CN106237648B - Low-temperature carbon dioxide separator - Google Patents

Low-temperature carbon dioxide separator Download PDF

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Publication number
CN106237648B
CN106237648B CN201610875761.0A CN201610875761A CN106237648B CN 106237648 B CN106237648 B CN 106237648B CN 201610875761 A CN201610875761 A CN 201610875761A CN 106237648 B CN106237648 B CN 106237648B
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tower
interior
main cooling
storage
low temperature
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CN106237648A (en
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宋春风
孙亚伟
刘庆岭
纪娜
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Tianjin University
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Tianjin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D7/00—Sublimation
    • B01D7/02—Crystallisation directly from the vapour phase

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

The invention discloses a kind of low temperature CO2Separator, precools tower, main cooling tower and storage tower as cylindrical shape, is vertically arranged successively by upper, middle and lower；Precool in tower and be provided with interior tower A, interior tower B is provided with main cooling tower.Unstripped gas is entered the condenser pipe of interior tower A by air inlet, and the temperature of interior tower A is 60 DEG C, realizes the liquefaction of water vapour；Since the temperature in interior tower A is higher than CO2Solidification point, CO2Just enter the interior tower B of main cooling tower with other gases, the temperature of interior tower B is 120 DEG C, less than CO2Solidification point, CO therein2Solid is frozen into, is frozen in heat exchanger surface, then make solid-state CO by rotating scraping board2Fall into storage tower, it is achieved thereby that H2O and CO2In the separation of different parts.The present invention can realize CO under cryogenic2Separation, the rate of recovery 96%, energy consumption is 1.5MJ/Kg CO2。

Description

Low-temperature carbon dioxide separator
Technical field
The present invention relates to a kind of new low temperature gas separater, more particularly to a kind of low temperature CO2Gas fractionation unit.
Background technology
Low temperature process carbon trapping technique, belongs to after burning CO in flue gas2One kind of trapping technique, it is based in mixed gas The molten boiling point difference of different component realizes separated method.Low temperature CO2Isolation technics has potential to become a kind of lower energy cost very much Flue gas in CO2Isolation technics, because chemical reagent is not required in Cryogenic Separating Process, and is not required pressure drop.Recently, low temperature CO2 Isolation technics causes people widely to pay close attention to, but still has some problems to need to be solved.(1) CO of heat exchanger surface solidification2 Heat transfer will be seriously affected, and arresting efficiency can be reduced.(2) important parameter of refrigeration machine is COP (coefficient of performance), one The coefficient of performance of a little refrigeration machines is too low.Sterlin refrigerator causes the research interest of people due to its some good characteristics.It Working media can be air, hydrogen or helium.Compared with traditional refrigeration machine (CFCs, HCFCs, HFCs), its ozone It is 0 to destroy gesture.In ideal conditions, Stirling cycle is reversible.In addition sterlin refrigerator can be in very wide temperature In the range of (- 120 DEG C -70 DEG C) work, and under low heat load, its coefficient of performance can exceed that 2.5.
State when being captured according to carbon dioxide is different, and low temperature process carbon trapping technique contains two kinds of trapping forms：The One kind is liquefaction separation, i.e. cryogenic condensation or rectifying, using the boiling point difference with other compositions in mixed gas, using low temperature skill Art is by CO2Liquefy and separate；Second is separation of sublimating, it mainly using other in de-sublimation temperature and mixed gas into Point difference, using cryogenic technique by CO2Cure and separate.CO2It is separated in solid form by way of sublimating Come, in the range of a certain concentration, there are power savings advantages.
Research both domestic and external is retrieved, cryogenic separation Technical comparing maturation is used for CO in natural gas2Removal, such as The CryoCell technologies of CoolEnergy companies exploitation, using a low-temperature process CO2Removing is fallen from natural gas.
Retrieve research both domestic and external, CO in cryogenic trapping flue gas2Device it is fewer.Clodic and Younes etc. it is proposed that Low temperature CO under one normal pressure2Separator.Solidified by evaporated refrigerant working medium in heat exchanger cold side, so as to reach trapping Purpose.Within the system, two evaporimeter frosting defrosting process alternate runs, a frosting, another then defrosts.But he System the shortcomings that be：Water content is as small as possible in raw material, prevents the ice that water is formed from blocking pipeline or producing in operation A raw big pressure drop；In the CO that heat exchanger surface is formed2Solid layer, can seriously affect the heat transfer of heat exchanger, reduce effect Rate；Expensive heat exchanger must be transformed into regeneration cycle at different temperature, and operation will be paid special attention to, and avoid excessive machinery Pressure.Dutch scientist M.J.Tuinier etc. develops the CO based on low temperature packed bed2Trapping technique, based on different dew points And sublimation point, realize CO2, H2The separation of O and other infiltration gases.Compared to the cryogenic trapping of the propositions such as Clodic and Younes System, does not increase pressure drop and produces blockage problem, but the operation of this packed bed is more complicated, first to lead to nitrogen refrigeration, then Unstrpped gas is passed through again.CO2Recycle heat is equally more complicated during trapping, and the requirement to filler particles is higher.
The present invention is the new type low temperature CO based on free-piston type sterlin refrigerator2Isolation technics, according to sublimating a little Difference is separated, H2O and CO2It can be condensed and sublimate in the different piece of trapping system, remaining gas outflow system does not have The change of phase.Water is concentrated in the process of precooling, is flowed out by concentration tube, is avoided blockage problem.CO2It is to be captured with solid phase, Avoid in other capture methods using solvent and consideration stress problems.It is remaining to be arranged for condensed gas by gas vent Go out.
The content of the invention
The purpose of the present invention, is to overcome existing CO2The shortcomings that trapping technique energy consumption is high, and product recovery rate is low and A kind of deficiency, there is provided new low temperature CO2Separator, CO is carried out according to the difference sublimated a little2Separation.This device CO2Trap energy Consume low, can realize CO under cryogenic2Separation, last CO2It is saved with solid-state, the rate of recovery is high.
The present invention is achieved by the following technical solutions：
A kind of low temperature CO2Separator, including precool tower, main cooling tower and storage tower three parts, it is characterised in that institute State and precool tower 1, main cooling tower 2 and storage tower 3 as cylindrical shape, be vertically arranged successively by upper, middle and lower；
Precool and interior tower A6 is provided with tower 1, it is vacuum state to precool between tower 1 and Nei Ta A6；Set in main cooling tower 2 Interior tower B11 is equipped with, is also vacuum state between main cooling tower 2 and Nei Ta B11；Precool tower 1 and main cooling tower 2 and interior tower A6 and Do not connect between interior tower B11；
Interior tower A6, interior tower B11 and storage tower 3 are respectively arranged with refrigeration machine A4, refrigeration machine B9 and refrigeration machine C16, refrigeration machine The heat exchanger 10 of B9 is arranged on the middle position of interior tower B11；The periphery of heat exchanger 10 is provided with rotation and scrapes sassafras plate 14；Main cooling tower 2 are additionally provided with motor 13 to control rotation to scrape sassafras plate 14；
Condenser pipe 7 is provided with interior tower A6, the top for precooling tower 1 is provided with the air inlet 5 of condenser pipe 7, precools tower 1 Side wall be provided with the condensation-water drain 8 of condenser pipe 7, the lower end of condenser pipe 7 is extended in interior tower B11；Interior tower B11 with below Storage tower 3 connect；The side wall of storage tower 3 is provided with gas discharge outlet 15；
Gas preprocessor 17, valve 18,19 and of flow controller are additionally provided with the front end of the air inlet 5 of condenser pipe 7 Pressure controller 20.
Set temperature is -60 DEG C in the interior tower A6 for precooling tower 1, set temperature in the interior tower B11 of main cooling tower 2 For -120 DEG C, set temperature is -80 DEG C in storage tower 3.
The refrigeration machine A4, refrigeration machine B9 and refrigeration machine C16 are free-piston type sterlin refrigerator.
Precooling tower 1, main cooling tower 2 and the storage tower 14 are stainless steel material.
The interior tower A6, the outer surface of interior tower B11 are provided with aluminum foil material.
The outer surface for precooling tower 1, main cooling tower 2 and storage tower 3 is provided with pearl cotton heat-insulating material.
Beneficial effects of the present invention are as follows：
1. the present invention devises the low temperature CO based on free-piston type sterlin refrigerator2Separator.Low temperature CO2's Isolation technics separates CO compared to more ripe chemical absorption method2, it is not necessary to chemical reagent, it is therefore prevented that the pollution of reagent, in addition The regeneration of solvent is not required, therefore saves the energy.
2. low temperature CO2Isolation technics, with membrane separation process trap CO2Compare, it is not necessary to pressure differential, and the production of pressure differential It is raw to need compressor or vacuum pump, consume the energy, for this respect, low temperature CO2Isolation technics be also save the energy.
3. for the present invention using own piston Stirling cooler, it has compact-sized, light-weight, oil-free, movement portion Part is few, and the high and low noise of reliability, low vibration, not easy to wear, long lifespan, refrigerating capacity facilitate the advantages that adjustable.
4. the present invention is in low temperature CO2During separation, the water vapour in unstripped gas is concentrated in precooling process, passes through concentration tube Outflow, avoids blockage problem.Water and CO2It can be condensed and sublimate in the different piece of trapping system, remaining gas outflow System does not have the change of phase.CO2It is to be captured with solid phase, avoids in other capture methods using solvent and consideration pressure Problem.96% CO is realized at optimal temperature and flow rate2The rate of recovery, energy consumption are only 1.5MJ/Kg CO2.
Brief description of the drawings
Fig. 1 is low temperature CO of the present invention2The structure diagram of separator；
Fig. 2 is low temperature CO of the present invention2The process diagram of separation process.
Attached drawing table of the present invention and as follows：
1 --- precooling tower 2 --- main cooling tower
3 --- storage tower 4 --- refrigeration machine A
5 --- air inlet 6 --- interior tower A
7 --- condenser pipe 8 --- condensation-water drains
9 --- refrigeration machine B 10 --- heat exchangers
11 --- interior tower B 12 --- solid-state CO2
13 --- motor 14 --- rotate scraping board
15 --- gas discharge outlet 16 --- refrigeration machine C
17 --- gas preprocessor 18 --- valves
19 --- flow controller 20 --- pressure controllers
Embodiment
The present invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is low temperature CO of the present invention2The structure diagram of separator, Fig. 2 are low temperature CO of the present invention2The work of separation process Skill schematic diagram.
Referring to attached drawing, a kind of low temperature CO of the invention2Separator, including：Precool tower 1, main cooling tower 2, storage tower 3 Three parts, are vertically arranged successively by upper, middle and lower, are stainless steel material, its outer surface is provided with pearl cotton heat-insulating material.Precool Interior tower A6 is provided with tower 1, it is vacuum state to precool between tower 1 and Nei Ta A6；Interior tower B11 is provided with main cooling tower 2, it is main Also it is vacuum state between cooling tower 2 and Nei Ta B11；Precool between tower 1 and main cooling tower 2 and interior tower A6 and Nei Ta B11 not Connect；Interior tower A6, the outer surface of interior tower B11 are provided with aluminum foil material.
Interior tower A6, interior tower B11 and storage tower 3 are respectively arranged with refrigeration machine A4, refrigeration machine B9 and refrigeration machine C16, refrigeration machine The heat exchanger 10 of B9 is arranged on the middle position of interior tower B11；The periphery of heat exchanger 10 is provided with rotation and scrapes sassafras plate 14, main cooling tower 2 are additionally provided with motor 13 to control rotation to scrape sassafras plate 14；
Condenser pipe 7 is provided with interior tower A6, the top for precooling tower 1 is provided with the air inlet 5 of condenser pipe 7, precools tower 1 Side wall be provided with the condensation-water drain 8 of condenser pipe 7, the lower end of condenser pipe 7 is extended in interior tower B11；Interior tower B11 with below Storage tower 3 connect；The side wall of storage tower 3 is provided with gas discharge outlet 15；
Gas preprocessor 17, valve 18,19 and of flow controller are additionally provided with the front end of the air inlet 5 of condenser pipe 7 Pressure controller 20.
Unstripped gas is by gas preprocessor 17, valve 18, flow controller 19 and pressure controller 20, from air inlet 5 Into the condenser pipe 7 for the interior tower A6 for precooling tower 1, the temperature of interior tower A6 is -60 DEG C, it is possible to achieve the liquefaction of water vapour, forms The water of liquid, liquid water in condenser pipe outlet 8 by discharging.Since the temperature in interior tower A6 is higher than CO2Solidification point, CO2With it is other Gas (such as N2、O2) enter main cooling tower 2 in a gaseous form.Main cooling tower 2 by the sterlin refrigerator B9 that is connected with it, Temperature in controlling in tower B11 is -120 DEG C, less than CO2Solidification point, the CO in interior tower B112Solid is frozen into, is frozen in The surface of heat exchanger 10, it is achieved thereby that H2O and CO2In the separation of different parts.It is frozen in the solid-state CO of heat exchanger surface212, The rotation scraping board 14 driven by motor 13 is scraped, and it is fallen into storage tower 3.Storage tower 3 with it by being connected Sterlin refrigerator C16, it is -80 DEG C to control in storage tower 3 temperature, the CO of high-purity2It is stored in the form of solid.It is not cold Solidifying N2Discharged with other gases by gas discharge outlet 15.
Embodiment 1
With CO2/N2/H2Component after the mixed gas simulated combustion of O in flue gas, wherein CO2For 13vol%, N2For 82vol%, H2O is 5vol%.Low temperature CO using the present invention2Gas fractionation unit, CO is carried out with low temperature process2Separation, specifically Implementation process is as follows：
Mixed gas first passes through the SO in the removing flue gas of gas preprocessor 17x、NOxAnd flying dust, then pass through flow controller 19 control flow rates, then gaseous mixture admission pressure is controlled by pressure controller 20.Mixed gas enters from air inlet 5 to be condensed Pipe 7, the interior tower A6 for precooling tower 1 are connected with sterlin refrigerator A4, control in temperature in tower A6 be -60 DEG C.At a temperature of this Water vapour liquefies, and forms liquid water (preventing the blocking to form ice to pipeline), and the water of liquid is discharged from condenser pipe outlet 8. Since temperature is higher than CO at this time2Solidification point (about -78.5 DEG C) and N2Solidification point (about -209.86 DEG C), make CO2And N2With gaseous state Smoothly enter the interior tower B11 of main cooling tower 2.
The interior tower B11 of main cooling tower 2 is connected with sterlin refrigerator B9, and the set temperature of interior tower B9 is -120 DEG C, by It is less than CO in temperature at this time2Solidification point, make CO2Solid is frozen into, is frozen in the surface of heat exchanger 10, and this temperature is still Higher than N2Solidification point, so N2Storage tower 3 is still entered with gaseous state.It is frozen in the CO on 10 surface of heat exchanger212, pass through motor The 13 rotation scraping boards 14 driven are scraped, and make solid-state CO212 fall into storage tower 3.
Storage tower 3 is connected with sterlin refrigerator C16, and the set temperature of storage tower 3 is -80 DEG C, the CO of high-purity2With Solid form is stored, uncooled N2Discharged in a gaseous form by gas discharge outlet 15.
The low temperature CO that mixed gas passes through the present invention2Gas fractionation unit, realizes low temperature CO2Separation.Finally, water steams Vapour is discharged from the interior tower A6 for precooling tower in liquid form, CO2It is stored in solid form in storage tower, uncooled gas Body (N2), the gas discharge outlet discharge out of storage tower.

Claims (6)

  1. A kind of 1. low temperature CO2Separator, including precool tower, main cooling tower and storage tower three parts, it is characterised in that it is described Tower (1), main cooling tower (2) and storage tower (3) are precooled as cylindrical shape, is vertically arranged successively by upper, middle and lower；
    Precool and interior tower A (6) is provided with tower (1), it is vacuum state to precool between tower (1) and interior tower A (6)；Main cooling tower (2) interior tower B (11) is provided with, is also vacuum state between main cooling tower (2) and interior tower B (11)；Precool tower (1) and master is cold But do not connect between tower (2) and interior tower A (6) and interior tower B (11)；
    Interior tower A (6), interior tower B (11) and storage tower (3) are respectively arranged with refrigeration machine A (4), refrigeration machine B (9) and refrigeration machine C (16), the heat exchanger (10) of refrigeration machine B (9) is arranged on the middle position of interior tower B (11)；The periphery of heat exchanger (10) is provided with rotation Turn to scrape sassafras plate (14)；Main cooling tower (2) is additionally provided with motor (13) to control rotation to scrape sassafras plate (14)；
    Condenser pipe (7) is provided with interior tower A (6), precools the air inlet (5) that condenser pipe (7) are provided with the top of tower (1), in advance The side wall of cooling tower (1) is provided with the condensation-water drain (8) of condenser pipe (7), and the lower end of condenser pipe (7) extends to interior tower B (11) In；Interior tower B (11) connects with storage tower (3) below；The side wall of storage tower (3) is provided with gas discharge outlet (15)；
    Gas preprocessor (17), valve (18), flow controller are additionally provided with the front end of the air inlet (5) of condenser pipe (7) (19) and pressure controller (20).
  2. 2. low temperature CO according to claim 12Separator, it is characterised in that the interior tower A (6) for precooling tower (1) Interior set temperature is -60 DEG C, and the interior set temperature of interior tower B (11) of main cooling tower (2) is -120 DEG C, and temperature is set in storage tower (3) Spend for -80 DEG C.
  3. 3. low temperature CO according to claim 12Separator, it is characterised in that the refrigeration machine A (4), refrigeration machine B (9) It is free-piston type sterlin refrigerator with refrigeration machine C (16).
  4. 4. low temperature CO according to claim 12Separator, it is characterised in that the precooling tower (1), main cooling tower (2) and storage tower (3) is stainless steel material.
  5. 5. low temperature CO according to claim 12Separator, it is characterised in that the interior tower A (6), interior tower B (11) it is outer Surface is provided with aluminum foil material.
  6. 6. low temperature CO according to claim 12Separator, it is characterised in that the precooling tower (1), main cooling tower (2) and the outer surface of storage tower (3) is provided with pearl cotton heat-insulating material.
CN201610875761.0A 2016-09-29 2016-09-29 Low-temperature carbon dioxide separator Active CN106237648B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107019998A (en) * 2017-03-23 2017-08-08 天津大学 A kind of collecting carbonic anhydride method that film infiltration is combined with low temperature phase change
CN106890546A (en) * 2017-03-23 2017-06-27 天津大学 Film permeates the carbon dioxide capture device being combined with low temperature phase change
CN107806742A (en) * 2017-09-30 2018-03-16 南京宏博环保实业有限公司 A kind of low-temperature liquefaction method produces CO2Method and device
CN108956232B (en) * 2018-08-03 2021-03-30 中国核动力研究设计院 Sample preparation method and sample preparation equipment for carbon-14 in biological sample
JP7203401B2 (en) * 2020-05-01 2023-01-13 東邦瓦斯株式会社 Carbon dioxide capture device
CN115382240B (en) * 2022-08-25 2023-05-23 北京航天试验技术研究所 Mars atmosphere carbon dioxide capturing system and method adopting freezing method

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* Cited by examiner, † Cited by third party
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RU2440178C2 (en) * 2006-03-10 2012-01-20 Дуглас К. КОМРИ Materials and methods for sequestering carbon dioxide
CN201954916U (en) * 2010-12-20 2011-08-31 华北电力大学 CO2 separation and compression integrated device
CN202066300U (en) * 2011-03-25 2011-12-07 东南大学 Device for separating carbon dioxide from flue gas by liquefying
CN206198739U (en) * 2016-09-29 2017-05-31 天津大学 A kind of low-temperature carbon dioxide separator

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