tank 14, is incorporated into out in the material processing device 50 with discharging pump 15 subsequently.The waste gas that will pass condenser 13 at last is incorporated in the dehydrating tower 17 with exhaust gas blower 16.It is pointed out that in condenser 13 heat exchange with water for industrial use makes (for example 5 ℃) about the waste gas cool to room temperature.
In dehydrating tower 17, waste gas is further dehydrated and removes harmful gas component.By removing moisture contained in waste gas, carbon dioxide contained in the waste gas can reclaim subsequently effectively.
Waste gas is to be introduced in the dehydrating tower 17 in the lower end of dehydrating tower 17.The waste gas (for example, 5 ℃) of introducing dehydrating tower 17 is flow through by pack into the cooling agent DME that is used for cooling exhaust of dehydrating tower 17 of bubbling method.The waste gas that is incorporated into dehydrating tower 17 is by being cooled to chilling temperature with the DME heat exchange, and contained moisture and harmful gas component such as nitrogen oxide are liquefied or solidify in waste gas under this temperature, and carbon dioxide does not solidify.By waste gas being cooled to this temperature, harmful gas component is liquefied or solidifies and therefore separate with waste gas, and carbon dioxide remains gas in waste gas.
In order to confirm that dehydrating tower 17 has the function that removes harmful gas component from waste gas, measure the sulfur dioxide (SO that is dissolved in cooling agent 2) and nitric oxide (NO) amount.Fig. 4 B shows the installation drawing that is used for this measurement.As shown in this Fig, the cooling simulated exhaust that this device 210 has a blender that can produce simulated exhaust 211, a simulation dehydrating tower 17 with cooled containers 212 (for example, test tube or beaker), one simulated exhaust be incorporated into the air inlet pipe 213 of cooled containers 212 and gas that will be accumulated in cooled containers 212 tops be discharged into blast pipe 214 beyond the cooled containers, they connect like that according to shown in the figure.
Cooled containers 212 contains toluene (0 to 5 ℃, the amount of 100cc) as cooling agent.Air inlet pipe is set at below the liquid level that its opening is positioned at toluene.In addition, by carbon dioxide (CO that blender mixed 2), sulfur dioxide (SO 2), nitric oxide (NO) and nitrogen (N 2) mixture as simulated exhaust.Fig. 4 C shows the composition of simulated exhaust.Under the condition that simulated exhaust is introduced with the constant speed of 1l/h, measure.
Fig. 4 D shows measurement result.In the figure, with cooling agent (toluene) temperature and sulfur dioxide (SO 2) and nitric oxide (NO) meltage (ppm) between the relation curve map measurement result is shown.Two curves drawing in this curve map are represented the sulfur dioxide (SO that calculated according to SRK (Soave-Redlich-Kwong) respectively 2) and the theoretical value of nitric oxide (NO) meltage (ppm).The circle of mark is represented the measured value obtained by measuring, sulfur dioxide (SO on curve map 2) measured value of meltage is that the measured value of 48 (ppm) and nitric oxide (NO) meltage is 0.1 (ppm).Here, under the temperature corresponding with the mark circle, sulfur dioxide (SO 2) theoretical value of meltage is that the theoretical value of 36 (ppm) and nitric oxide (NO) meltage is 0.07 (ppm).As can be seen, any one among the measured value almost conforms to its theoretical value.
Measure confirmation from above, can obtain sulfur dioxide (SO theoretically according to coolant temperature 2) and nitric oxide (NO) meltage, and can in dehydrating tower 17, harmful gas component be separated from waste gas effectively.
Will be in dehydrating tower 17 from the DME circulation-supplied of the DME cooling tower 18 used of cooling DME.Circulate through DME cooling tower 18 with the cooling agent (liquid nitrogen) of circulating pump 19 44 coolings of refrigerator/heat exchanger.DME is by being cooled with the cooling agent heat exchange.
By making waste gas flow through dehydrating tower 17, DME and then contain moisture and liquefaction or the harmful gas component that solidifies is introduced in the solid-liquid separation column 28 subsequently.Attention is in this stage, and DME and moisture and harmful gas component coagulum are in husky ice state (slurry).Solid-liquid separation column 28 is separated DME and moisture and harmful gas component coagulum.28 isolated DME are introduced in DME knockout tower 20 so that re-use this DME by solid-liquid separation column.The DME that is introduced in DME knockout tower 20 can more residual moisture and harmful gas component.
The DME that is incorporated into DME knockout tower 20 from dehydrating tower 17 is by elevate the temperature with the seawater indirect heat exchange (for example being elevated to 5 ℃).Under this temperature, moisture and harmful gas component are liquid or solids, and DME is a gas.Therefore, DME gas rises to the top of DME knockout tower 20, separated thus going out.The DME that rises to DME knockout tower 20 tops is reclaimed and is incorporated in the DME cooling tower 18 from this place, and introduce dehydrating tower 17 again.In this way, recycle DME.Like this, by recycling cooling agent DME, the exhaust treatment system integral body of the present embodiment is operated and is efficiently utilized cooling agent.Simultaneously, liquid or solid moisture and the harmful gas component of staying in the DME knockout tower 20 is incorporated into out in the material processing device 50.
The waste gas that comprises carbon dioxide that rises to dehydrating tower 17 tops is incorporated in the reversible heat exchanger 23.The waste gas of introducing reversible heat exchanger 23 is cooled by carry out heat exchange with waste gas from cyclone separator 25 (hereinafter description) in reversible heat exchanger 23, is introduced into then in the dry ice sublimation device 24.The waste gas of introducing in the dry ice sublimation device 24 is cooled by carry out indirect heat exchange with the cooling agent that cycles through by refrigerator/heat exchanger 40 (liquid nitrogen) in dry ice sublimation device 24.
In order to confirm the carbon dioxide (CO in the dry ice sublimation device 24 2) rate of recovery, measure carbon dioxide (CO 2) relation of the rate of recovery and analog gas temperature.Fig. 4 E, 4F show the layout of the dry ice sublimation device 440 that is used for this measurement.Fig. 4 E is that the side view of dry ice sublimation device 440 and Fig. 4 F are the side views of the dry ice sublimation device 440 seen by arrow A direction indication among Fig. 4 E.As shown in the figure, dry ice sublimation device 440 comprises two upright first cylinders of arranging 441 (for example being made by SUS304), horizontally disposed under first cylinder 441 (that is) second cylinder 442, perpendicular to first cylinder 441, the inside UNICOM of it and first cylinder 441.In first cylinder 441, be furnished with the coolant flow tubes 444 (material: copper that cooling agent (for example liquid nitrogen) cycles through; Long 900mm, 20 circles, external area 7.1m 2).Forming helical form fin (not shown) on coolant flow tubes 444 outer surfaces increases and carbon dioxide (CO 2) contact area.Each personal stopper 446 sealing of the two ends of first cylinder 441 and second cylinder 442.
15% carbon dioxide (CO 2) and 85% nitrogen (N 2) mixture as analog gas.The outlet 449 that the inlet 448 that sets from the pre-position of one of first cylinder 441 with 670 liters/minute flow velocity when analog gas is introduced and set from the pre-position of another first cylinder 441 is discharged and is measured when making it flow through equipment.The analog gas of introducing dry ice sublimation device 440 inner spaces 447 contacts to be cooled to by the outside with coolant flow tubes 444 and can make carbon dioxide (CO 2) solidify but nitrogen (N 2) temperature that can not solidify.Like this, the carbon dioxide in the analog gas just becomes dry ice, is deposited in second cylinder 442.Simultaneously, the nitrogen component in the analog gas is discharged from exporting 449.
Fig. 4 G shows measurement result.In the figure, use carbon dioxide (CO 2) concentration is 15% analog gas, with graphical representation from exporting the temperature and the carbon dioxide (CO of 449 analog gas of discharging 2) relation between the rate of recovery.Shown in this measurement result, confirmed to reclaim carbon dioxide (CO effectively with dry ice sublimation device 24 2).
The dry ice that produces in the dry ice sublimation device 24 is introduced cyclone separator 25, separate dry ice and waste gas.Wherein, waste gas is introduced in the reversible heat exchanger 23 and plays the cooling agent effect as previously mentioned.Because institute's waste gas cooled is as the cooling agent in the reversible heat exchanger 23 in the dry ice sublimation device 24, the cooling energy consumption of whole system is reduced, and has therefore realized efficient processing.The waste gas that is used as cooling agent in the reversible heat exchanger 23 is introduced heat exchanger 11 and in heat exchanger 11, be used as cooling agent once more.Then, by chimney 51 it is discharged into beyond the system.Discharge the exhaust in the atmosphere be for a part of toxic emission beyond the system to reduce waste gas gathering in system.Therefore, it is very low to be discharged in the waste gas of atmosphere concentration of carbon dioxide.
25 isolated dry ice of cyclone separator are introduced in the dry ice melting unit 26, made dry ice pressurization and liquefaction.By with dry ice liquefaction, carbon dioxide is being improved aspect storability and the conveying property, and become and be easy to disposal.For a large amount of dry ice that produce that liquefy efficiently, a kind of in Japanese Patent Application Publication publication No.2000-317302 etc. the equipment or the similar devices of disclosed employing screw type ejecting mechanism can be used as dry ice melting unit 26.Carbon dioxide after the liquefaction is stored in the liquefaction carbonic acid storage tank 27 and can be used as liquefaction carbonic acid and is used for various purposes.
If the layout that comprises dry ice sublimation device 24 and cyclone separator 25 that need not be shown in Figure 3, can change the layout of the dry ice sublimation device 440 that adopts Fig. 4 E, in this case, can use first cylinder 441 more than three or three, be not limited to they two.
Here, by utilizing the heat of evaporation of LNG 60, the ethylene glycol that refrigerator/heat exchanger 44 will cycle through heat exchanger 11 cools off with the cooling agent such as the liquid nitrogen that cycle through DME cooling tower 18, dry ice sublimation device 24 etc.For example in using the power plant of LNG as gaseous fuel, LNG transports and is stored in LNG jar or the similar devices under the liquid state of-165 ℃ of temperature at-150 ℃.When LNG when the gaseous fuel, LNG obtains heat of evaporation raise temperature and gasification from atmosphere or seawater, refrigerator/heat exchanger 44 utilizes this heat of evaporation to cool off cooling agent such as ethylene glycol and liquid nitrogen simultaneously.That is to say that waste gas or cooling agent are that the heat of evaporation that is produced when utilizing LNG to be used as gaseous fuel is cooled off.By the heat of evaporation of using LNG solidify with separate waste gas in the technology of contained carbon dioxide for example be disclosed among the Japanese Patent Application Publication publication No.H08-12314 etc.
As mentioned above, the exhaust treatment system of the present embodiment can effectively remove moisture and harmful gas component from the waste gas that comprises harmful gas component such as nitrogen oxide of combustion LNG boiler or similar devices discharging, and can reclaim carbon dioxide when effectively removing moisture and harmful gas component from waste gas effectively.
Here, the pernicious gas that need remove from waste gas for example comprises carbon monoxide, nitrogen oxide (NO x) as nitric oxide, oxysulfide (SO x) as sulfur monoxide and halogen compounds such as hydrogen fluoride.The setting temperature by suitable setting carbon dioxide and the liquefaction or the setting temperature of harmful gas component are also selected suitable cooling agent, can remove harmful gas component effectively.That is to say, make it to be cooled to first temperature by allowing the waste gas that comprises another type pernicious gas flow through cooling agent, contained pernicious gas is liquefied or solidifies and separate from waste gas in this waste gas, and by waste gas being cooled to second temperature that is lower than first temperature, make carbon dioxide contained in the waste gas be solidified and from waste gas, separate, be achieved this exhaust treatment system like this.
=the three embodiment=
Fig. 5 shows the schematic diagram according to the exhaust treatment system of third embodiment of the invention.The exhaust treatment system of the present embodiment provides an energy effectively to reclaim the technological process that institute's carbonated can effectively remove contained humidity and harmful gas component in the waste gas simultaneously from the waste gas that comprises harmful gas component such as nitrogen oxide and oxysulfide of exhaust gas source 10 as dischargings such as the blast furnace of the coal-burning boiler of power plant, chemical plant installations etc. or burning heavy oil boiler and iron-smelter, coke oven, converters.
In the exhaust treatment system of this programme, in its preprocessing process, to be incorporated into from the waste gas that comprises harmful gas component such as nitrogen oxide and oxysulfide of exhaust gas source 10 discharging the heat exchanger 11 contained water for industrial use and condenser 13, thereby about cool to room temperature.Then, in first process, in dehydrating tower 17, be cooled to first temperature that carbon dioxide is solidified, thereby make contained humidity in the waste gas, oxysulfide and nitrogen oxide liquefaction or solidify and from waste gas, separate being cooled to waste gas about room temperature.Then, in second process, the waste gas of therefrom isolating moisture, nitrogen oxide and oxysulfide is introduced in the carbon dioxide separator 30, made carbon dioxide cooling contained in the waste gas and solidify it is separated, then with the co 2 liquefaction and the discharging of separating.
Although isolated harmful gas component and cooling agent mix in first process.But preferably cooling agent is circulated and is effectively used, so that can operate exhaust treatment system efficiently.Therefore, in the present embodiment, utilize the evaporating temperature between cooling agent and the harmful gas component poor, the employing method of evaporating makes cooling agent separate with harmful gas component and is recovered, and the cooling agent that reclaims is used as cooling agent once more.Need heat energy although it is pointed out that method of evaporating, can reduce this heat energy by adopting the low boiling cooling agent.
In order to reclaim carbon dioxide contained in the waste gas effectively in second process, carbon dioxide must be able to not liquefy or solidify when liquefying or solidifying moisture and harmful gas component.Carbon dioxide in the thermo-power station waste gas can be frozen into dry ice when being lower than predetermined temperature.Therefore, in order not allow carbon dioxide solidify, the gas temperature in dehydrating tower 17 exits must be higher than this predetermined temperature.
In first process, require cooling agent harmful gas component be liquefied or the temperature of solidifying under itself do not solidify so that from liquefaction or the harmful gas component that solidifies, isolate cooling agent.In addition, in order to liquefy effectively or to solidify harmful gas component, require cooling agent to have the characteristic of easy absorption harmful gas component.And,, require cooling agent to have carbon dioxide and be difficult for dissolving performance wherein in order in second process, from waste gas, to reclaim carbon dioxide effectively.
The specific cooling agent that satisfies these requirements is dimethyl ether (below be called DME).Can use except that dimethyl ether other material as cooling agent, as long as they satisfy the requirement of cooling agent.For example, can satisfy the inorganic salts (sodium chloride of these requirements, potassium chloride etc.), bromine compounds (lithium bromide, bromo bromide (bromo bromide), or the like), ether (dimethyl ether, methyl ether etc.), alcohol (methyl alcohol, ethanol etc.), silicone oil, paraffin hydrocarbon (propane, butane etc.), olefin(e) etc. can be used as cooling agent.For the harmful gas component that will liquefy or solidify separates with cooling agent, there is very big boiling-point difference more favourable between cooling agent and harmful gas component.Consider that from this type of viewpoint ether and alcohol are preferably as cooling agent.
It is 10% the analog gas measurement result that gas concentration lwevel changes in the analog gas when flowing through DME according to embodiments of the present invention that Fig. 6 shows when making gas concentration lwevel.As shown in this Fig, when analog gas began to flow through DME, concentration of carbon dioxide temporarily descended in the analog gas because analog gas is dissolved among the DME, after a period of time, became the concentration (10%) when cycling through before the DME gradually.This be because carbon dioxide in DME saturated after, almost no longer include carbon dioxide and be dissolved in DME.In order to confirm that DME easily absorbs harmful gas component such as nitrogen oxide and oxysulfide, the inventor has done one and has allowed and comprise harmful gas component (ammonia: analog gas 10ppm) cycles through the experiment of DME for nitrogen dioxide: 60ppm, sulfur dioxide: 80ppm.The result has confirmed in after analog gas begins to flow through DME about 1 hour that all harmful gas component concentration become 1ppm or lower in the analog gas.
Then, describe the idiographic flow of the exhaust treatment system of the present embodiment in detail.At first, in preliminary treatment, be introduced in the heat exchanger 11 from the waste gas that comprises harmful gas component such as nitrogen oxide and oxysulfide of exhaust gas source 10 dischargings, in heat exchanger 11, introduced by the seawater (for example, 25 ℃) of sea water pump 12 supplies and cooling agent such as the ethylene glycol that comes from refrigerator 40 circulations.The waste gas of introducing from exhaust gas source 10 (for example 55 ℃) pass heat exchanger 11 and by seawater and coolant cools to the room temperature.
The waste gas that will be cooled in heat exchanger 11 about room temperature is incorporated in the condenser 13 subsequently, and the waste gas that will introduce condenser 13 imports in the contained water for industrial use of condenser 13.Thus, moisture contained in the waste gas, harmful gas component, dust and analog are removed.The liquefaction water that comprises moisture, harmful gas component, dust and analog that shifts out from waste gas temporarily is stored in the discharging storage tank 14, is incorporated into out in the material processing device 50 with discharging pump 15 subsequently.The waste gas that will pass condenser 13 at last is incorporated in the dehydrating tower 17 with exhaust gas blower 16.It is pointed out that in condenser 13 heat exchange with water for industrial use makes waste gas be cooled to for example 5 ℃ from about room temperature.
In dehydrating tower 17, waste gas is further dehydrated and removes harmful gas component.By removing moisture contained in waste gas, carbon dioxide contained in the waste gas can reclaim subsequently effectively.
Waste gas is to be introduced in the dehydrating tower 17 in the lower end of dehydrating tower 17.The waste gas (for example, 5 ℃) of introducing dehydrating tower 17 is flow through by pack into the cooling agent DME that is used for cooling exhaust of dehydrating tower 17 of bubbling method.The waste gas that is incorporated into dehydrating tower 17 is by being cooled to chilling temperature with the DME heat exchange, and contained moisture and harmful gas component such as nitrogen oxide and oxysulfide are liquefied or solidify in the waste gas under this temperature, and carbon dioxide does not solidify.By waste gas being cooled to this temperature, harmful gas component is liquefied or solidifies and therefore separate with waste gas, and carbon dioxide remains gas in waste gas.
Will be in dehydrating tower 17 from the DME circulation-supplied of DME cooling tower 18.With circulating pump 19 cooling agent (liquid nitrogen) circulation that refrigerator 40 cools off is supplied to DME cooling tower 18.In DME cooling tower 18, DME is by being cooled with the cooling agent heat exchange.
The DME that flows through dehydrating tower 17 is incorporated in the DME knockout tower 20.This DME contains the harmful gas component of moisture and liquefaction or curing.Be introduced in the DME knockout tower 20 DME by with the seawater indirect heat exchange temperature (for example, being elevated to-20 ℃) that raises.Under this temperature, moisture and harmful gas component are liquid or solids, and DME is a gas.Therefore, DME rises to the top of DME knockout tower 20, separates with other component thus.The DME that rises to DME knockout tower 20 tops is reclaimed and is incorporated in the DME cooling tower 18 from this place, and introduce dehydrating tower 17 again.In this way, recycle DME.Like this, by recycling cooling agent DME, the exhaust treatment system integral body of the present embodiment is operated and is efficiently utilized cooling agent.
Liquid or solid moisture and the harmful gas component stayed in the DME knockout tower 20 are incorporated in the component knockout tower 22 with delivery pump 21.Introduce the moisture of component knockout tower 22 and harmful gas component by in component knockout tower 22 with the seawater indirect heat exchange temperature (for example bringing up to 5 ℃) that raises.Under this temperature, moisture and nitrogen dioxide are liquid and sulfur dioxide is gas.Sulfur dioxide gas is discharged and is incorporated into the heat exchanger 11 from component knockout tower 22 tops, thus serve as cooling agent and cool off waste gas (for example being 55 ℃) from exhaust gas source 10.By in this way sulfur dioxide being used as cooling agent, the cooling of whole system is reduced with energy consumption, realizes efficient the processing thus.
Will be as the waste gas after the cooling agent by the heat exchange temperature (being increased to for example 45 ℃) that raises, and be discharged to outside the system through chimney 51.Simultaneously, will stay liquefaction water in the component knockout tower 22 and harmful gas component such as nitrogen dioxide except that sulfur dioxide is incorporated into out in the material processing device 50.
The waste gas that comprises carbon dioxide that rises to dehydrating tower 17 tops is incorporated in the reversible heat exchanger 23.The waste gas of introducing reversible heat exchanger 23 is cooled therein and is incorporated in the carbon dioxide separator 30.Carbon dioxide separator 30 is separated carbon dioxide and is liquefied from waste gas, with isolated carbon dioxide discharging.The detailed placement and the effect of carbon dioxide separator 30 will be explained below.
Carbon dioxide after the liquefaction is transferred and is stored in the liquefaction carbonic acid storage tank 27.The waste gas that simultaneously will be therefrom isolate carbon dioxide in carbon dioxide separator 30 is introduced in the reversible heat exchanger 23 as cooling agent, and then introduces in the heat exchanger 11.After in heat exchanger 11, being used as cooling agent, with waste gas in chimney 51 is discharged into atmosphere outside the system.Discharge the exhaust in the atmosphere be for a part of toxic emission beyond the system to reduce waste gas gathering in system.Therefore, it is very low to be discharged in the waste gas of atmosphere concentration of carbon dioxide.
Here, refrigerator 40 is by utilizing energy such as electric energy and compress repeatedly and expansion nitrogen making nitrogen be cooled to cooling agent.The liquid nitrogen that cooling down operation produced be used to cool off via the ethylene glycol of heat exchanger 11 circulations with cooling agent is for example cooled off through the liquid nitrogen of the different passages in the office of liquid nitrogen therewith of circulations such as DME cooling tower 18, dry ice sublimation device 24.The refrigeration plant 43 that refrigerator 40 comprises turbocompressor 41 (nitrogen supercharging equipment), circulating nitrogen gas compressor 42, the cooling agent that is used to expand obtains low temperature, carry out heat exchanger 44 of exchange heat or the like as cooling agent and ethylene glycol with by the liquid nitrogen of other channel cycle with liquid nitrogen.
As mentioned above, effectively remove moisture and harmful gas component the waste gas that comprises harmful gas component such as nitrogen oxide and oxysulfide that the exhaust treatment system of the present embodiment can discharge from blast furnace, coke oven or the converter of coal-burning boiler, heavy oil combustion boiler or iron-smelter, and can when effectively removing moisture and harmful gas component, from waste gas, reclaim carbon dioxide effectively.
Here, the pernicious gas that need remove from waste gas for example comprises carbon monoxide, nitrogen oxide (NO x) as nitric oxide, oxysulfide (SO x) as sulfur monoxide and halogen compounds such as hydrogen fluoride.The setting temperature by suitable setting carbon dioxide and the liquefaction or the setting temperature of harmful gas component are also selected suitable cooling agent, can remove harmful gas component effectively.That is to say, make it to be cooled to first temperature by allowing the waste gas that comprises another type pernicious gas flow through cooling agent, contained pernicious gas is liquefied or solidifies and separate from waste gas in this waste gas, and by waste gas being cooled to second temperature that is lower than first temperature, make carbon dioxide contained in the waste gas be solidified and from waste gas, separate, be achieved this exhaust treatment system like this.
＜carbon dioxide separator 30 〉
Describe the layout and the effect of carbon dioxide separator 30 below in detail.Fig. 7 illustrates the layout of carbon dioxide separator 30 according to embodiments of the present invention.In the figure, pressure vessel 310 is to be the container of rectangle substantially by what metal (for example stainless steel) was made, and length and width and Gao Yue have several meters.Leave a gas access 321 so that the waste gas of drawing from reversible heat exchanger 23 flows into through this in the pre-position of pressure vessel 310 end faces.And, leave a gas vent 322 in the precalculated position of pressure vessel 310 bottom surfaces so that in the waste gas component outside the removing carbon dioxide emit.And a liquid outlet 323 is left so that the liquefied carbon dioxide of pressure vessel 310 bottoms accumulation is discharged in the pre-position that separates with gas vent 322 in pressure vessel 310 bottom surfaces.For making through the gas access 321 waste gas that flow into stop preset time or for more time in pressure vessel 310, gas vent 322 is opened at one has the position of preset distance with gas access 321.
The pipeline (gas inflow pipe 331) that is connected to gas access 321 is equipped with a control valve 341 that is used for regulating the waste gas influx.And the pipeline (gas discharge pipe 332) that is connected to gas vent 322 is equipped with a control valve 342 that is used for regulating discharge amount of exhaust gas.And the pipeline (liquid discharge tube 333) that is connected to liquid outlet 323 is equipped with a control valve 343 that is used for regulating liquid carbon dioxide output.By closing whole control valves 341,342,343, then this pressure vessel 310 is in hermetic closed state.
In pressure vessel 310, dispose the coolant flow tubes (cooler) 312 that metal (for example copper or stainless steel) is made, as the liquid nitrogen (LN of cooling agent 2) circulate through this pipe.Liquid nitrogen as cooling agent is provided by refrigerator 40.The control valve 341 that is used to control coolant flow is contained in the upstream of coolant flow tubes 312.And flowing through in order to ensure coolant flow tubes 312 has enough contacts area between the waste gas of pressure vessel 310, is divided into two parts coolant flow tubes 312.Coolant flow tubes 312 is back-shaped arranging in this pressure vessel, further guaranteed thus and gas between enough contacts area are arranged.
Heat-transfer pipe (heat-transfer equipment) 313 is embedded in the wall of pressure vessel 310.The heating medium flow that a control valve (not shown) is controlled the heat-transfer pipe 313 of flowing through is equipped with in the upstream of heat-transfer pipe 313.Heat medium for example is dry air and is to be transported to heat-transfer pipe 313 from thermal source 314.Circulate next cooling agent as heat medium by using from refrigerator 40, and then the energy of whole system is effectively used.If heat-transfer pipe 313 is not to imbed in the wall of pressure vessel 310, then replaceable one-tenth is contained in it in pressure vessel 310.In addition, if without heat-transfer pipe 313, then can change into and use electric heater (for example, silicon rubber heater or fluororesin heater).
Pressure vessel 310 is equipped with various sensors as the sensor of measuring gas temperature in the pressure vessel 310 and the sensor of measuring coolant flow tubes 312 surface temperatures.The output valve of each sensor is imported in measurement device or the computer (not shown) and by the operator and monitors.A wicket (not shown) is housed in the pre-position of pressure vessel 310, sees through the inside that this window can be observed pressure vessel 310.
To the method for the carbon dioxide separation in the waste gas being come out with carbon dioxide separator 30 be described with reference to technological process shown in Figure 8.Suppose that under original state control valve 341,342,343 all is closed (S801).
At first, open control valve 344, cooling agent (liquid nitrogen) begins to flow through coolant flow tubes 312 (S802).Here, the surface temperature of coolant flow tubes 312 will be reduced to and carbon dioxide solidified and temperature that harmful gas component such as nitrogen oxide can not liquefy.Fig. 9 is T-P (temperature and pressure) figure of carbon dioxide.As shown in the drawing, the sublimation point of carbon dioxide is-78.5 ℃ under 1 atmospheric pressure.Therefore, if be assumed to be 1 atmospheric pressure, then the surface temperature of coolant flow tubes 312 is at least-78.5 ℃ or lower.
When the surface temperature of coolant flow tubes 312 reaches said temperature, then open control valve 341,342, with the gas of desiring the to isolate carbon dioxide control valve 341 of flowing through, begin to flow through pressure vessel 310 (S803).The gas that flows through pressure vessel 310 312 coolings of agent stream pipe that are cooled, thus make carbon dioxide contained in the gas precipitate into dry ice 350 (S804) in the outside of coolant flow tubes 312.Simultaneously, the waste gas of inflow pressure vessel 310 flows through pressure vessel 310 and discharges outside the pressure vessels 310 (S805) via control valve 342.
When the amount of the dry ice 350 of coolant flow tubes 312 surface precipitations has reached scheduled volume (S806: be), then closed control valve 341,342 comes bubble-tight shut-off pressure vessel 310 (S807).In addition, closed control valve 344 stops cooling agent (liquid nitrogen) and flows through coolant flow tubes 312 (S808).It is inner or determine according to the method whether time has reached predetermined period whether the amount of the dry ice 350 that precipitated reaches scheduled volume for example adopt to see through wicket perusal pressure vessel 310.
Then, open control valve 345, allow heat medium flow through heat-transfer pipe 313 (S809) so that the internal temperature of pressure vessel 310 is raise.Along with the rising of pressure vessel 310 internal temperatures, dry ice 350 start vaporizers (distillation) that coolant flow tubes 312 surfaces are upward precipitated (S810).Simultaneously, by the evaporation of dry ice 350, the internal pressure of pressure vessel 310 can raise.As shown in Figure 9, the three phase point of carbon dioxide is 5.11 atmospheric pressure and-56.6 ℃.Therefore, when because dry ice 350 evaporation, pressure vessel 310 temperature inside and pressure become when being higher than the value of its three phase point, and a part of carbon dioxide begins liquefaction in the pressure vessel 310, and can be accumulated in the bottom (S811) of pressure vessel 310 by the liquid carbon dioxide that liquefaction is produced.
Then, when the dry ice 350 that is deposited in coolant flow tubes 312 surfaces evaporates fully or liquefies (S811: be), open control valve 343.Liquid carbon dioxide with the accumulation of pressure vessel 310 bottoms utilizes pressure vessel 310 pressure inside to be discharged to (S813) outside the pressure vessel 310 via liquid outlet 323 thus.For example adopt to see through wicket perusal pressure vessel 310 whether fully inner or determine dry ice 350 evaporation or liquefy according to the method whether time has reached predetermined period.Remain on one by liquid discharge tube 33 inside that will connect liquid outlet 323 and can keep under the temperature and pressure that carbon dioxide is a liquid, make carbon dioxide be discharged from pressure vessel 310 under the state of liquid remaining.
As mentioned above, adopt the carbon dioxide separator 30 of the present embodiment, can isolate carbon dioxide contained in the gas efficiently.After the control valve 345 of closed control valve 344 and heat-transfer pipe 313,, can from the waste gas that reversible heat exchanger 23 is drawn continuously, isolate carbon dioxide (S814: not) continuously by repeating the process of S801 and back.
Adopt carbon dioxide separator 30, carbon dioxide can be solidified in same pressure vessel 310 or liquefy.In addition, as mentioned above, carbon dioxide separator 30 layouts are simple, thereby can implement under low cost.And,,, therefore be easy to carry out continuously or operation automatically so the inner passage of heat-transfer pipe 313 can not blocked because dry ice 350 is precipitations outside heat-transfer pipe (coolant flow tubes 312) in the carbon dioxide separator 30.And, need not to use special liquefaction device, the carbon dioxide energy is so that the liquid form discharge of transportation and storage.
Control valve 341 to 345 for example can be a magnetic valve, is connected to computer by control line and controls, and carry out Long-distance Control by computer hardware and the control software that moves on this hardware.In addition, all or part said process can be arranged to according to the output valve of each sensor and automatically carry out.
=the four embodiment=
Figure 10 illustrates the layout according to the exhaust treatment system of four embodiment of the invention.This exhaust treatment system can effectively remove contained humidity and harmful gas component in the waste gas simultaneously as effectively reclaiming institute's carbonated the waste gas that comprises harmful gas component such as nitrogen oxide of combustion LNG boiler emissions such as power plant, chemical plant installations from exhaust gas source 10
In this exhaust treatment system, in its preprocessing process, will be incorporated into from the waste gas that comprises harmful gas component such as nitrogen oxide of exhaust gas source 10 discharging the heat exchanger 11 contained water for industrial use and condenser 13, thereby about cool to room temperature.Then, in first process, in dehydrating tower 17, be cooled to first temperature that carbon dioxide is solidified, thereby make in the waste gas contained humidity and nitrogen oxide liquefaction or solidify and from waste gas, separate being cooled to waste gas about room temperature.Then, in second process, the waste gas of therefrom isolating moisture and nitrogen oxide is introduced in the carbon dioxide separator 30, made carbon dioxide cooling contained in the waste gas and solidify it is separated, then with the co 2 liquefaction and the discharging of separating.
The detailed process of the exhaust treatment system of the present embodiment then, is described successively.At first, in preprocessing process, be introduced in the heat exchanger 11 from the waste gas that comprises harmful gas component such as nitrogen oxide of exhaust gas source 10 as combustion LNG boiler emission, in heat exchanger 11, introduced by the seawater (for example, 25 ℃) of sea water pump 12 supplies and cooling agent such as the ethylene glycol that comes from refrigerator 40 circulations.The waste gas of introducing from exhaust gas source 10 (for example 55 ℃) pass heat exchanger 11 and by seawater and coolant cools to the room temperature.
Cooled waste gas is incorporated in the condenser 13, imports then in the contained water for industrial use of condenser 13.Thus, moisture contained in the waste gas, harmful gas component, dust and analog are removed.The liquefaction water that comprises moisture, harmful gas component, dust and analog that shifts out from waste gas temporarily is stored in the discharging storage tank 14, is incorporated into out in the material processing device 50 with discharging pump 15 subsequently.The waste gas that will pass condenser 13 at last is incorporated in the dehydrating tower 17 with exhaust gas blower 16.It is pointed out that in condenser 13 heat exchange with water for industrial use makes waste gas be cooled to for example 5 ℃ from about room temperature.
In dehydrating tower 17, waste gas is further dehydrated and removes harmful gas component.By removing moisture contained in waste gas, can reclaim effectively in the removal process that contained carbon dioxide carries out subsequently in the waste gas.
Waste gas is to be introduced in the dehydrating tower 17 in the lower end of dehydrating tower 17.The waste gas (for example, 5 ℃) of introducing dehydrating tower 17 is flow through by pack into the cooling agent DME (for example-90 ℃) that is used for cooling exhaust of dehydrating tower 17 of bubbling method.The waste gas that is incorporated into dehydrating tower 17 is by being cooled to chilling temperature with the DME heat exchange, and contained moisture and harmful gas component such as nitrogen oxide are liquefied or solidify in the waste gas under this temperature, and carbon dioxide does not solidify.Therefore though moisture is liquefied with nitrogen dioxide or solidifies and separate with waste gas, and carbon dioxide remains gas in waste gas.The waste gas that comprises carbon dioxide rises to the top of dehydrating tower 17 and is added in the reversible heat exchanger 23.
Will be in dehydrating tower 17 from DME circulation-supplied after the cooling of DME cooling tower 18.Circulate through DME cooling tower 18 with the cooling agent (liquid nitrogen) of circulating pump 19 44 coolings of refrigerator/heat exchanger.DME is by being cooled with the cooling agent heat exchange.
The DME that has imported waste gas in dehydrating tower 17 is incorporated in the solid-liquid separation column 28.Attention is in this stage, and the coagulum of DME and moisture and harmful gas component is in husky ice state (slurry).Solid-liquid separation column 28 is separated the coagulum of DME and moisture and harmful gas component.28 isolated DME are introduced in DME knockout tower 20 so that re-use this DME by solid-liquid separation column.The DME that is introduced in DME knockout tower 20 can more residual moisture and harmful gas component.
The DME that is incorporated into DME knockout tower 20 from dehydrating tower 17 is by elevate the temperature with the seawater indirect heat exchange (for example being elevated to 5 ℃).Under this temperature, moisture and harmful gas component are liquid or solids, and DME is a gas.Therefore, DME gas rises to the top of DME knockout tower 20, separated thus going out.The DME that rises to DME knockout tower 20 tops is reclaimed and is incorporated in the DME cooling tower 18 from this place, and introduce dehydrating tower 17 again.In this way, recycle DME.Like this, by recycling cooling agent DME, the exhaust treatment system integral body of the present embodiment is operated and is efficiently utilized cooling agent.Simultaneously, liquid or solid moisture and the harmful gas component of staying in the DME knockout tower 20 is incorporated into out in the material processing device 50.
To be incorporated into waste gas the reversible heat exchanger 23 from dehydrating tower 17 cools off therein and is incorporated in the carbon dioxide separator 30.Carbon dioxide separator 30 is separated carbon dioxide and is liquefied from waste gas, with isolated carbon dioxide discharging.The detailed placement and the effect of carbon dioxide separator 30 will be explained below.
The liquefied carbon dioxide of being discharged is transferred and is stored in the liquefaction carbonic acid storage tank 27.The waste gas that simultaneously will be therefrom isolate carbon dioxide in carbon dioxide separator 30 is introduced in the reversible heat exchanger 23 as cooling agent, and then introduces in the heat exchanger 11.After in heat exchanger 11, being used as cooling agent, with waste gas in chimney 51 is discharged into atmosphere outside the system.Discharge the exhaust in the atmosphere be for a part of toxic emission beyond the system to reduce waste gas gathering in system.Therefore, it is very low to be discharged in the waste gas of atmosphere concentration of carbon dioxide.
Here, by utilizing the heat of evaporation of LNG, the ethylene glycol that refrigerator/heat exchanger 44 will cycle through heat exchanger 11 cools off with the cooling agent such as the liquid nitrogen that cycle through DME cooling tower 18, dry ice sublimation device 24 etc.For example in using the power plant of LNG as gaseous fuel, LNG transports and is stored in LNG jar or the similar devices under the liquid state of-165 ℃ of temperature at-150 ℃.When LNG when the gaseous fuel, LNG obtains heat of evaporation raise temperature and gasification from atmosphere or seawater, refrigerator/heat exchanger 44 utilizes this heat of evaporation to cool off cooling agent such as ethylene glycol and liquid nitrogen simultaneously.That is to say that waste gas or cooling agent are that the heat of evaporation that is produced when utilizing LNG to be used as gaseous fuel is cooled off.By the heat of evaporation of using LNG solidify with separate waste gas in the technology of contained carbon dioxide for example be disclosed among the Japanese Patent Application Publication publication No.H08-12314 etc.
As mentioned above, the exhaust treatment system of the present embodiment can remove moisture and harmful gas component efficiently from the waste gas that comprises harmful gas component such as nitrogen oxide of combustion LNG boiler or similar devices discharging, and can further reclaim carbon dioxide from waste gas efficiently.
Although above having described the harmful gas component that desire removes from waste gas is the situation of nitrogen dioxide, by selecting suitable cooling agent, the technological process identical with the present embodiment can be applied to such as carbon monoxide, other nitrogen oxide (NO x) as nitric oxide and halogen compounds such as hydrofluoric other harmful gas component.
Control valve 341 to 345 for example can be a magnetic valve, is connected to computer by control line and controls, and carry out Long-distance Control by computer hardware and the control software that moves on this hardware.In addition, all or part said process can be arranged to according to the output valve of each sensor and automatically carry out.
Though embodiment of the present invention have been described, above embodiment be provide in order to help to understand the present invention be not the restriction the present invention.It should be understood that under the situation that does not break away from the spirit and scope of the present invention and can do various variations and change, and the present invention includes their equivalent.

Claims (53)

1. waste gas processing method is characterized in that it comprises:
Allow waste gas flow through cooling agent and make it to be cooled to make nitrogen oxide liquefaction or solidify but first temperature that carbon dioxide can not solidify, thereby thus with harmful gas component nitrogen oxide liquefaction contained in the waste gas or solidify first process that they are separated from waste gas; With
Waste gas is cooled to second temperature that carbon dioxide is solidified, thereby thus carbon dioxide contained in the waste gas is solidified second process that it is separated from waste gas.
2. according to the waste gas processing method of claim 1, it is characterized in that it comprises:
Allow waste gas flow through cooling agent and make it to be cooled to make nitrogen oxide and oxysulfide liquefaction or solidify but first temperature that can not solidify carbon dioxide, thus with in the waste gas contained as harmful gas component nitrogen oxide and oxysulfide liquefaction or solidify and first process that they are separated from waste gas; With
Second temperature that waste gas is cooled to solidify carbon dioxide, thus second process that it is separated thus carbon dioxide contained in the waste gas is solidified from waste gas.
3. according to the waste gas processing method of claim 2, it is characterized in that it comprises:
First process is elevated to the evaporative cooling agent but the temperature of not evaporating harmful gas component from the temperature of the isolated harmful gas component of waste gas, the process of separating harmful gas component and cooling agent thus.
4. according to the waste gas processing method of claim 3, it is characterized in that it comprises:
The cooling agent that will separate with harmful gas component is as a kind of process that waste gas is circulated through its cooling agent that flows through.
5. according to any one waste gas processing method of claim 2-4, it is characterized in that it comprises:
First process temperature of isolated harmful gas component from waste gas brought up to evaporate oxysulfide but the temperature of non-vaporized nitrogen oxide, thus that harmful gas component is contained oxysulfide and nitrogen oxide separating process.
6. according to any one waste gas processing method of claim 2-5, be characterised in that cooling agent comprises any in dimethyl ether, methyl alcohol, ethanol, toluene and the ethylbenzene.
7. according to any one waste gas processing method of claim 2-6, first process that is characterised in that comprises a process of isolating the waste gas contained humidity from waste gas.
8. according to any one waste gas processing method of claim 2-7, second process that is characterised in that comprises a process that drikold (dry ice) is liquefied.
9. according to any one waste gas processing method of claim 2-8, be characterised in that will carry out one before first process will be cooled to waste gas after about room temperature by carrying out the preprocessing process that heat exchange removes contained humidity in the waste gas, harmful gas component and dust with water.
10. exhaust treatment system is characterized in that it comprises:
First device, this device is used for implementing one to be allowed waste gas flow through cooling agent to make it to be cooled to make nitrogen oxide liquefaction or solidify but first temperature that can not solidify carbon dioxide, thus with harmful gas component nitrogen oxide liquefaction contained in the waste gas or solidify and process that they are separated from waste gas; With
Second device, this device is used for implementing one waste gas is cooled to solidify second temperature of carbon dioxide, institute's carbonated solidifies the process that it is separated in the waste gas from waste gas thereby make thus.
11., it is characterized in that it comprises according to the exhaust treatment system of claim 10:
First device, this device is used for implementing one to be allowed waste gas flow through cooling agent to make it to be cooled to make nitrogen oxide and oxysulfide liquefaction or solidify but first temperature that can not solidify carbon dioxide, thereby with contained harmful gas component nitrogen oxide and oxysulfide liquefaction in the waste gas or solidify and process that they are separated from waste gas; With
Second device, this device is used for implementing one waste gas is cooled to solidify second temperature of carbon dioxide, thereby makes carbon dioxide contained in the waste gas solidify the process that it is separated thus from waste gas.
12., it is characterized in that it comprises according to the exhaust treatment system of claim 11:
To bring up to first device isolated harmful gas component temperature from waste gas and make the refrigerant evaporates of mixing but the temperature that harmful gas component can not evaporate, separate the device of harmful gas component and cooling agent thus with harmful gas component.
13., it is characterized in that it comprises according to the exhaust treatment system of claim 11:
The cooling agent that will separate with harmful gas component is as a kind of device that waste gas is circulated through its cooling agent that flows through
14., it is characterized in that it comprises according to any one exhaust treatment system of claim 11-13:
To bring up to the evaporation oxysulfide but the temperature of non-vaporized nitrogen oxide, the device that thus that harmful gas component is contained oxysulfide separates with nitrogen oxide with first device temperature of isolated harmful gas component from waste gas.
15., be characterised in that cooling agent comprises any in dimethyl ether, methyl alcohol, ethanol, toluene and the ethylbenzene according to any one exhaust treatment system of claim 11-14.
16., be characterised in that first device comprises that an energy isolates the device of waste gas contained humidity from waste gas according to any one exhaust treatment system of claim 11-15.
17. according to any one exhaust treatment system of claim 11-16, be characterised in that second device comprise one can be with the device of drikold (dry ice) liquefaction.
18., it is characterized in that it comprises according to any one exhaust treatment system of claim 11-17:
Before the process of implementing first device, to implement the waste gas after being cooled to about room temperature by carrying out the device that heat exchange removes the preprocessing process of contained humidity in the waste gas, harmful gas component and dust with water.
19. waste gas processing method is characterized in that it comprises:
Allow the waste gas of combustion LNG boiler emission flow through cooling agent and make it to be cooled to make nitrogen oxide liquefaction or solidify but first temperature that carbon dioxide can not solidify, thereby thus with harmful gas component nitrogen oxide liquefaction contained in the waste gas or solidify first process that it is separated from waste gas; With
Waste gas is cooled to second temperature that carbon dioxide is solidified, thereby thus carbon dioxide contained in the waste gas is solidified second process that it is separated from waste gas.
20., it is characterized in that it comprises according to the waste gas processing method of claim 19:
The nitrogen oxide that first process is solidified is incorporated into solid-liquid separator, thus the process of separating nitrogen oxide and cooling agent.
21., it is characterized in that it comprises according to the waste gas processing method of claim 20:
The temperature of the fluid temperature that solid-liquid separator separated being brought up to the evaporative cooling agent but not evaporating harmful gas component is isolated the process of cooling agent thus.
22., it is characterized in that it comprises according to the waste gas processing method of claim 21:
Will be from liquid isolated cooling agent is as the process that allows waste gas circulate through its cooling agent that flows through.
23., be characterised in that cooling agent comprises any in dimethyl ether, methyl alcohol, ethanol, toluene and the ethylbenzene according to any one waste gas processing method of claim 19-22
24. according to any one waste gas processing method of claim 19-23, first process that is characterised in that comprises a process of isolating the waste gas contained humidity from waste gas
25. according to any one waste gas processing method of claim 19-24, second process that is characterised in that comprises a process that drikold (dry ice) is liquefied.
26., be characterised in that will carry out one before first process will be cooled to waste gas after about room temperature by carrying out the preprocessing process that heat exchange removes contained humidity and harmful gas component in the waste gas with water according to any one waste gas processing method of claim 19-25.
27., it is characterized in that at least one waste gas or the heat of evaporation that produced during as gaseous fuel because of LNG of cooling agent of first and second processes is cooled according to any one waste gas processing method of claim 19-26.
28. exhaust treatment system is characterized in that it comprises:
First device, this device is used for implementing a waste gas that allows combustion LNG boiler emission and flows through cooling agent and make it to be cooled to make nitrogen oxide liquefaction or solidify but first temperature that can not solidify carbon dioxide, thus with harmful gas component nitrogen oxide liquefaction contained in the waste gas or solidify and process that they are separated from waste gas; With
Second device, this device is used for implementing one waste gas is cooled to solidify second temperature of carbon dioxide, institute's carbonated solidifies the process that it is separated in the waste gas from waste gas thereby make thus.
29., it is characterized in that it comprises according to the exhaust treatment system of claim 28:
The nitrogen oxide that first device is solidified is incorporated into solid-liquid separator, thus the device of separating nitrogen oxide and cooling agent.
30., it is characterized in that it comprises according to the exhaust treatment system of claim 29:
The fluid temperature that solid-liquid separator separated is brought up to the temperature of can the evaporative cooling agent but not evaporating harmful gas component, isolate the device of cooling agent thus.
31., it is characterized in that it comprises according to the exhaust treatment system of claim 30:
Will be from liquid isolated cooling agent is as the device that waste gas is circulated through its cooling agent that flows through.
32., be characterised in that cooling agent comprises any in dimethyl ether, methyl alcohol, ethanol, toluene and the ethylbenzene according to any one exhaust treatment system of claim 28-31.
33., be characterised in that first device comprises the device of isolating the waste gas contained humidity from waste gas according to any one exhaust treatment system of claim 28-32.
34. according to any one exhaust treatment system of claim 28-33, be characterised in that second device comprise one can be with the device of drikold (dry ice) liquefaction.
35., it is characterized in that it comprises according to any one exhaust treatment system of claim 28-34:
Before the process of implementing first device, to implement the waste gas after being cooled to about room temperature by carrying out the device that heat exchange removes the preprocessing process of contained humidity and harmful gas component in the waste gas with water.
36., it is characterized in that being cooled in the waste gas or the heat of evaporation that produced during as gaseous fuel because of LNG of cooling agent of first and second devices at least one according to any one exhaust device system of claim 28-35.
37. exhaust treatment system is characterized in that it comprises:
First device, this device flows through cooling agent with waste gas to be made it to be cooled to make nitrogen oxide and oxysulfide liquefaction or solidifies but the temperature that can not solidify carbon dioxide, thereby with contained harmful gas component nitrogen oxide and oxysulfide liquefaction in the waste gas or solidify and they are separated from waste gas; With
Second device, this device makes the waste gas that removes nitrogen oxide and oxysulfide flow through a pressure vessel to cool off and solidify carbon dioxide, this pressure vessel of bubble-tight shut-off, the temperature of rising drikold is evaporated, owing to evaporating the carbon dioxide that makes the pressure rising make co 2 liquefaction and will liquefy in pressure vessel, carbon dioxide is discharged to outside the pressure vessel.
38., it is characterized in that it comprises according to the exhaust treatment system of claim 37:
To bring up to first device isolated harmful gas component temperature from waste gas and make the refrigerant evaporates of mixing but the unvaporized temperature of harmful gas component, separate the device of harmful gas component and cooling agent thus with harmful gas component.
39., it is characterized in that it comprises according to the exhaust treatment system of claim 37 or 38:
To bring up to the evaporation oxysulfide but the temperature of non-vaporized nitrogen oxide, the device that thus that harmful gas component is contained oxysulfide separates with nitrogen oxide with first device temperature of isolated harmful gas component from waste gas.
40. exhaust treatment system is characterized in that it comprises:
First device, this device is used for implementing a waste gas that allows combustion LNG boiler emission and flows through cooling agent and make it to be cooled to make nitrogen oxide liquefaction or solidify but first temperature that can not solidify carbon dioxide, thus with harmful gas component nitrogen oxide liquefaction contained in the waste gas or solidify and process that they are separated from waste gas; With
Second device, the waste gas that this device will remove nitrogen oxide flows through a pressure vessel and cools off and solidify carbon dioxide, this pressure vessel of bubble-tight shut-off, the temperature of rising drikold is evaporated, owing to evaporating the carbon dioxide that makes the pressure rising make co 2 liquefaction and will liquefy in pressure vessel, carbon dioxide is discharged to outside the pressure vessel.
41., it is characterized in that it comprises according to the exhaust treatment system of claim 40:
The nitrogen oxide that first device is solidified is incorporated into solid-liquid separator, thus the device of separating nitrogen oxide and cooling agent.
42., it is characterized in that it comprises according to the exhaust treatment system of claim 41:
The temperature of the fluid temperature that solid-liquid separator separated being brought up to the evaporative cooling agent but not evaporating harmful gas component is isolated the device of cooling agent thus.
43., be characterised in that cooling agent comprises any in three methyl ethers, methyl alcohol, ethanol, toluene and the ethylbenzene according to any one exhaust treatment system of claim 37-42.
44., be characterised in that the carbon dioxide cooling carried out with second device is to be undertaken by the coolant flow tubes outside that has cooling agent to flow through that allows carbonated gas contact pressure vessel to provide with solidifying according to any one exhaust treatment system of claim 37-43.
45., be characterised in that coolant flow tubes is back-shaped arranging according to any one exhaust treatment system of claim 37-44.
46. the method for separating carbon dioxide is characterized in that it comprises:
Allow the gas that contains carbon dioxide flow through a pressure vessel and cool off and solidify carbon dioxide;
This pressure vessel of bubble-tight shut-off;
The temperature of rising drikold is evaporated;
Owing to evaporating in pressure vessel, carbon dioxide make the pressure rising make co 2 liquefaction; With
The carbon dioxide that has liquefied is discharged to outside the pressure vessel.
47., be characterised in that cooling is to be undertaken by the coolant flow tubes outside that has cooling agent to flow through that allows carbonated gas contact pressure vessel to provide with solidifying operation according to the method for the separating carbon dioxide of claim 46.
48. the method according to the separating carbon dioxide of claim 47 is characterised in that coolant flow tubes is back-shaped arranging
49. according to the method for the separating carbon dioxide of claim 46, being characterised in that raises by the heat-transfer pipe that disposes in the pressure vessel or electric heater solidifies the temperature of carbon dioxide.
50. the method according to the separating carbon dioxide of claim 46 is characterised in that pressure vessel comprises:
Allow the gas that contains carbon dioxide flow into gas feed in the pressure vessel;
Make the gas in the pressure vessel discharge the outer gas vent of pressure vessel; With
Make liquefied carbon dioxide discharge the outer liquid outlet of pressure vessel.
51. the method according to the separating carbon dioxide of claim 46 or 47 is characterised in that gas comprises nitrogen oxide or oxysulfide.
52. the method for separating carbon dioxide, this method has used one to have the gas feed that allows gas flow into wherein, make the gas vent that gas wherein discharges and make the pressure vessel of the liquid outlet that liquid wherein discharges, and is installed in the cooler in the pressure vessel and is used to improve the heat-transfer equipment of pressure vessel internal temperature; Be characterised in that it comprises:
Allow the gas that contains carbon dioxide flow into pressure vessel through gas feed;
Make gas contact cooler, thereby cool off and solidify carbon dioxide;
Close gas feed and gas vent, thereby make the pressure vessel bubble-tight shut-off;
Temperature with heat-transfer equipment rising drikold is evaporated;
Owing to evaporating in pressure vessel, carbon dioxide make the pressure rising make co 2 liquefaction; With
Through gas vent liquefied carbon dioxide is discharged to outside the pressure vessel.
53. the device of separating carbon dioxide is characterized in that it comprises:
The pressure vessel of the control valve of the amount of liquid that the control valve of the gas flow of have the gas feed that allows gas flow into wherein, make gas vent that gas wherein discharges, make liquid outlet that liquid wherein discharges, the control valve of the gas flow of control gas coming through import, control being discharged via gas vent and control are discharged via liquid outlet;
Be installed in the cooler in the pressure vessel; With
Be used to improve the heat-transfer equipment of pressure vessel internal temperature.
CNA2005800111997A 2004-03-02 2005-03-02 Method and system for treating exhaust gas, and method and apparatus for separating carbon dioxide Pending CN1956768A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP057604/2004 2004-03-02
JP057603/2004 2004-03-02
JP2004057603 2004-03-02
JP091852/2004 2004-03-26
JP091853/2004 2004-03-26

Publications (1)

Publication Number Publication Date
CN1956768A true CN1956768A (en) 2007-05-02

Family

ID=38063667

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2005800111997A Pending CN1956768A (en) 2004-03-02 2005-03-02 Method and system for treating exhaust gas, and method and apparatus for separating carbon dioxide

Country Status (1)

Country Link
CN (1) CN1956768A (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102257341A (en) * 2008-12-19 2011-11-23 乔治洛德方法研究和开发液化空气有限公司 Method for trapping carbon dioxide by cryocondensation
CN102343163A (en) * 2010-07-21 2012-02-08 库珀·威拉德 Cryogenic process for separation of carbon dioxide from the atmosphere using a superconducting wind turbine
CN102395657A (en) * 2009-02-12 2012-03-28 红叶资源公司 Carbon management and sequestration from encapsulated control infrastructures
CN102836617A (en) * 2011-06-21 2012-12-26 株式会社东芝 Carbon dioxide capturing device and carbon dioxide capturing method
CN101855169B (en) * 2007-07-11 2014-03-26 乔治洛德方法研究和开发液化空气有限公司 Process and apparatus for the separation of a gaseous mixture
US8961652B2 (en) 2009-12-16 2015-02-24 Red Leaf Resources, Inc. Method for the removal and condensation of vapors
CN102326044B (en) * 2008-12-19 2015-08-19 乔治洛德方法研究和开发液化空气有限公司 Use the CO of cryogenic condensation 2recovery method
US9242190B2 (en) 2009-12-03 2016-01-26 Red Leaf Resources, Inc. Methods and systems for removing fines from hydrocarbon-containing fluids
CN113546516A (en) * 2021-09-03 2021-10-26 郑州大学环境技术咨询工程有限公司 CO for boiler2Collecting device
CN114593560A (en) * 2022-03-11 2022-06-07 苏州金宏气体股份有限公司 Removal of NO from NO2、N2O purification device and purification method
JP2022531667A (en) * 2019-05-06 2022-07-08 中建材硝子新材料研究院集団有限公司 Manufacturing method and equipment for chalcogen-containing compound semiconductors
CN115038508A (en) * 2020-02-13 2022-09-09 乔治洛德方法研究和开发液化空气有限公司 Containing CO 2 Use of the gaseous effluent of

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101855169B (en) * 2007-07-11 2014-03-26 乔治洛德方法研究和开发液化空气有限公司 Process and apparatus for the separation of a gaseous mixture
CN102326044B (en) * 2008-12-19 2015-08-19 乔治洛德方法研究和开发液化空气有限公司 Use the CO of cryogenic condensation 2recovery method
CN102257341A (en) * 2008-12-19 2011-11-23 乔治洛德方法研究和开发液化空气有限公司 Method for trapping carbon dioxide by cryocondensation
CN102395657A (en) * 2009-02-12 2012-03-28 红叶资源公司 Carbon management and sequestration from encapsulated control infrastructures
US9242190B2 (en) 2009-12-03 2016-01-26 Red Leaf Resources, Inc. Methods and systems for removing fines from hydrocarbon-containing fluids
US9482467B2 (en) 2009-12-16 2016-11-01 Red Leaf Resources, Inc. Method for the removal and condensation of vapors
US8961652B2 (en) 2009-12-16 2015-02-24 Red Leaf Resources, Inc. Method for the removal and condensation of vapors
CN102343163B (en) * 2010-07-21 2014-03-19 库珀·威拉德 Cryogenic process for separation of carbon dioxide from the atmosphere using a superconducting wind turbine
CN102343163A (en) * 2010-07-21 2012-02-08 库珀·威拉德 Cryogenic process for separation of carbon dioxide from the atmosphere using a superconducting wind turbine
CN102836617A (en) * 2011-06-21 2012-12-26 株式会社东芝 Carbon dioxide capturing device and carbon dioxide capturing method
CN102836617B (en) * 2011-06-21 2016-01-27 株式会社东芝 Carbon dioxide recovering apparatus and process for carbon dioxide recovery
JP2022531667A (en) * 2019-05-06 2022-07-08 中建材硝子新材料研究院集団有限公司 Manufacturing method and equipment for chalcogen-containing compound semiconductors
CN115038508A (en) * 2020-02-13 2022-09-09 乔治洛德方法研究和开发液化空气有限公司 Containing CO 2 Use of the gaseous effluent of
CN113546516A (en) * 2021-09-03 2021-10-26 郑州大学环境技术咨询工程有限公司 CO for boiler2Collecting device
CN113546516B (en) * 2021-09-03 2022-08-12 郑州大学环境技术咨询工程有限公司 Boiler CO 2 Collection method
CN114593560A (en) * 2022-03-11 2022-06-07 苏州金宏气体股份有限公司 Removal of NO from NO2、N2O purification device and purification method

Similar Documents

Publication Publication Date Title
CN1956768A (en) Method and system for treating exhaust gas, and method and apparatus for separating carbon dioxide
CN1171062C (en) Process for separating hydrocarbon gas constituents
CN1283914C (en) Heat engines and associated methods of producing mechanical energy and their application to vehicle
CN1214849C (en) Carbon dioxide absorption agent
CN1476346A (en) Method and system for extracting carbon dioxide by anti-sublimatin for storage thereof
CN1266445C (en) Method for refrigerating liquefied gas and installation therefor
CN1089740C (en) Hydrocarbon gas processing
CN1041034A (en) The liquefaction again of natural gas vaporization loss
CN1942557A (en) Process and plant for conversion of waste material to liquidfuel
CN1160283C (en) Method for separating a C4 hydrocarbon mixture
CN1807555A (en) Treatment, retracting device and method for gas-state hydrocarbon
CN1517514A (en) Vapour compression refrigerant cycle system with refrigeration cycle and Rankine cycle
CN1532472A (en) Refrigerant circulation device
CN1756583A (en) Method of extracting carbon dioxide and sulphur dioxide by means of anti-sublimation for the storage thereof
CN1518656A (en) LNG production in cryogenic natural gas processing plants
CN1608190A (en) Adsorption heat pump and use of adsorbent as adsorbent for adsorption heat pump
CN1671463A (en) Low emission thermal plant
Botero et al. Redesign, optimization, and economic evaluation of a natural gas combined cycle with the best integrated technology CO2 capture
CN101059259A (en) Heat-storing air conditioner
CN1105103A (en) Gas compressor
CN1069117A (en) Gas liquefaction process control system
CN1747774A (en) Method and apparatus for separating and recovering carbon dioxide
CN1042407A (en) The liquefaction again of natural gas vaporization gas
CN1871481A (en) Freezing apparatus installation method and freezing apparatus
CN1172243A (en) Improved cooling process and installation in particular for liquenfaction of natural gas

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20070502