CN103212271A - Gas separating system and method for separating gas by using system thereof - Google Patents
Gas separating system and method for separating gas by using system thereof Download PDFInfo
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Abstract
The invention discloses a gas separating system and a method for separating gas by using the system, the system comprises at least an adsorption tower and at least an adsorption-desorption tower which are communicated through a pipeline, an adsorption-desorption medium enables cycle between the adsorption tower and the adsorption-desorption tower, wherein before the adsorption-desorption medium reaches adsorption saturation, the adsorption-desorption tower can be the adsorption tower for absorbing the adsorption gas; when the adsorption-desorption medium can reach adsorption saturation or is close to saturation, and the adsorption-desorption tower is taken as a desorption tower for desorbing the adsorbed gas. The separating system can effectively prolong the adsorption time of the adsorption-desorption medium, the desorption time is shortened, and the adsorption and desorption efficiency can be increased.
Description
Technical field
The method that the present invention relates to a kind of gas separation system and use this system's divided gas flow particularly, relates to the piece-rate system of a kind of absorption and desorption specific gas and uses this system to separate the method for above-mentioned specific gas from waste gas or admixture of gas.
Background technology
Along be extensive use of fuel such as oil, natural gas, coal in industry, sphere of life, the toxic emission problem that these fuel produce in combustion process receives publicity for a long time as the environmental problem of global scale.Contain great amount of carbon dioxide in the above-mentioned waste gas, and a main cause of global warmingization is because atmospheric carbon dioxide levels increases.And for example, also may comprise composition, for example oxysulfide (SO outside the removing carbon dioxide in many industrial exhaust gas discharged
X), and oxysulfide helps the formation of acid rain.Because still considerable to above-mentioned Fuel Demand from now on, therefore how handling the waste gas of generation or the carbon dioxide in the gaseous mixture or other toxic gases will be the problem of a sternness.
In fact, some gas in waste gas or the gaseous mixture is the raw material that need supply, for example CO in some industrial process
2, CO, CH
4, NH
4Deng can be separated the purification back recycle as product material.Such as, catch and store (CCS) and improve in oil recovering (EOR) field carbon dioxide raw material that are absolutely necessary at carbon, buy the cost of carbon dioxide in order to obtain high concentration carbon dioxide or reduction, can separate and reclaim carbon dioxide from gaseous mixture expediently is an important channel that addresses the above problem.
In the past few decades, about separating and reclaim some specific gases from waste gas after burning or gaseous mixture is the problem of several studies always, wherein alternating temperature absorption (TSA) method is to utilize the equilibrium adsorption capacity of adsorbent with the characteristic that the temperature rising reduces, and adopts the method for operating of normal temperature absorption, desorption by heating.Because the amount of carbon dioxide is more in waste gas after fuel combustion or the gaseous mixture, a lot of researchs are to begin from the carbon dioxide of how recycling the waste gas, these researchs in early days at be " wet " separation and the recovery method of so-called carbon dioxide, promptly based on appropriate solution or solvent wash gaseous mixture that can the selective absorption carbon dioxide, and reclaim the method for adsorbed carbon dioxide by heating adsorbent solution or solvent.But the problem that the method runs into is that wash solution is vulnerable to the influence of its component oxidative phenomena, and, also comprise sulphur and nitrogen oxide (SO in waste gas or the gaseous mixture usually
XAnd NO
X), with some component reaction in the wash solution, therefore other hazardous compounds that can produce stable salt and be difficult to remove and handle need often to replace wash solution.
In recent years, research both at home and abroad mainly concentrates on the solid absorbent separation and reclaims on the system and method for carbon dioxide, US6 for example, 387,337 disclose a kind of from gaseous mixture the technology of separating carbon dioxide, wherein used in the adsorptive reactor to be reduced into the alkali metal that can use repeatedly or the adsorbent of alkaline-earth metal through the desorption carbon dioxide, between a double bed type heat reactor, moved.This technology comprises: first reactor is the adsorption tower that is filled with the adsorbent of reduction, and the gaseous mixture that will contain carbon dioxide feeds in first reactor, thereby carbon dioxide is adsorbed on the described adsorbent; The adsorbent with crossing that is adsorbed with carbon dioxide is moved to second reactor so that reduce, and the gas that is used for the carbon dioxide on the desorption adsorbent can comprise the synthesis gas of natural gas, methane, carbon monoxide, hydrogen and carbon monoxide and hydrogen; Then, the adsorbent that reduces is moved to first reactor, make it proceed adsorption process.The flow process of this technology and simple to operate, efficient, but the carbon dioxide purity after the introducing of exogenous reducing gas will directly cause separating reduces, and then need carry out extra gas lock out operation.
US6,755,892 disclose a kind of from waste gas the system of separating carbon dioxide, this system comprises: the carbon dioxide adsorbent bed of loading the adsorbent that contains amine and nitrile functionality; The pipeline that is communicated with carbonated exhaust gas source and described adsorbent bed; The outlet conduit of described adsorbent bed; From described adsorption tower, discharge the regenerating unit of carbon dioxide; Can control the control valve of the turnover gas of described adsorbent bed with at least one.This system is by the airflow direction in above-mentioned control valve or the control device converting system that adds, thereby carries out adsorption process and desorption process.And the above-mentioned regenerating unit that is used for the desorption carbon dioxide is a heater, utilizes the peripheral hardware heater to heat described adsorbent bed in the system, so that reach the temperature of desorption carbon dioxide.In addition, the method for also mentioning available feeding steam during this invents reaches desorption carbon dioxide purpose.This invention system carries out carbon dioxide separation and reclaims required equipment complexity, costliness, is difficult to operation, thereby means the with high investment and high maintenance costs of needs.In addition, also exist peripheral hardware source hot in nature heat transfer efficiency problem, separate back carbon dioxide purity, hot high pressure steam problems such as wearing and tearing to adsorbent.
In fact, US6,755,892 disclosed carbon dioxide separating systems have comprised at least two carbon dioxide absorber beds, wherein when an adsorbent bed in when absorption, another adsorbent bed is at desorption, but because desorption rate is more faster than adsorption rate usually, two adsorbent beds can't reach at full capacity simultaneously, and therefore, the adsorption efficiency of this piece-rate system and desorption efficient are not high.
US7,153,344 disclose a kind of method of separating and reclaim carbon dioxide from the oxide waste gas of burning.This method comprises: waste gas is fed in the semipermeable materials, from described waste gas, separate the air-flow that comprises high concentration carbon dioxide by the gas semipermeable materials, wherein at least a portion is comprised that the air-flow of high concentration carbon dioxide is used as industrial raw material pan feeding and/or stores the air-flow that at least a portion comprises high concentration carbon dioxide.
In fact, at US7,153, in the 344 disclosed piece-rate systems, backflow enters in the system part again as desorption gas through heating after as the air-flow that comprises high concentration carbon dioxide of product gas, is used to heat described semipermeable materials, so that the carbon dioxide desorption of its absorption.
The disclosure of above-mentioned all patent documentations is introduced with for referencial use in full at this.
Obviously, to other specific gas, for example CO, CH in waste gas or the gaseous mixture
4, SO
X, NO
X, H
2S or NH
4Deng the principle of carrying out system and method that adsorption-desorption handles and the adsorption-desorption system and method for carbon dioxide is identical.Undoubtedly, under the situation of the suitable adsorbent of change, absorption is equally applicable to separating of other gas or purification with the system of desorption carbon dioxide and the method for separating carbon dioxide thereof.
Although disclose a lot of system and methods in the prior art by adsorption-desorption mechanism divided gas flow, but common existence is owing to the problem that the inconsistent adsorption plant that causes of speed is oversize or separative efficiency is low of cryogenic absorption and high temperature desorption, and how addressing this problem to reduce the adsorption plant size or to improve separative efficiency is problem demanding prompt solution in gas separation and the recovery field.
For solving the problem that is faced in the above-mentioned prior art, the invention provides a kind of system and method that from admixture of gas, separates some specific gas, system is simple to operate, cost is low, efficient is high, can carry out continuity to these specific gas under the cryogenic absorption condition adsorbs fast, and can improve the desorption effect not introducing under the condition of exogenous desorption gas, thereby separablely obtain highly purified specific gas.
In addition, system and method of the present invention is by design cleverly, under the situation that does not change adsorbent kind and piece-rate system structure, prolonged the adsorption time of adsorbent, shortened the time of desorbing gas, thereby make that by improving adsorption efficiency and desorption efficient simultaneously the adsorption plant size reduces to improve greatly with the gas separative efficiency, and then overcome above-mentioned technical barrier of the prior art.
Summary of the invention
First aspect according to the present invention provides a kind of gas separation system, and it comprises at least one adsorption tower and at least one adsorption-desorption tower, and the two is connected by pipeline, so that the adsorption-desorption medium circulates between adsorption tower and adsorption-desorption tower; Its feature that is different from prior art is: described adsorption-desorption medium reach absorption saturated before, the adsorption-desorption tower adsorbs the place as adsorption tower to the gas in the admixture of gas, so that fully adsorbed gas improves adsorption efficiency; And reaching the saturated or absorption of absorption near after saturated at described adsorption-desorption medium, the adsorption-desorption tower carries out desorption as desorption column to the gas of absorption, so that improve desorbing gas efficient.
Randomly, the mode of available direct heating or indirect heats reaching to adsorb saturated or adsorb near saturated described adsorption-desorption medium, so that be attracted to adsorbed gas desorption in the described adsorption-desorption medium, directly heating refers to the direct described adsorption-desorption medium of heating of modes such as heat exchanger, electrical heating, heating using microwave and/or radiation heating; And indirect refers to first heating desorption gas, then desorption gas is made it to contact with described adsorption-desorption medium as heat carrier and heat, heat exchanger flow through wherein tube coil type heat exchanger of heat exchange medium preferably wherein, described heat exchange medium for example is a high-pressure water vapor, hydrogen, carbon dioxide and/or high temperature inert gas or the like.
Reach the saturated or absorption of absorption near after saturated at described adsorption-desorption medium, adsorption tower is proceeded absorption to the gas in the mixture, the adsorption-desorption tower carries out desorption as the attached tower of holder to the gas that is adsorbed onto in the adsorption-desorption medium simultaneously, preferably, at least a portion product gas of desorption in described adsorption-desorption tower can be back in the adsorption-desorption tower as desorption gas.When above-mentioned absorption and desorption are carried out in adsorbed gas, the way of contact of described admixture of gas and described adsorption-desorption medium is arbitrarily, for example following current or counter current contacting, reaching the saturated or absorption of absorption equally also is arbitrarily near the saturated described adsorption-desorption medium and the way of contact of desorption gas, for example following current or counter current contacting.
Said system comprises at least one adsorption tower and at least one adsorption-desorption tower, is possessing under the situation of two or more adsorption towers, and the connected mode between the described adsorption tower can be a serial or parallel connection; Equally, under the situation that possesses two or more adsorption-desorption towers, the connected mode between the described adsorption-desorption tower also can be a serial or parallel connection.
The gas of absorption and desorption can be selected according to actual needs in the said system, and described adsorption-desorption gas can be CO
2, CO, CH
4, SO
X, NO
X, H
2S or NH
4In one or more gases.
Described adsorption-desorption medium is reaching the saturated or absorption of absorption near after saturated, adsorption tower adsorbs the adsorbed gas in the admixture of gas, the adsorption-desorption tower carries out desorption as desorption column to the gas that adsorbs simultaneously, in this process, except that a part of product gas being refluxed as the desorption gas, also can feed the required desorption gas that is used for the adsorbed gas of desorption adsorption-desorption medium of adsorption-desorption tower, so that system carries out desorption to the gas that adsorbs from system is outside.But the parsing gas of any kind that the desorption gas those of ordinary skills from system's outside feeding adsorption-desorption tower know preferably, is the gas identical with product gas from the outside desorption gas that feeds the adsorption-desorption tower of system.
The adsorption-desorption medium that said system is used can be selected according to the type of adsorption-desorption gas, and described adsorption-desorption medium is selected from one or more adsorbents of following material: calcium oxide, magnesia, aluminium oxide, silica gel, active carbon, CNT, zeolite, diatomite, molecular sieve, ion exchange resin, containing metal compound material modified, contain the material modified of amine functional group or contain the material modified of nitrile functional group.Obviously, because of reasons such as himself life cycles, described system also can comprise adsorption-desorption medium feeding mouth and adsorption-desorption medium discharging opening useless and that do not re-use, so that the adsorption-desorption medium that periodic replacement can't be regenerated.
In fact, described adsorption-desorption tower is realized changing between adsorption tower and the desorption column by pipeline and valve, promptly when the adsorption-desorption tower uses as adsorption tower, contain the admixture of gas of adsorbed gas and/or fresh adsorption-desorption medium by pipeline to wherein importing, and when the adsorption-desorption tower uses as desorption column, close above-mentioned input channel by valve, simultaneously also move to the admixture of gas in the adsorption-desorption tower in the adsorption tower and proceed gas absorption therein or it is shifted out outside the system by pipeline, again reaching in the adsorption tower adsorbed saturated or adsorbed near saturated adsorption-desorption medium and move in the adsorption-desorption tower by pipeline, and realize desorbing gas and regeneration therein, said process can intersected with each otherly repeat.
Second aspect according to the present invention provides a kind of method with the said system divided gas flow, and this method may further comprise the steps in order:
1) admixture of gas that will contain described adsorbed gas feeds in described adsorption tower and the adsorption-desorption tower, thereby described adsorbed gas is adsorbed onto in the adsorption-desorption medium that circulates between adsorption tower and adsorption-desorption tower;
2) reach the saturated or absorption of absorption near after saturated at described adsorption-desorption medium, to in admixture of gas in the adsorption-desorption tower and/or the fresh adsorption-desorption medium immigration adsorption tower absorption be proceeded in the described adsorbed gas in the admixture of gas, to adsorb saturated simultaneously or adsorb and from adsorption tower, move in the adsorption-desorption tower near saturated adsorption-desorption medium, and the adsorption-desorption medium in the adsorption-desorption tower is heated to more than the adsorbed gas desorption temperature, thereby desorption is carried out in the described adsorbed gas that is adsorbed in the adsorption-desorption medium
3) gas behind the desorption is shifted out outside the system as product gas;
4) will shift out outside the system through the admixture of gas that adsorbing separation goes out adsorbed gas.
Preferably, the heating of adsorption-desorption medium is realized by feed desorption gas in the adsorption-desorption tower, and at least a portion product gas can be used as desorption gas and is back in the described adsorption-desorption tower, and wherein the product gas of Hui Liuing need be heated to more than the desorption temperature before in being back to described adsorption-desorption tower.
Generally speaking, can select desorption gas to the adsorption-desorption characteristic of specific gas according to the adsorption-desorption medium, as mentioned above, desorption gas can be from outside the system, the also product gas that can reflux from a part is back to 10～60 (volume) % that product gas in the described adsorption-desorption tower accounts for the gas gross that desorption produces in described adsorption-desorption tower usually as desorption gas.
In said method, the product gas that desorption is obtained further passes through at least one cyclone cluster, pneumatic filter, drier and/or gas compressor, thereby form the higher product gas of purity, described fresh adsorption-desorption medium is also from the adsorption-desorption medium of regenerating through gas desorption in the adsorption-desorption tower, each step of said method can circulate in order, so that realize the continuous separation of gas.
Description of drawings
Fig. 1 is the structural representation of an embodiment of gas separation system of the present invention.
Fig. 2 is the structural representation of another embodiment of gas separation system of the present invention.
The specific embodiment
Be further explained in detail the present invention by description below with reference to accompanying drawing, but following description only is used to make the general technical staff of the technical field of the invention can be expressly understood principle of the present invention and marrow more, and does not mean that the present invention is carried out any type of restriction.Parts that be equal in the accompanying drawing or corresponding or feature are represented with identical reference numerals.
Fig. 1 is embodiment of gas separation system of the present invention, and it is set at carbon dioxide with specific gas for absorption and the 10a of desorption system in this embodiment.System 10a is at relative low temperature, for example be lower than under 60 ℃ of temperature absorbing carbon dioxide from admixture of gas, at relatively-high temperature, for example be higher than under 100 ℃ of temperature the carbon dioxide of desorption absorption from adsorbent, thereby reach the purpose of from admixture of gas, separating and reclaim carbon dioxide.The system of Fig. 1 mainly comprises a first fluidized bed (being adsorption tower) 20, one second fluid bed (being the adsorption-desorption tower) 30, the separator 40 and second separator 50, the admixture of gas conveyance conduit 11 of the first fluidized bed 20, the mixed gas pipeline road 35 of second fluid bed 30, the output channel 23 of the first fluidized bed 20, the desorption gas pipeline 33 of second fluid bed 30, the subsidiary conduit 65 of the bypass line 60 of desorption gas pipeline 33 and conveying desorption gas, wherein, be filled with the adsorbent that can absorbing carbon dioxide then can discharge carbon dioxide again in the first fluidized bed 20 and second fluid bed 30 by desorption, it is renewable adsorbent, for example calcium oxide and/or magnesia, the first fluidized bed 20 is communicated with the lower end of second fluid bed 30 by the separator 40 that its top is provided with, second fluid bed 30 is communicated with the lower end of the first fluidized bed 20 by second separator 50 that its top is provided with, thereby described adsorbent is circulated between the first fluidized bed 20 and second fluid bed 30.Adsorbent reach absorption saturated before, the first fluidized bed and second fluid bed all carry out adsorption treatment to carbon dioxide, make its fully absorbing carbon dioxide; And reach the saturated or absorption of absorption near after saturated at described adsorbent, adsorbent in the first fluidized bed (adsorption tower) is moved in second fluid bed (adsorption-desorption tower) by separator 40 and pipeline 34, by the pump (not shown) admixture of gas in second fluid bed (adsorption-desorption tower) is moved in the first fluidized bed (adsorption tower) simultaneously, and to wherein adding fresh adsorbent, so that the first fluidized bed continues carbon dioxide is carried out adsorption treatment, second fluid bed carries out the desorption processing to the carbon dioxide that is adsorbed onto in the adsorbent simultaneously, thereby improves the absorption and the desorption efficient of carbon dioxide simultaneously.The primary clustering reference numerals explanation of system shown in Figure 1 is referring to following table 1.
Table 1
| 10a | Whole system | 40 | Separator |
| 11 | The gaseous mixture input channel of the first fluidized bed | 50 | |
| 20 | The first fluidized bed | 60 | The bypass line that desorption gas refluxes |
| 21 | The import of first fluidized bed admixture of gas | 61 | The control valve of bypass line |
| 22 | The adsorbent import | 62 | The heat exchanger of the desorption gas that refluxes |
| 23 | First fluidized bed admixture of gas output channel | 63 | The second fluidized bed gas mixture conveyance conduit switch |
| 24 | The connecting pipe of the first fluidized bed | 64 | The bypass line switch that desorption gas refluxes |
| 30 | Second fluid bed | 65 | Auxiliary desorption gas conveyance conduit |
| 31 | The admixture of gas import of second fluid bed | 66 | Auxiliary desorption gas heat exchanger |
| 32 | The spent sorbents outlet | 67 | Auxiliary desorption gas |
| 33 | The desorption gas output channel of second fluid bed | 70 | Pneumatic filter |
| 34 | The connecting pipe of second fluid bed | 80 | Drier |
| 35 | The second fluidized bed gas mixture input channel | 81 | The gaseous carbon dioxide conveyance conduit |
| 36 | The heat exchanger of heated air mixture | 90 | Gas compressor |
| 37 | The control valve of admixture of gas conveyance conduit | 91 | The liquid carbon dioxide conveyance conduit |
At the beginning of system starts or before described adsorbent reaches capacity, open the admixture of gas conveyance conduit switch 63 of second fluid bed 30, and close the bypass line switch 64 that auxiliary desorption gas conveyance conduit switch 67 and desorption gas reflux, admixture of gas in the admixture of gas conveyance conduit 35 of admixture of gas conveyance conduit 11 neutralization second fluid bed of the first fluidized bed is fed in the first fluidized bed 20 and second fluid bed 30 simultaneously, so that the carbon dioxide in the abundant adsorbed gas mixture of described adsorbent wherein.
Carbonated admixture of gas enters in the first fluidized bed 20 by its admixture of gas import 21 along the admixture of gas conveyance conduit 11 of the first fluidized bed 20, carbonated admixture of gas is with fresh and/or do not adsorb saturated adsorbent and contact in the first fluidized bed 20, carbon dioxide in the admixture of gas is adsorbed onto in the described adsorbent gradually, and the gas vent of removing to the admixture of gas of small part or most of carbon dioxide from the first fluidized bed 20 shifts out outside the system along its output channel 23.Simultaneously, carbonated admixture of gas enters in second fluid bed 30 by its admixture of gas import 31 along the admixture of gas conveyance conduit 35 of second fluid bed 30 equally, carbonated admixture of gas contacts with fresh and/or unsaturated adsorbent equally in second fluid bed 30, carbon dioxide in the admixture of gas is adsorbed onto in the described adsorbent, and the gas vent of removing to the admixture of gas of small part or most of carbon dioxide from second fluid bed 30 shifts out outside the system along its output channel (not shown).Remove to the admixture of gas of small part or most of carbon dioxide and can require directly enter in the atmosphere, or be for further processing, in this article this is repeated no more according to operation.
The top of the described first fluidized bed 20 is provided with separator 40, and separator 40 can be gas-solid separator, for example cyclone cluster, with absorbent powder and/or the adsorbent that will be carried secretly and removed to the admixture of gas of small part or most of carbon dioxide and be separated, the admixture of gas that separates carbon dioxide shifts out outside the system along its output channel 23 from the top of separator 40, and then the connecting pipe 24 along the first fluidized bed 20 moves to second fluid bed 30 from the bottom of separator 40 for absorbent powder and solid absorbent.Be provided with second separator 50 at second fluid bed, 30 tops, the also gas-solid separator of second separator 50, can select the separator identical with separator 40, cyclone cluster for example, perhaps can select other separators different with separator 40, with with absorbent powder and/or adsorbent and removed to small part, or the admixture of gas of most of carbon dioxide is separated, the admixture of gas that separates carbon dioxide shifts out outside the system along its output channel (not shown) from the top of second separator 50, then the connecting pipe 34 along second fluid bed 30 moves to the first fluidized bed 20 from the bottom of separator 50 for absorbent powder and solid absorbent, thereby finishes the circulation of adsorbent between the first fluidized bed 20 and second fluid bed 30 during the absorbing carbon dioxide.
The adsorbent of loading in the first fluidized bed 20 and second fluid bed 30 is a reproducible adsorbent behind desorbing gas, but the regenerable sorbent that described adsorbent those of ordinary skills know, can be selected from calcium oxide, magnesia, active carbon, CNT, zeolite, diatomite, molecular sieve, ion exchange resin, containing metal compound material modified, contain the amine functional group material modified, contain the material modified of nitrile functional group and their mixture.The time of staying and the operating temperature of admixture of gas in the first fluidized bed 20 and second fluid bed 30 of need handling depends on the absorption and the desorption character of adsorbent.
Reach the saturated or absorption of absorption near after saturated at described adsorbent, described system 10a can move under several different conditions, as under first kind of running status, close auxiliary desorption gas conveyance conduit switch 67 and open the admixture of gas conveyance conduit switch 63 of second fluid bed and the bypass line switch 64 of desorption gas backflow, desorption is adsorbed the carbon dioxide that agent is adsorbed in described second fluid bed 30 so that the admixture of gas in the admixture of gas conveyance conduit 35 of the desorption gas in the bypass line 60 and second fluid bed feeds through the heating back.Under second kind of running status, close the admixture of gas conveyance conduit switch 63 of second fluid bed and open auxiliary desorption gas conveyance conduit switch 67 and the bypass line switch 64 of desorption gas backflow, so that carbon dioxide in the bypass line 60 that desorption gas refluxes and the carbon dioxide in the auxiliary desorption gas conveyance conduit 65 are adsorbed the carbon dioxide of agent absorption through desorption in described second fluid bed 30 of heating back feeding.Under the third running status, close the admixture of gas conveyance conduit switch 63 of the auxiliary desorption gas conveyance conduit switch 67 and second fluid bed and open the bypass line switch 64 that desorption gas refluxes, desorption is adsorbed the carbon dioxide that agent is adsorbed in described second fluid bed 30 so that the carbon dioxide in the bypass line 60 of desorption gas backflow feeds through the heating back.
Among the described system 10a, when CO 2 total amount that desorption in second fluid bed 30 obtains carbon dioxide, can select described system under first kind of state or second kind of state, to move through being not enough to the desorption adsorbent after the heating and in the first fluidized bed 20 and/or second fluid bed 30, adsorbing.When carbon dioxide that total carbon dioxide capacity that desorption in second fluid bed 30 obtains adsorbs in the first fluidized bed 20 and/or second fluid bed 30 with the desorption adsorbent through the heating metapedes, can select described system under the third state, to move.
As mentioned above, under first kind of running status, will assist desorption gas conveyance conduit switch 67 to close, and the admixture of gas conveyance conduit switch 63 of second fluid bed and the bypass line switch 64 of desorption gas backflow will be opened.
The admixture of gas that contains carbon dioxide enters in the first fluidized bed 20 by its gas feed 21 along the admixture of gas conveyance conduit 11 of the first fluidized bed 20, carbonated admixture of gas contacts with adsorbent in the first fluidized bed 20, carbon dioxide in the admixture of gas is adsorbed onto on the described adsorbent, and its gas vent of top of removing to the admixture of gas of small part or most of carbon dioxide from the first fluidized bed 20 shifts out outside the system along its output channel 23.
As mentioned above, the top of the first fluidized bed 20 is provided with gas-solid separator 40, thereby with absorbent powder and/or solid absorbent and removed to small part, or the admixture of gas of most of carbon dioxide is separated, admixture of gas shifts out outside the system along its output channel 23 from the top of separator 40 subsequently, and the adsorbent of absorbing carbon dioxide or absorbing carbon dioxide have reached saturated or approaching saturated adsorbent moves to second fluid bed 30 by gas-solid separator 40 and connecting pipe 24 from the first fluidized bed 20 lower end, in second fluid bed 30, also reached saturated or be heated to more than the desorption temperature near the adsorbent in the second saturated fluid bed 30 from the adsorbent of the first fluidized bed 20 and absorbing carbon dioxide, for example contact with the thermal desorption gas that gas feed 31 from second fluid bed 30 feeds, emit carbon dioxide after making it reach the carbon dioxide desorption temperature, the carbon dioxide that is come out by desorption shifts out outside the system by the desorption gas pipeline 33 of second fluid bed 30 subsequently.
Here it should be noted that: the hot gas that is fed by gas feed 31 is that desorption gas comprises: the admixture of gas that feeds in second fluid bed 30 along the admixture of gas conveyance conduit 35 of second fluid bed, and the product gas that feeds in second fluid bed 30 along the bypass line 60 that desorption gas refluxes, and along auxiliary desorption gas conveyance conduit 65 feed in second fluid bed 30 from the desorption gas outside the system.Therefore, the gas by second fluid bed, 30 desorption gas pipelines 33 has not only comprised the carbon dioxide of above-mentioned adsorbent desorption, but also comprises the desorption gas that is used for the desorption carbon dioxide.The purity or the concentration that shift out the carbon dioxide outside the system as if the desorption gas pipeline by second fluid bed 30 do not reach requirement, a part of product gas in the desorption gas pipeline 33 can be emitted and not do recycling outside the system, the bypass line 60 that another part product gas in the desorption gas pipeline 33 then refluxes along desorption gas feeds in second fluid bed 30 to be used as desorption gas.Simultaneously, feed control valve 61 controls of the bypass line 60 that the gas flow in second fluid bed 30 refluxes by the control valve 37 and the desorption gas of admixture of gas conveyance conduit 35 along the admixture of gas conveyance conduit 35 of second fluid bed 30 and along the bypass line 60 that desorption gas refluxes, along gas the mixings conveyance conduit 35 of second fluid bed 30 and the heater 62 that feeds the bypass line 60 that the temperature of the gas of second fluid bed 30 then refluxes by the heater 36 and the desorption gas of admixture of gas conveyance conduit 35 along the bypass line 60 that desorption gas refluxes control.
In second fluid bed 30, the temperature that absorbing carbon dioxide reaches capacity or approaching saturated adsorbent contacts with above-mentioned thermal desorption gas makes adsorbent raises and reaches more than the desorption temperature, thereby desorption goes out carbon dioxide, and the result obtains adsorbent fresh or regeneration.The top of described second fluid bed 30 is provided with the second gas-solid separator 50, thereby adsorbent and product gas fresh or regeneration are separated, product gas shifts out outside the system along desorption gas pipeline 33 from the top of separator 50, then the connecting pipe 34 along second fluid bed 30 moves to the first fluidized bed 20 adsorbent of fresh or regeneration from the bottom of separator 50, thereby finishes the desorption circulation of adsorbent between the first fluidized bed 20 and second fluid bed 30.
Generally speaking, the used repeatedly adsorbent of a part need regularly be replaced.Therefore, in the 10a of system, the first fluidized bed 20 lower ends are provided with adsorbent import 22, be provided with spent sorbents outlet 32 in second separator, 50 lower ends of second fluid bed 30, so that when needs replenish fresh adsorbent, add an amount of adsorbent, also can export 32 simultaneously and remove an amount of spent sorbents by spent sorbents by adsorbent import 22.
It should be noted that: under the situation of the heater 36 that does not start second fluid bed 30, the adsorbent in the adsorbent in the first fluidized bed 20 and second fluid bed 30 is simultaneously at absorbing carbon dioxide; And after starting the heater 36 of second fluid bed 30, the adsorbent in the first fluidized bed 20 continues at absorbing carbon dioxide, and the adsorbent in second fluid bed 30 under the heat effect of thermal desorption gas at the desorption carbon dioxide.
Under second kind of running status, when second fluid bed 30 carries out desorb, the switch 63 of the admixture of gas conveyance conduit 35 of second fluid bed 30 cuts out, and will assist the switch 67 of desorption gas conveyance conduit 65 and the switch 64 of the bypass line 60 that desorption gas refluxes to open.
Carbonated admixture of gas enters in the first fluidized bed 20 by its gas feed 21 along the admixture of gas conveyance conduit 11 of the first fluidized bed, carbonated admixture of gas contacts with adsorbent in the first fluidized bed 20, and the carbon dioxide in the gas mixing fog is adsorbed onto in the described adsorbent gradually.Remove to small part, or the output channel 23 of the admixture of gas of most of carbon dioxide from the outlet of the admixture of gas of the first fluidized bed 20 along separator 40 tops is moved out of outside the system, and the adsorbent of absorbing carbon dioxide or absorbing carbon dioxide reach capacity or move to the lower end of second fluid bed 30 by separator 40 and connecting pipe 24 near saturated adsorbent from the first fluidized bed 20, in second fluid bed 30 from the adsorbent of the first fluidized bed 20 with absorbing carbon dioxide has also reached capacity or be heated to more than the desorption temperature near the saturated adsorbent in second fluid bed 30, for example contact with the thermal desorption gas that gas feed 31 from second fluid bed 30 feeds, emit carbon dioxide after making it reach the carbon dioxide desorption temperature, the carbon dioxide that is come out by desorption is moved out of system by the desorption gas pipeline 33 of second fluid bed 30.
Under this running status, the thermal desorption gas that is fed by gas feed 31 comprises: the product carbon dioxide that the bypass line 60 that refluxes along desorption gas feeds in second fluid bed 30, and the carbon dioxide outside the system that auxiliary desorption gas conveyance conduit 65 feeds in second fluid bed 30.Select the reason of this running status to be: the product total carbon dioxide capacity that is refluxed by the desorption gas backflow bypass line 60 of second fluid bed 30 is failed to reach and be enough to all carbon dioxide that the desorption adsorbent adsorbs in the first fluidized bed 20 and/or second fluid bed 30, under this running status, the desorption gas of desorption carbon dioxide is the carbon dioxide after the heating, do not add other gas beyond the carbon dioxide, so it is higher to shift out the carbon dioxide purity of system from the desorption gas pipeline 33 of second fluid bed.Simultaneously, along the desorption gas flow of assisting desorption gas conveyance conduit 65 and feed in second fluid bed 30 along desorption gas backflow bypass line 60 is to be controlled by the control valve 61 of control valve (not marking) of assisting desorption gas conveyance conduit 65 and desorption gas backflow bypass line 60, and along assisting desorption gas conveyance conduit 65 and feeding heater 62 controls of the temperature of the desorption gas in second fluid bed 30 by the bypass line 60 of heater 66 of assisting desorption gas conveyance conduit 65 and desorption gas backflow along desorption gas backflow bypass line 60.
In second fluid bed 30, when desorb or desorption, absorbing carbon dioxide reaches capacity or near saturated adsorbent contacts with above-mentioned thermal desorption gas self temperature is increased to more than the desorption temperature, thus the desorption carbon dioxide, and the result obtains adsorbent fresh or that regenerate.Connecting pipe 34 along second fluid bed 30 moves to the first fluidized bed 20 from second separator, 50 bottoms at second fluid bed, 30 tops with the adsorbent of fresh or regeneration, thereby finishes the desorption circulation of adsorbent between the first fluidized bed 20 and second fluid bed 30.Desorption gas conveyance conduit 33 along second fluid bed 30 shifts out system to the product carbon dioxide that desorption obtains from the top of second separator 50.
As mentioned above, under the third running status, when second fluid bed 30 carries out desorb, the switch 63 of the admixture of gas conveyance conduit 35 of second fluid bed 30 and the switch 67 of auxiliary desorption gas conveyance conduit 65 are closed, and with desorption gas, be that the switch 64 of product gas backflow bypass line 60 is opened.
Carbon dioxide is identical with adsorption process under second kind of running status in the adsorption process under the third running status, the output channel 23 of the admixture of gas that is removed to small part or most of carbon dioxide from its gas vent of the first fluidized bed 20 along separator 40 tops shifts out outside the system, and the adsorbent of absorbing carbon dioxide or absorbing carbon dioxide reach capacity or move to second fluid bed 30 near the saturated connecting pipe 24 of adsorbent from separator 40 bottoms along the first fluidized bed 20.
With the adsorbent of absorbing carbon dioxide or absorbing carbon dioxide reaches capacity or move to the lower end of second fluid bed 30 from the first fluidized bed 20 by separator 40 and connecting pipe 24 near saturated adsorbent, absorbing carbon dioxide reaches capacity or contacts with thermal desorption gas from gas feed 31 feedings of second fluid bed 30 near saturated adsorbent in second fluid bed 30, emit carbon dioxide after making it reach the carbon dioxide desorption temperature, the carbon dioxide that is come out by desorption shifts out system by the desorption gas pipeline 33 of second fluid bed 30.Under this running status, when desorb or desorption, the thermal desorption gas that is fed by gas feed 31 is the product carbon dioxide that feeds in second fluid bed 30 along desorption gas backflow bypass line 60.Desorption gas output channel 33 by second fluid bed 30 shifts out at least a portion carbon dioxide of system in desorption gas backflow bypass line 60 feedings second fluid bed 30, be used for the carbon dioxide of desorption adsorbent in the first fluidized bed 20 and/or 30 absorption of second fluid bed, preferably, be used for 10～60 (volume) % that product carbon dioxide quantity that desorption is adsorbed the carbon dioxide of agent absorption accounts for the total CO 2 quantity that described system produces by described desorption gas backflow bypass line 60.Under this running status, desorption gas is the product carbon dioxide after the heating, does not add other gas beyond the carbon dioxide, so it is higher to shift out the carbon dioxide purity of system from the desorption gas output channel 33 of second fluid bed 30.Control by the control valve 61 of desorption gas backflow bypass line 60 along the product gas flow that desorption gas backflow bypass line 60 feeds in second fluid bed 30, and backflow product gas temperature is by heater 62 controls of desorption gas backflow bypass line 60.
In second fluid bed 30, absorbing carbon dioxide reaches capacity or near saturated adsorbent contacts with above-mentioned thermal desorption gas self temperature is increased to more than the desorption temperature, thus the desorption carbon dioxide, and the result obtains adsorbent fresh or that regenerate.Connecting pipe 34 along second fluid bed 30 moves to the first fluidized bed 20 from second separator, 50 bottoms at second fluid bed, 30 tops with the adsorbent of fresh or regeneration, thereby finishes the desorption circulation of adsorbent between the first fluidized bed 20 and second fluid bed 30.The carbon dioxide that desorption obtains the then desorption gas pipeline 33 from second separator, 50 tops along second fluid bed 30 shifts out system.
Under above three kinds of running statuses, the CO 2 that desorption obtains shifts out system from second fluid bed 30 after, also can be for further processing according to demand, after product gas or the desorption gas desorption gas pipeline 33 from second separator, 50 tops along second fluid bed 30 shifts out system, can make it pass through various gas, solid, liquid separator, for example pneumatic filter 70 and drier 80 are exported the gaseous state high-purity carbon dioxide product that obtains after treatment along gaseous carbon dioxide product conveyance conduit 81 afterwards.Perhaps, make it further by gas compressor 90, after compression along liquid carbon dioxide conveyance conduit 91 dispensing liquid high-purity carbon dioxide products again.
Fig. 2 is another embodiment of gas separation system of the present invention, it is the system 10b of absorption and desorption gas, its specific adsorbed gas still is carbon dioxide, the operation logic of system 10b is identical with the 10a of system, and different is, and the 10b of system compares with the 10a of system has saved second separator 50 that second fluid bed 30 is arranged at its top.The explanation of primary clustering reference numerals is also referring to table 1.System 10b mainly comprises a first fluidized bed (adsorption tower) 20, one second fluid bed (adsorption-desorption tower) 30, gas-solid separator 40, the admixture of gas conveyance conduit 11 of the first fluidized bed 20, the admixture of gas conveyance conduit 35 of second fluid bed 30, the gas output tube road 23 of the first fluidized bed 20, the desorption gas output channel 33 of second fluid bed 30, the desorption gas backflow bypass line 60 of desorption gas pipeline 33 and the auxiliary desorption gas conveyance conduit 65 that transports the desorption gas outside system, wherein, in the first fluidized bed 20 and second fluid bed 30 regenerable sorbent is housed, the first fluidized bed 20 is communicated with second fluid bed 30 by the separator 40 that its top is provided with, the upper end of second fluid bed 30 is communicated with the lower end of the first fluidized bed 20, thereby described adsorbent is circulated between the first fluidized bed 20 and second fluid bed 30.
It should be noted: as illustrated in fig. 1 and 2, in the 10a of system, the mode that carbon dioxide contacts with adsorbent all is the following current contact, and in the 10b of system, the mode that carbon dioxide contacts with adsorbent in the first fluidized bed is the following current contact, and the mode that carbon dioxide contacts with adsorbent in second fluid bed also is the following current contact.
Above-mentioned three kinds of methods of operation and embodiment illustrated in figures 1 and 2 only are to enumerate and demonstrate, the not used method of operation and the embodiment of limit gas separation system of the present invention, the present invention does not get rid of other method of operation and the embodiment that meets essence of the present invention and principle.
Embodiment
Embodiment 1
With separating carbon dioxide the admixture of gas of gas separation system of the present invention behind coal combustion shown in Figure 1, this piece-rate system is laboratory scale separator, and the chemical composition of admixture of gas raw material is formed as shown in table 1:
Table 1
| Unit | CO 2 | SO 2 | H 2O | N 2 | Total amount |
| Volume % | 17.65 | 0.05 | 7.15 | 75.15 | 100 |
| Weight % | 25.67 | 0.11 | 4.26 | 69.96 | 100 |
In this gas separation system, the adsorption-desorption medium of selecting, be that adsorbent is that (weight ratio is 1: 1 DEA-MCM-41 to the solid amine carbon dioxide absorber, be purchased from U.S. FISHER or Uop Inc.), its particle diameter is the 60-80 micron, water content is less than 1 weight %, and the absorption and the desorption properties of carbon dioxide are as shown in table 2:
Table 2
Take above-mentioned the third running status, promptly desorption gas is the CO 2 gas that refluxes fully, and after system started and moves normally, the operating pressure of fluid bed 20 was 0.133MPa, and operating temperature is 40-51 ℃; And the operating pressure of fluid bed 30 also is 0.133MPa, and operating temperature is 40-51 ℃ during its absorption; Operating temperature is 113 ℃ during desorption, and each technological parameter of other of system is as shown in table 3:
Table 3
| Material flow | Flow (kilogram/hour) | Temperature (℃) | Pressure (MPa) |
| The admixture of gas raw material | 100 | 40 | 0.121 |
| Fresh or regenerate adsorbent | 12.8 | 43 | 0.133 |
| Adsorb saturated adsorbent | 38.47 | 51 | 0.133 |
| Admixture of gas behind the separating carbon dioxide | 74.33 | 51 | 0.101 |
| The CO 2 that refluxes | 24.6 | 113 | 0.125 |
| The CO 2 total amount | 25.67 | 113 | 0.101 |
Fluid bed 30 operating temperature when adsorbing with desorption is different, in order to realize the transformation between its adsorption tower and the desorption column rapidly, the heat exchanger (not shown) can be set in the inside of fluid bed 30 or when the absorption beginning, feed the lower admixture of gas raw material of temperature, make fresh or reproducing adsorbent contact with the gas mixture material back temperature reach about 40-43 ℃, and fresh from separator 50 the flow ipes 24 or reproducing adsorbent temperature is also higher, also can be in pipeline 24 or the inside of fluid bed 20 the heat exchanger (not shown) is set or when the absorption beginning, in fluid bed 20, also feeds the lower admixture of gas raw material of temperature, make wherein fresh or reproducing adsorbent contact with the gas mixture material afterwards that temperature also reaches about 40-43 ℃.
As shown in table 2, the desorption rate of adsorbent is 7.1 times of its adsorption rate, and therefore, adsorbent carries out a desorb or desorption stop 7 times in fluid bed 20 and 30 after in fluid bed 30, thereby finishes total circulation of absorption and desorption.
The chemical composition of the admixture of gas behind desorption or the separating carbon dioxide is formed as shown in table 4:
Table 4
| Unit | CO 2 | SO 2 | H 2O | N 2 | Total amount |
| Volume % | 1.68 | 0.06 | 8.54 | 89.72 | 100 |
| Weight % | 2.68 | 0.14 | 5.58 | 91.60 | 100 |
Carbon dioxide weight adsorption rate is: (25.67-2.68 * (100-25.67)/(100-2.68))/25.67=92%; And the volume adsorption rate of carbon dioxide is: (17.65-1.68 * (100-17.68)/(100-1.68))/17.65=92%.
Can find out from the embodiment of the invention 1: the present invention utilizes the difference of adsorption-desorption medium adsorption rate and desorption rate to improve existing adsorption-desorption gas separation system, make the adsorption plant size decreases, and increased absorption and desorption efficient simultaneously, thereby the efficient of gas separation and the operability of equipment have finally been improved greatly.
Term that this specification is used and form of presentation only are used as descriptive and nonrestrictive term and form of presentation, the feature that will represent and describe unintentionally when using these terms and form of presentation or any equivalent exclusion of its part.
Although represented and described several embodiments of the present invention, the present invention is not restricted to described embodiment.On the contrary, those of ordinary skills should recognize under the situation that does not break away from principle of the present invention and spirit can carry out any accommodation and improvement to these embodiments, and protection scope of the present invention is determined by appended claim and equivalent thereof.
Claims (19)
1. gas separation system comprises:
At least one adsorption tower and at least one adsorption-desorption tower, the two is connected by pipeline, so that the adsorption-desorption medium circulates between described adsorption tower and adsorption-desorption tower,
It is characterized in that: described adsorption-desorption medium reach absorption saturated before, the adsorption-desorption tower adsorbs the gas in the admixture of gas as adsorption tower, so that fully adsorbed gas improves adsorption efficiency; And it is saturated or near after saturated to reach absorption at described adsorption-desorption medium, and the adsorption-desorption tower carries out desorption as desorption column to the gas of absorption, so that improve desorbing gas efficient.
2. system according to claim 1, wherein the mode with direct heating or indirect heats reaching to adsorb saturated or adsorb near saturated described adsorption-desorption medium, so that be attracted to the adsorbed gas desorption in the described adsorption-desorption medium.
3. system according to claim 2, wherein directly heating refers to directly heat described adsorption-desorption medium with the mode of heat exchanger, electrical heating, heating using microwave and/or radiation heating; And indirect refers to first heating desorption gas, then desorption gas is made it to contact with described adsorption-desorption medium as heat carrier and heats.
4. system according to claim 3, wherein heat exchanger refers to flow through wherein tube coil type heat exchanger of heat exchange medium.
5. system according to claim 1, wherein at least a portion product gas through described adsorption-desorption tower desorption is back in the adsorption-desorption tower as desorption gas.
6. system according to claim 1 is wherein in absorption and/or make described admixture of gas and described adsorption-desorption medium carry out following current or counter current contacting during desorption gas and/or make saturated or approaching saturated adsorption-desorption medium and the desorption gas of absorption carry out following current or counter current contacting.
7. system according to claim 1, between the wherein said adsorption tower and the connected mode between the described adsorption-desorption tower be serial or parallel connection.
8. system according to claim 1, wherein said adsorbed gas is CO
2, CO, CH
4, SO
X, NO
X, H
2S or NH
4In one or more gases.
9. system according to claim 1 is the gas identical with described product gas from the outside desorption gas that feeds the described adsorption-desorption tower of described system wherein.
10. system according to claim 1, wherein said adsorption-desorption medium is one or more adsorbents that are selected from the following material: calcium oxide, magnesia, aluminium oxide, silica gel, active carbon, CNT, zeolite, diatomite, molecular sieve, ion exchange resin, containing metal compound material modified, contain the material modified of amine functional group or contain the material modified of nitrile functional group.
11. system according to claim 1, wherein said adsorption-desorption tower is by the transformation between pipeline and valve realization adsorption tower and the desorption column.
12. one kind with the method according to one of any described system divided gas flow of aforementioned claim 1-11, this method may further comprise the steps in order:
1) admixture of gas that will contain described adsorbed gas feeds in described adsorption tower and the described adsorption-desorption tower, thereby described adsorbed gas is adsorbed onto in the adsorption-desorption medium that circulates between adsorption tower and adsorption-desorption tower;
2) reach the saturated or absorption of absorption near after saturated at described adsorption-desorption medium, admixture of gas in the adsorption-desorption tower and/or fresh adsorption-desorption medium are moved in the adsorption tower, and to the described adsorbed gas in the admixture of gas proceed absorption, to adsorb saturated simultaneously or adsorb and from adsorption tower, move in the adsorption-desorption tower near saturated adsorption-desorption medium, and the adsorption-desorption medium in the adsorption-desorption tower is heated to more than the adsorbed gas desorption temperature, thereby desorption is carried out in the described adsorbed gas that is adsorbed in the adsorption-desorption medium;
3) gas behind the desorption is shifted out outside the system as product gas;
4) will shift out outside the system through the admixture of gas that adsorbing separation goes out adsorbed gas.
13. method according to claim 12 wherein realizes by feed desorption gas in the adsorption-desorption tower the heating of adsorption-desorption medium.
14. method according to claim 13, wherein at least a portion product gas is back in the described adsorption-desorption tower as desorption gas.
15. method according to claim 14, wherein the product gas of Hui Liuing accounts for 10～60 (volume) % of product gas total amount.
16. method according to claim 15, wherein the product gas of Hui Liuing is heated to more than the desorption temperature before in being back to described adsorption-desorption tower.
17. method according to claim 12 wherein makes described product gas further by at least one cyclone cluster, pneumatic filter, drier and/or gas compressor, thereby forms the higher product gas of purity.
18. method according to claim 12, wherein said fresh adsorption-desorption medium is the adsorption-desorption medium of regenerating through gas desorption from the adsorption-desorption tower.
19. method according to claim 12, above-mentioned steps 1 wherein circulates)-4).
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| CN106118777A (en) * | 2016-08-24 | 2016-11-16 | 深圳前海中盛环保科技有限公司 | A kind of marsh gas purifying purifies the method for methane |
| CN115818571A (en) * | 2022-12-14 | 2023-03-21 | 福建久策气体股份有限公司 | System for preparing hydrogen from methanol and water vapor |
| CN117065517A (en) * | 2023-10-13 | 2023-11-17 | 中国华能集团清洁能源技术研究院有限公司 | Cross-flow low-temperature adsorption tower with cross bed layers and low-temperature flue gas adsorption system |
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