CN103212271B - 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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- CN103212271B CN103212271B CN201210019373.4A CN201210019373A CN103212271B CN 103212271 B CN103212271 B CN 103212271B CN 201210019373 A CN201210019373 A CN 201210019373A CN 103212271 B CN103212271 B CN 103212271B
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- 238000003795 desorption Methods 0.000 claims abstract description 203
- 238000002336 sorption--desorption measurement Methods 0.000 claims abstract description 108
- 238000001179 sorption measurement Methods 0.000 claims abstract description 80
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
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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 present invention relates to a kind of gas separation system and use the method for this systematic position gas, particularly, relate to a kind of piece-rate system of adsorption and desorption specific gas and use this system from waste gas or admixture of gas, be separated the method for above-mentioned specific gas.
Background technology
Widely use the fuel such as oil, natural gas, coal along with in industry, sphere of life, the toxic emission problem that these fuel produce in combustion receives publicity for a long time as the environmental problem of global scale.Containing great amount of carbon dioxide in above-mentioned waste gas, and global warming main cause is because atmospheric carbon dioxide levels increases.And for example, composition, the such as oxysulfide (SO outside removing carbon dioxide may also be comprised in the waste gas of many industrial discharges
x), and oxysulfide contributes to the formation of acid rain.Due to still considerable to the demand of above-mentioned fuel from now on, therefore how processing carbon dioxide in the waste gas of generation or gaseous mixture or other toxic gases will be a severe problem.
In fact, some gas in waste gas or gaseous mixture is the raw material needing supply in some industrial process, such as CO
2, CO, CH
4, NH
4etc. can separated purification be afterwards used as product material recycle.Such as, catch and store (CCS) at carbon and improve carbon dioxide in oil recovering (EOR) field and to be absolutely necessary raw material, in order to obtain high concentration carbon dioxide or reduce the cost buying carbon dioxide, from gaseous mixture, can be separated and reclaim carbon dioxide is expediently the important channel solved the problem.
In the past few decades, about being separated from the waste gas after burning or gaseous mixture and reclaiming the problem that some specific gases are some research always, wherein Temp .-changing adsorption (TSA) method is the characteristic utilizing the equilibrium adsorption capacity of adsorbent to raise with temperature and reduce, and adopts the method for operating of normal temperature absorption, desorption by heating.Because the amount of carbon dioxide is more in the waste gas after fuel combustion or gaseous mixture, a lot of research is from the carbon dioxide how recycled in waste gas, these researchs in early days for be that so-called carbon dioxide " wet " and is separated and recovery method, namely based on can the appropriate solution of selective absorption carbon dioxide or solvent wash gaseous mixture, and the method for adsorbed carbon dioxide be reclaimed by heating adsorption solution or solvent.But the problem that the method runs into is that wash solution is vulnerable to the impact of its component oxidative phenomena, and, usually also comprise sulphur and nitrogen oxide (SO in waste gas or gaseous mixture
xand NO
x), with some component reaction in wash solution, other hazardous compounds that can produce stable salt and be difficult to removing and process, therefore need often to replace wash solution.
In recent years, domestic and international research mainly concentrates on solid absorbent separation and reclaims on the system and method for carbon dioxide, such as US6,387,337 techniques disclosing a kind of separating carbon dioxide from gaseous mixture, wherein employ in adsorptive reactor that be reduced into through desorption carbon dioxide can the alkali metal of Reusability or the adsorbent of alkaline-earth metal, move between a double bed type heat reactor.This technique comprises: the first reactor is the adsorption tower of the adsorbent being filled with reduction, is passed in the first reactor by the gaseous mixture containing carbon dioxide, thus by carbon dioxide adsorption on described adsorbent; By be adsorbed with carbon dioxide with cross adsorbent move to the second reactor to reduce, the gas of the carbon dioxide on desorption adsorbent can comprise the synthesis gas of natural gas, methane, carbon monoxide, hydrogen and carbon monoxide and hydrogen; Then, the adsorbent of reduction is moved to the first reactor, make it proceed adsorption process.The flow process of this technique and simple to operate, efficient, but the introducing of exogenous reducing gas will directly cause the carbon dioxide purity after being separated to reduce, and then need to carry out extra gas separaion operation.
US6,755,892 systems disclosing a kind of separating carbon dioxide from waste gas, this system comprises: the carbon dioxide adsorption bed loading the adsorbent containing amine and nitrile functionality; Be communicated with the pipeline of carbonated exhaust gas source and described adsorbent bed; The outlet conduit of described adsorbent bed; The regenerating unit of carbon dioxide is discharged from described adsorption tower; The control valve of the turnover gas of described adsorbent bed can be controlled with at least one.This system by the airflow direction in above-mentioned control valve or the control device converting system that adds, thus carries out adsorption process and desorption process.And the above-mentioned regenerating unit for desorption carbon dioxide is heater, peripheral hardware heater in system, is utilized to heat described adsorbent bed, to reach the temperature of desorption carbon dioxide.In addition, also mention the available method passing into steam in this invention and reach desorption carbon dioxide object.This invention system carries out carbon dioxide separation and equipment needed for reclaiming is complicated, expensive, be difficult to operation, thus means the with high investment and high maintenance costs of needs.In addition, also there is peripheral hardware source hot in nature heat transfer efficiency problem, be separated rear carbon dioxide purity, high-pressure hot steam to problems such as the wearing and tearing of adsorbent.
In fact, US6,755, carbon dioxide separating system disclosed in 892 includes at least two carbon dioxide absorber beds, and wherein when an adsorbent bed is when adsorbing, another adsorbent bed is at desorption, but because desorption rate is usually faster than adsorption rate, two adsorbent beds cannot reach at full capacity simultaneously, and therefore, adsorption efficiency and the desorption efficiency of this piece-rate system are not high.
US7,153,344 disclose a kind of method being separated and reclaiming carbon dioxide from the oxide waste gas of burning.The method comprises: passed into by waste gas in semipermeable materials, from described waste gas, be separated the air-flow comprising high concentration carbon dioxide by gas semipermeable materials, wherein the air-flow comprising high concentration carbon dioxide be at least partially used as industrial raw material pan feeding and/or store the air-flow comprising high concentration carbon dioxide at least partially.
In fact, at US7,153, in piece-rate system disclosed in 344, a part enters in system as desorption gas backflow after heating again as the air-flow comprising high concentration carbon dioxide of product gas, for heating described semipermeable materials, and the carbon dioxide desorption adsorbed to make it.
The disclosure of above-mentioned all patent documents is introduced with for referencial use in full at this.
Obviously, to other specific gas, such as CO, the CH in waste gas or gaseous mixture
4, SO
x, NO
x, H
2s or NH
4identical etc. the principle of the adsorption-desorption system and method for the system and method with carbon dioxide that carry out adsorption-desorption process.Certainly, when become more suitably adsorbent, the system of adsorption and desorption carbon dioxide and the method for separating carbon dioxide thereof are equally applicable to separation or the purification of other gas.
Although disclose a lot by the system and method for adsorption-desorption mechanism divided gas flow in prior art, but common existence is due to the problem that the inconsistent adsorption plant caused of speed is oversize or separative efficiency is low of cryogenic absorption and elevated temperature desorption, how addressing this problem to reduce adsorption plant size or improving separative efficiency is problem demanding prompt solution in gas separaion and recovery field.
For solving institute's problems faced in above-mentioned prior art, the invention provides a kind of system and method being separated some specific gas from admixture of gas, Dynamic System is simple, cost is low, efficiency is high, continuity quick adsorption can be carried out to these specific gas under cryogenic absorption condition, and desorption effect can be improved under the condition not introducing exogenous desorption gas, thus separablely obtain highly purified specific gas.
In addition, present system and method are by conceiving cleverly, when not changing adsorbent species and piece-rate system structure, extend the adsorption time of adsorbent, shorten the time of desorbing gas, thus make adsorption plant size reduce by improving adsorption efficiency and desorption efficiency simultaneously and gas separative efficiency improves greatly, and then overcome above-mentioned technical barrier of the prior art.
Summary of the invention
According to the present invention first aspect, provide a kind of gas separation system, it comprises at least one adsorption tower and at least one adsorption-desorption tower, and the two is connected by pipeline, circulates between adsorption tower and adsorption-desorption tower to make adsorption-desorption medium; Its feature being different from prior art is: described adsorption-desorption medium is before reaching absorption and be saturated, and adsorption-desorption tower carry out absorption place as adsorption tower to the gas in admixture of gas, so that fully adsorbed gas improves adsorption efficiency; And reaching the saturated or absorption of absorption close to after saturated at described adsorption-desorption medium, adsorption-desorption tower carries out desorption, to improve desorbing gas efficiency as desorption column to the gas adsorbed.
Optionally, the mode of available direct heating or indirect heats close to saturated described adsorption-desorption medium reaching the saturated or absorption of absorption, to make to be attracted to the adsorbed gas desorption in described adsorption-desorption medium, directly heating refers to directly heat described adsorption-desorption medium by modes such as heat exchanger, electrical heating, heating using microwave and/or radiation heatings; And indirect refers to first heating desorption gas, then desorption gas is made it to heat with described adsorption-desorption medium contact as heat carrier, wherein heat exchanger is preferably heat exchange medium and flows through tube coil type heat exchanger wherein, described heat exchange medium is such as high-pressure water vapor, hydrogen, carbon dioxide and/or high temperature inert gas etc.
Saturated or the absorption of absorption is reached close to after saturated at described adsorption-desorption medium, adsorption tower proceeds absorption to the gas in mixture, adsorption-desorption tower carries out desorption as attaching tower to the gas be adsorbed onto in adsorption-desorption medium simultaneously, preferably, the product gas at least partially of desorption in described adsorption-desorption tower can be back in adsorption-desorption tower as desorption gas.When carrying out above-mentioned adsorption and desorption to adsorbed gas, the way of contact of described admixture of gas and described adsorption-desorption medium is arbitrary, such as following current or counter current contacting, reaching the saturated or absorption of absorption equally is also arbitrary close to the way of contact of saturated described adsorption-desorption medium and desorption gas, such as following current or counter current contacting.
Said system comprises at least one adsorption tower and at least one adsorption-desorption tower, and when possessing two or more adsorption towers, the connected mode between described adsorption tower can be serial or parallel connection; Equally, when possessing two or more adsorption-desorption towers, the connected mode between described adsorption-desorption tower also can be serial or parallel connection.
In said system, the gas of adsorption and desorption can be selected according to actual needs, 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 close to after saturated, adsorption tower adsorbs the adsorbed gas in admixture of gas, adsorption-desorption tower carries out desorption as the gas of desorption column to absorption simultaneously, in the process, except a part of product gas being refluxed as except desorption gas, also the desorption gas of the gas adsorbed for desorption adsorption-desorption medium needed for adsorption-desorption tower can be passed into from its exterior, so that the gas of system to absorption carries out desorption.But from the parsing gas of any type that desorption gas those of ordinary skill in the art that its exterior passes into adsorption-desorption tower know, preferably, be the gas identical with product gas from its exterior desorption gas passed into adsorption-desorption tower.
The adsorption-desorption medium that said system uses 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: silica gel, active carbon, CNT, zeolite, diatomite, molecular sieve, ion exchange resin, metal-containing compound material modified, containing the material modified of amine functional group or material modified containing nitrile functional group.Obviously, because of reasons such as himself life cycles, described system also can comprise adsorption-desorption medium feeding mouth and give up and the adsorption-desorption pipe outlet do not re-used, to regularly replace the adsorption-desorption medium that cannot regenerate.
In fact, described adsorption-desorption tower realizes changing between adsorption tower and desorption column by pipeline and valve, namely when adsorption-desorption tower uses as adsorption tower, admixture of gas containing adsorbed gas and/or fresh adsorption-desorption medium is inputted wherein by pipeline, and when adsorption-desorption tower uses as desorption column, above-mentioned input channel is closed by valve, also the admixture of gas in adsorption-desorption tower to be moved in adsorption tower by pipeline simultaneously and proceed gas absorption wherein or it is shifted out outside system, again by adsorption tower reaching absorption saturated or absorption move in adsorption-desorption tower close to saturated adsorption-desorption medium by pipeline, and realize desorbing gas and regeneration wherein, said process can intersected with each otherly repeat.
According to the present invention second aspect, provide a kind of method with above-mentioned systematic position gas, the method comprises the following steps in order:
1) admixture of gas containing described adsorbed gas is passed in described adsorption tower and adsorption-desorption tower, thus described adsorbed gas is adsorbed onto in the adsorption-desorption medium circulated between adsorption tower and adsorption-desorption tower;
2) the saturated or absorption of absorption is reached close to after saturated at described adsorption-desorption medium, admixture of gas in adsorption-desorption tower and/or fresh adsorption-desorption medium are moved in adsorption tower absorption is proceeded to the described adsorbed gas in admixture of gas, saturated for absorption or absorption are moved in adsorption-desorption tower close to saturated adsorption-desorption medium from adsorption tower simultaneously, and by more than the adsorption-desorption dielectric heating in adsorption-desorption tower to adsorbed gas desorption temperature, thus desorption is carried out to the described adsorbed gas be adsorbed in adsorption-desorption medium
3) gas after desorption is shifted out outside system as product gas;
4) admixture of gas going out adsorbed gas through adsorbing separation is shifted out outside system.
Preferably, to adsorption-desorption dielectric heating by passing into desorption gas to realize in adsorption-desorption tower, and product gas can be used as desorption gas and is back in described adsorption-desorption tower at least partially, the product gas wherein refluxed needs to be heated to more than desorption temperature being back to before in described adsorption-desorption tower.
Generally speaking, desorption gas can be selected according to the adsorption-desorption characteristic of adsorption-desorption medium to specific gas, as mentioned above, desorption gas can from outside system, also from the product gas of part backflow, 10 ~ 60 (volume) % of the gas gross that desorption produces in described adsorption-desorption tower can usually be accounted for as the desorption gas product gas be back in described adsorption-desorption tower.
In the above-mentioned methods, the product gas that desorption can be made to obtain is further by least one cyclone cluster, pneumatic filter, drier and/or gas compressor, thus form the higher product gas of purity, described fresh adsorption-desorption medium may also be the adsorption-desorption medium from regenerating through gas desorption in adsorption-desorption tower, each step of said method can circulate in order, to realize being continuously separated of gas.
Accompanying drawing explanation
Fig. 1 is the structural representation of a gas separation system of the present invention embodiment.
Fig. 2 is the structural representation of another embodiment of gas separation system of the present invention.
Detailed description of the invention
The present invention is further explained in detail by the description below with reference to accompanying drawing, but below describe only for enabling general technical staff of the technical field of the invention clearly understand principle of the present invention and marrow, and do not mean that any type of restriction is carried out to the present invention.In accompanying drawing, equivalent or corresponding parts or the identical reference numerals of feature represent.
Fig. 1 is gas separation system of the present invention embodiment, and it is adsorption and desorption system 10a, in this embodiment specific gas is set as carbon dioxide.System 10a relative low temperature, such as lower than 60 DEG C of temperature under from admixture of gas absorbing carbon dioxide, relatively-high temperature, such as higher than 100 DEG C of temperature under the carbon dioxide of desorption absorption from adsorbent, thus reach and to be separated from admixture of gas and to reclaim the object of carbon dioxide.The system of Fig. 1 mainly comprises a first fluidized bed (i.e. adsorption tower) 20, second fluid bed (i.e. adsorption-desorption tower) 30, separator 40 and the second separator 50, the admixture of gas conveyance conduit 11 of the first fluidized bed 20, the mixed gas pipeline road 35 of the second fluid bed 30, the output channel 23 of the first fluidized bed 20, the desorption gas pipeline 33 of the second fluid bed 30, the bypass line 60 of desorption gas pipeline 33 and the subsidiary conduit 65 of conveying desorption gas, wherein, energy absorbing carbon dioxide then discharges again carbon dioxide adsorbent by desorption is filled with in the first fluidized bed 20 and the second fluid bed 30, the separator 40 that the first fluidized bed 20 is arranged by its top is communicated with the lower end of the second fluid bed 30, the second separator 50 that second fluid bed 30 is arranged by its top is communicated with the lower end of the first fluidized bed 20, thus described adsorbent is circulated between the first fluidized bed 20 and the second fluid bed 30.Adsorbent reach absorption saturated before, the first fluidized bed and the second fluid bed all carry out adsorption treatment to carbon dioxide, can abundant absorbing carbon dioxide, and reach the saturated or absorption of absorption close to after saturated at described adsorbent, adsorbent in the first fluidized bed (adsorption tower) is moved in the second fluid bed (adsorption-desorption tower) by separator 40 and pipeline 34, by pump (not shown), the admixture of gas in the second fluid bed (adsorption-desorption tower) is moved in the first fluidized bed (adsorption tower) simultaneously, and add fresh adsorbent wherein, so that the first fluidized bed continues to carry out adsorption treatment to carbon dioxide, second fluid bed carries out desorption process to the carbon dioxide be adsorbed onto in adsorbent simultaneously, thus improve the adsorption and desorption efficiency of carbon dioxide simultaneously.The primary clustering reference numerals of system shown in Figure 1 illustrates see table 1 below.
Table 1
| 10a | Whole system | 40 | Separator |
| 11 | The gaseous mixture input channel of the first fluidized bed | 50 | Second separator |
| 20 | The first fluidized bed | 60 | The bypass line of desorption gas backflow |
| 21 | First fluidized bed gas mixture inlet | 61 | The control valve of bypass line |
| 22 | Adsorbent import | 62 | The heat exchanger of the desorption gas of backflow |
| 23 | First fluidized bed admixture of gas output channel | 63 | Second fluid bed admixture of gas conveyance conduit switch |
| 24 | The connecting pipe of the first fluidized bed | 64 | The bypass line switch of desorption gas backflow |
| 30 | Second fluid bed | 65 | Auxiliary desorption gas conveyance conduit |
| 31 | The gas mixture inlet of the second fluid bed | 66 | Auxiliary desorption gas heat exchanger |
| 32 | Spent sorbents exports | 67 | Auxiliary desorption gas conveyance conduit switch |
| 33 | The desorption gas output channel of the second fluid bed | 70 | Pneumatic filter |
| 34 | The connecting pipe of the second fluid bed | 80 | Drier |
| 35 | Second fluid bed admixture of gas input channel | 81 | 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 | 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 the second fluid bed 30, and close the bypass line switch 64 of auxiliary desorption gas conveyance conduit switch 67 and desorption gas backflow, the admixture of gas that the admixture of gas conveyance conduit 11 of the first fluidized bed neutralizes in the admixture of gas conveyance conduit 35 of the second fluid bed is passed into simultaneously in the first fluidized bed 20 and the second fluid bed 30, 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 along the admixture of gas conveyance conduit 11 of the first fluidized bed 20 by its gas mixture inlet 21, in the first fluidized bed 20, carbonated admixture of gas is with fresh and/or do not adsorb saturated adsorbent and contact, carbon dioxide in admixture of gas is adsorbed onto in described adsorbent gradually, and removing admixture of gas that is at least part of or most of carbon dioxide shifts out system from the gas vent of the first fluidized bed 20 along its output channel 23.Simultaneously, carbonated admixture of gas enters in the second fluid bed 30 along the admixture of gas conveyance conduit 35 of the second fluid bed 30 by its gas mixture inlet 31 equally, in the second fluid bed 30, carbonated admixture of gas contacts with fresh and/or unsaturated adsorbent equally, by the carbon dioxide adsorption in admixture of gas in described adsorbent, and removing admixture of gas that is at least part of or most of carbon dioxide shifts out system from the gas vent of the second fluid bed 30 along its output channel (not shown).Removing admixture of gas that is at least part of or most of carbon dioxide directly can enter in air according to operation requirements, or is for further processing, and repeats no more in this article to this.
The top of the described first fluidized bed 20 is provided with separator 40, and separator 40 can be gas-particle separation device, such as cyclone cluster, with by the absorbent powder of entrained with and/or adsorbent and removed at least partly or the admixture of gas of most of carbon dioxide be separated, the admixture of gas separating carbon dioxide shifts out system from the top of separator 40 along its output channel 23, and absorbent powder and solid absorbent then move to the second fluid bed 30 from the bottom of separator 40 along the connecting pipe 24 of the first fluidized bed 20.Second fluid bed 30 top is provided with the second separator 50, second separator 50 may also be gas-particle separation device, the separator identical with separator 40 can be selected, such as cyclone cluster, or other separators different from separator 40 can be selected, with by absorbent powder and/or adsorbent and removed at least partly, or the admixture of gas of most of carbon dioxide is separated, the admixture of gas separating carbon dioxide shifts out system from the top of the second separator 50 along its output channel (not shown), absorbent powder and solid absorbent then move to the first fluidized bed 20 from the bottom of separator 50 along the connecting pipe 34 of the second fluid bed 30, thus the circulation of adsorbent between the first fluidized bed 20 and the second fluid bed 30 during completing absorbing carbon dioxide.
The adsorbent loaded in the first fluidized bed 20 and the second fluid bed 30 is reproducible adsorbent after desorbing gas, but the regenerable sorbent that described adsorbent those of ordinary skill in the art know, can be selected from active carbon, CNT, zeolite, diatomite, molecular sieve, ion exchange resin, metal-containing compound material modified, containing material modified, material modified containing nitrile functional group of amine functional group, and their mixture.Need the time of staying of admixture of gas to be processed in the first fluidized bed 20 and the second fluid bed 30 and operating temperature, depend on the adsorption and desorption character of adsorbent.
Saturated or the absorption of absorption is reached close to after saturated at described adsorbent, described system 10a can run under several different conditions, as under the first running status, close auxiliary desorption gas conveyance conduit switch 67 and also open the admixture of gas conveyance conduit switch 63 of the second fluid bed and the bypass line switch 64 of desorption gas backflow, after heating, to pass in described second fluid bed 30 desorption by adsorbent carbon dioxide to make the admixture of gas in the admixture of gas conveyance conduit 35 of the desorption gas in bypass line 60 and the second fluid bed.Under the second running status, close the admixture of gas conveyance conduit switch 63 of the second fluid bed and open the bypass line switch 64 of auxiliary desorption gas conveyance conduit switch 67 and desorption gas backflow, the carbon dioxide in the carbon dioxide in the bypass line 60 reflux to make desorption gas and auxiliary desorption gas conveyance conduit 65 to pass in described second fluid bed 30 desorption by adsorbent carbon dioxide after heating.Under the third running status, close the admixture of gas conveyance conduit switch 63 of auxiliary desorption gas conveyance conduit switch 67 and the second fluid bed and open the bypass line switch 64 of desorption gas backflow, the carbon dioxide in the bypass line 60 reflux to make desorption gas to pass in described second fluid bed 30 desorption by adsorbent carbon dioxide after heating.
In described system 10a, when the CO 2 total amount that desorption in the second fluid bed 30 obtains is not enough to the carbon dioxide that desorption adsorbent adsorbs in the first fluidized bed 20 and/or the second fluid bed 30 after heating, described system can be selected to run under the first state or the second state.When the carbon dioxide that the total carbon dioxide capacity that desorption in the second fluid bed 30 obtains adsorbs with desorption adsorbent through heating metapedes in the first fluidized bed 20 and/or the second fluid bed 30, described system can be selected to run in the third state.
As mentioned above, under the first running status, auxiliary desorption gas conveyance conduit switch 67 cuts out, and the bypass line switch 64 of the admixture of gas conveyance conduit switch 63 of the second fluid bed and desorption gas backflow is opened.
Admixture of gas containing carbon dioxide enters in the first fluidized bed 20 along the admixture of gas conveyance conduit 11 of the first fluidized bed 20 by its gas feed 21, in the first fluidized bed 20, carbonated admixture of gas contacts with adsorbent, by the carbon dioxide adsorption in admixture of gas on described adsorbent, removing admixture of gas that is at least part of or most of carbon dioxide shifts out system from its gas vent of top of the first fluidized bed 20 along its output channel 23.
As mentioned above, the top of the first fluidized bed 20 is provided with gas-particle separation device 40, thus by absorbent powder and/or solid absorbent and removed at least partly, or the admixture of gas of most of carbon dioxide is separated, admixture of gas shifts out system from the top of separator 40 along its output channel 23 subsequently, and the adsorbent of absorbing carbon dioxide or absorbing carbon dioxide have been reached saturated or moved to the lower end of the second fluid bed 30 close to saturated adsorbent by gas-particle separation device 40 and connecting pipe 24 from the first fluidized beds 20, also reached saturated from the adsorbent of the first fluidized bed 20 and absorbing carbon dioxide in the second fluid bed 30 or be heated to more than desorption temperature close to the adsorbent in the second saturated fluid bed 30, the thermal desorption gas such as passed into the gas feed 31 from the second fluid bed 30 contacts, carbon dioxide is released after making it reach carbon dioxide desorption temperature, shifted out outside system by the desorption gas pipeline 33 of the second fluid bed 30 subsequently by desorption carbon dioxide out.
It is noted herein that: the hot gas passed into by gas feed 31 and desorption gas comprise: the admixture of gas conveyance conduit 35 along the second fluid bed passes into the admixture of gas in the second fluid bed 30, and pass into product gas in the second fluid bed 30 along the bypass line 60 of desorption gas backflow, and along auxiliary desorption gas conveyance conduit 65 pass in the second fluid bed 30 from the desorption gas outside system.Therefore, not only included the carbon dioxide of above-mentioned adsorbent desorption by the gas of the second fluid bed 30 desorption gas pipeline 33, but also comprise the desorption gas for desorption carbon dioxide.If shift out the purity of the carbon dioxide outside system by the desorption gas pipeline of the second fluid bed 30 or concentration does not reach requirement, system that a part of product gas in desorption gas pipeline 33 can be released do not recycle outward, another part product gas in desorption gas pipeline 33 then passes in the second fluid bed 30 along the bypass line 60 of desorption gas backflow and uses as desorption gas.Simultaneously, along the admixture of gas conveyance conduit 35 of the second fluid bed 30 and control along the control valve 61 that the bypass line 60 of desorption gas backflow passes into the bypass line 60 that the gas flow in the second fluid bed 30 is refluxed by the control valve 37 of admixture of gas conveyance conduit 35 and desorption gas, control along the gas and vapor permeation conveyance conduit 35 of the second fluid bed 30 and the heater 62 of bypass line 60 that then refluxed by heater 36 and the desorption gas of admixture of gas conveyance conduit 35 along the temperature that the bypass line 60 of desorption gas backflow passes into the gas of the second fluid bed 30.
In the second fluid bed 30, absorbing carbon dioxide reaches capacity or to contact with above-mentioned thermal desorption gas close to saturated adsorbent and the temperature of adsorbent raised reach more than desorption temperature, thus desorption goes out carbon dioxide, and result obtains adsorbent that is fresh or regeneration.The top of described second fluid bed 30 is provided with the second gas-particle separation device 50, thus adsorbent that is fresh or that regenerate and product gas are separated, product gas shifts out system from the top of separator 50 along desorption gas pipeline 33, adsorbent that is fresh or regeneration then moves to the first fluidized bed 20 from the bottom of separator 50 along the connecting pipe 34 of the second fluid bed 30, thus completes the de-adsorption cycle of adsorbent between the first fluidized bed 20 and the second fluid bed 30.
Generally speaking, the adsorbent that a part of Reusability is crossed needs regularly to be replaced.Therefore, in system 10a, the first fluidized bed 20 lower end is provided with adsorbent import 22, spent sorbents outlet 32 is provided with in the second separator 50 lower end of the second fluid bed 30, to add appropriate adsorbent when needing supplementary fresh adsorbent by adsorbent import 22, also remove appropriate spent sorbents by spent sorbents outlet 32 simultaneously.
It is to be noted that when not starting heater 36 of the second fluid bed 30, the adsorbent in the adsorbent in the first fluidized bed 20 and the second fluid bed 30 is simultaneously at absorbing carbon dioxide; And after the heater 36 of startup second fluid bed 30, adsorbent in the first fluidized bed 20 continues at absorbing carbon dioxide, and the adsorbent in the second fluid bed 30 under the heat effect of thermal desorption gas at desorption carbon dioxide.
Under the second running status, when the second fluid bed 30 carries out desorb, the switch 63 of the admixture of gas conveyance conduit 35 of the second fluid bed 30 cuts out, and the switch 64 of the bypass line 60 switch 67 of auxiliary desorption gas conveyance conduit 65 and desorption gas refluxed is opened.
Carbonated admixture of gas enters in the first fluidized bed 20 along the admixture of gas conveyance conduit 11 of the first fluidized bed by its gas feed 21, in the first fluidized bed 20, carbonated admixture of gas contacts with adsorbent, is adsorbed onto gradually in described adsorbent by the carbon dioxide in gas and vapor permeation mist.Removing at least partly, or the admixture of gas of most of carbon dioxide is moved out of system from the gas mixture outlet of the first fluidized bed 20 along the output channel 23 at separator 40 top, and the adsorbent of absorbing carbon dioxide or absorbing carbon dioxide reach capacity or moved to the lower end of the second fluid bed 30 from the first fluidized bed 20 by separator 40 and connecting pipe 24 close to saturated adsorbent, also reached capacity from the adsorbent of the first fluidized bed 20 and absorbing carbon dioxide in the second fluid bed 30 or be heated to more than desorption temperature close to the saturated adsorbent in the second fluid bed 30, the thermal desorption gas such as passed into the gas feed 31 from the second fluid bed 30 contacts, carbon dioxide is released after making it reach carbon dioxide desorption temperature, system is moved out of by the desorption gas pipeline 33 of the second fluid bed 30 by desorption carbon dioxide out.
Under this running status, the thermal desorption gas passed into by gas feed 31 comprises: the bypass line 60 along desorption gas backflow passes into the product carbon dioxide in the second fluid bed 30, and passes into the carbon dioxide outside the system in the second fluid bed 30 along auxiliary desorption gas conveyance conduit 65.The reason of this running status is selected to be: to fail to reach by the desorption gas of the second fluid bed 30 product carbon dioxide total amount that bypass line 60 refluxes that refluxes all carbon dioxide being enough to desorption adsorbent and adsorbing in the first fluidized bed 20 and/or the second fluid bed 30, under this running status, the desorption gas of desorption carbon dioxide is the carbon dioxide after heating, do not add other gas beyond carbon dioxide, so it is higher to shift out the carbon dioxide purity of system from the desorption gas pipeline 33 of the second fluid bed.Simultaneously, be controlled by the reflux control valve 61 of bypass line 60 of the control valve (not marking) of auxiliary desorption gas conveyance conduit 65 and desorption gas along auxiliary desorption gas conveyance conduit 65 and along the desorption gas backflow bypass line 60 desorption gas flow passed in the second fluid bed 30, and controlled by the heater 62 of the bypass line 60 of assisting the heater 66 of desorption gas conveyance conduit 65 and desorption gas backflow along auxiliary desorption gas conveyance conduit 65 and the temperature that passes into the desorption gas in the second fluid bed 30 along desorption gas backflow bypass line 60.
In the second fluid bed 30, when desorb or desorption, absorbing carbon dioxide reaches capacity or makes own temperature be increased to more than desorption temperature close to saturated adsorbent contacts with above-mentioned thermal desorption gas, thus desorption carbon dioxide, result obtains adsorbent that is fresh or regeneration.The connecting pipe 34 of adsorbent along the second fluid bed 30 bottom second separator 50 at the second fluid bed 30 top that be fresh or regeneration is moved to the first fluidized bed 20, thus completes the de-adsorption cycle of adsorbent between the first fluidized bed 20 and the second fluid bed 30.The desorption gas conveyance conduit 33 of the product carbon dioxide that desorption obtains from the top of the second separator 50 along the second fluid bed 30 shifts out system.
As mentioned above, under the third running status, when the second fluid bed 30 carries out desorb, the switch 67 of the switch 63 of the admixture of gas conveyance conduit 35 of the second fluid bed 30 and auxiliary desorption gas conveyance conduit 65 cuts out, and the switch 64 of desorption gas, i.e. product gas backflow bypass line 60 is opened.
The adsorption process of carbon dioxide under the third running status is identical with the adsorption process under the second running status, remove at least partly or the admixture of gas of most of carbon dioxide shift out system from its gas vent of the first fluidized bed 20 along the output channel 23 at separator 40 top, and the adsorbent of absorbing carbon dioxide or absorbing carbon dioxide reach capacity or move to the second fluid bed 30 along the connecting pipe 24 of the first fluidized bed 20 bottom separator 40 close to saturated adsorbent.
The adsorbent of absorbing carbon dioxide or absorbing carbon dioxide are reached capacity or from the first fluidized bed 20, is moved to the lower end of the second fluid bed 30 close to saturated adsorbent by separator 40 and connecting pipe 24, in the second fluid bed 30, absorbing carbon dioxide reaches capacity or contacts close to the thermal desorption gas that saturated adsorbent and the gas feed 31 from the second fluid bed 30 pass into, release carbon dioxide after making it reach carbon dioxide desorption temperature, shifted out system by desorption carbon dioxide out by the desorption gas pipeline 33 of the second fluid bed 30.Under this running status, when desorb or desorption, the thermal desorption gas passed into by gas feed 31 is the product carbon dioxide passed into along desorption gas backflow bypass line 60 in second fluid bed 30.The carbon dioxide at least partially being shifted out system by the desorption gas output channel 33 of the second fluid bed 30 passes in the second fluid bed 30 along desorption gas backflow bypass line 60, for the carbon dioxide that desorption adsorbent adsorbs in the first fluidized bed 20 and/or the second fluid bed 30, preferably, accounted for 10 ~ 60 (volume) % of the total CO 2 quantity that described system produces by the product carbon dioxide quantity of adsorbent carbon dioxide for desorption by described desorption gas backflow bypass line 60.Under this running status, desorption gas is the product carbon dioxide after heating, does not add other gas beyond carbon dioxide, so it is higher to shift out the carbon dioxide purity of system from the desorption gas output channel 33 of the second fluid bed 30.The product gas flow passed in the second fluid bed 30 along desorption gas backflow bypass line 60 is controlled by the control valve 61 of desorption gas backflow bypass line 60, and reflux product gas temperature is controlled by the heater 62 of desorption gas backflow bypass line 60.
In the second fluid bed 30, absorbing carbon dioxide reaches capacity or makes own temperature be increased to more than desorption temperature close to saturated adsorbent contacts with above-mentioned thermal desorption gas, thus desorption carbon dioxide, result obtains adsorbent that is fresh or regeneration.The connecting pipe 34 of adsorbent along the second fluid bed 30 bottom second separator 50 at the second fluid bed 30 top that be fresh or regeneration is moved to the first fluidized bed 20, thus completes the de-adsorption cycle of adsorbent between the first fluidized bed 20 and the second fluid bed 30.The carbon dioxide that desorption obtains then shifts out system from the second separator 50 top along the desorption gas pipeline 33 of the second fluid bed 30.
Under above three kinds of running statuses, after the CO 2 that desorption obtains shifts out system from the second fluid bed 30, also can be for further processing according to demand, after product gas or desorption gas shift out system from the second separator 50 top along the desorption gas pipeline 33 of the second fluid bed 30, it can be made by various gas, solid, liquid separator, such as pneumatic filter 70 and drier 80, export the gaseous state high-purity carbon dioxide product obtained after treatment afterwards along gaseous carbon dioxide product conveyance conduit 81.Or, then make it further by gas compressor 90, after compression along liquid carbon dioxide conveyance conduit 91 dispensing liquid high-purity carbon dioxide product.
Fig. 2 is another embodiment of gas separation system of the present invention, it is the system 10b of adsorption and desorption gas, its specific adsorbed gas is still carbon dioxide, the operation logic of system 10b is identical with system 10a, eliminates unlike system 10b the second separator 50 that the second fluid bed 30 is arranged at its top compared with system 10a.Primary clustering reference numerals illustrates also see table 1.System 10b mainly comprises a first fluidized bed (adsorption tower) 20, second fluid bed (adsorption-desorption tower) 30, gas-particle separation device 40, the admixture of gas conveyance conduit 11 of the first fluidized bed 20, the admixture of gas conveyance conduit 35 of the second fluid bed 30, the gas outlet duct 23 of the first fluidized bed 20, the desorption gas output channel 33 of the second fluid bed 30, desorption gas backflow bypass line 60 and the auxiliary desorption gas conveyance conduit 65 transporting the desorption gas outside system of desorption gas pipeline 33, wherein, in the first fluidized bed 20 and the second fluid bed 30, regenerable sorbent is housed, the separator 40 that the first fluidized bed 20 is arranged by its top is communicated with the second fluid bed 30, the upper end of the second fluid bed 30 is communicated with the lower end of the first fluidized bed 20, thus described adsorbent is circulated between the first fluidized bed 20 and the second fluid bed 30.
It should be noted: as illustrated in fig. 1 and 2, in system 10a, the mode that carbon dioxide and adsorbent carry out contacting is all co-current contact, and in system 10b, the mode that carbon dioxide carries out contacting with adsorbent in the first fluidized bed is co-current contact, and the mode that carbon dioxide carries out contacting with adsorbent in the second fluid bed is also co-current contact.
Above-mentioned three kinds of methods of operation and the embodiment shown in Fig. 1 and Fig. 2 are only enumerate and demonstrate, the not method of operation used of limit gas separation system of the present invention and embodiment, the present invention does not get rid of other method of operation and embodiment of meeting essence of the present invention and principle.
Embodiment
Embodiment 1
With the separating carbon dioxide from the admixture of gas after coal combustion of the gas separation system of the present invention shown in Fig. 1, this piece-rate system is laboratory scale separator, and the chemical composition composition of gas and vapor permeation raw material is 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 |
| % by weight | 25.67 | 0.11 | 4.26 | 69.96 | 100 |
In this gas separation system, adsorption-desorption medium, the i.e. adsorbent selected are that (weight ratio is the DEA-MCM-41 of 1:1 to solid amine carbon dioxide absorber, business's purchased from American FISHER or Uop Inc.), its particle diameter is 60-80 micron, water content is less than 1 % by weight, and the sorption and desorption characteristic of carbon dioxide is as shown in table 2:
Table 2
Take the third running status above-mentioned, namely desorption gas is the CO 2 gas of backflow completely, and after system startup also normal operation, the operating pressure of fluid bed 20 is 0.133MPa, and operating temperature is 40-51 DEG C; And the operating pressure of fluid bed 30 is also 0.133MPa, during its absorption, operating temperature is 40-51 DEG C; During desorption, operating temperature is 113 DEG C, and other each technological parameter of system is as shown in table 3:
Table 3
| Material flow | Flow (kg/hr) | Temperature (DEG C) | Pressure (MPa) |
| Gas and vapor permeation 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 after separating carbon dioxide | 74.33 | 51 | 0.101 |
| The CO 2 of backflow | 24.6 | 113 | 0.125 |
| CO 2 total amount | 25.67 | 113 | 0.101 |
Fluid bed 30 operating temperature when adsorption and desorption is different, in order to realize rapidly the transformation between its adsorption tower and desorption column, the lower gas and vapor permeation raw material of temperature can be passed at the arranging heat exchangers inside (not shown) of fluid bed 30 or when adsorbing and starting, after fresh or reproducing adsorbent is contacted with gas mixture material, temperature reaches about 40-43 DEG C, and it is also higher from the fresh or reproducing adsorbent temperature separator 50 flow ipe 24, also can in the conduit 24 the arranging heat exchangers inside (not shown) of fluid bed 20 or adsorb start time in fluid bed 20, also pass into the lower gas and vapor permeation raw material of temperature, after wherein fresh or reproducing adsorbent is contacted with gas mixture material, temperature also reaches about 40-43 DEG C.
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, thus completes total circulation of an adsorption and desorption.
The chemical composition composition of the admixture of gas after desorption or separating carbon dioxide is 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 |
| % by 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 volumetric 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 present invention 1: the present invention utilizes the difference of adsorption-desorption media adsorbs speed and desorption rate to improve existing adsorption-desorption gas separation system, adsorption plant size is diminished, and add adsorption and desorption efficiency, thus finally substantially improve the efficiency of gas separaion and the operability of equipment simultaneously.
The term that this description is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, are not intended to by any equivalents thereof exclude of the feature that represents and describe or its part outside when using these terms and form of presentation.
Although show and described several embodiment of the present invention, the present invention has not been restricted to described embodiment.On the contrary, those of ordinary skill in the art should recognize can carry out any accommodation and improvement to these embodiments when not departing from principle of the present invention and spirit, and protection scope of the present invention determined by appended claim and equivalent thereof.
Claims (9)
1. by a method for gas separation system divided gas flow,
Described gas separation system comprises:
At least one adsorption tower and at least one adsorption-desorption tower, the two is connected by pipeline, to make adsorption-desorption medium circulate between described adsorption tower and adsorption-desorption tower,
It is characterized in that: described adsorption-desorption medium is before reaching absorption and be saturated, and adsorption-desorption tower adsorbs the gas in admixture of gas as adsorption tower, so that fully adsorbed gas improves adsorption efficiency; And reach at described adsorption-desorption medium that absorption is saturated or close to after saturated, adsorption-desorption tower carries out desorption as desorption column to the gas adsorbed, to improve desorbing gas efficiency,
Wherein, described adsorption-desorption medium is one or more adsorbents be selected from following material: silica gel, active carbon, CNT, diatomite, molecular sieve, ion exchange resin, containing the material modified of amine functional group or material modified containing nitrile functional group,
Described separation method comprises the following steps in order:
1) pass into containing the admixture of gas of adsorbed gas in described adsorption tower and described adsorption-desorption tower, thus in the adsorption-desorption medium described adsorbed gas being adsorbed onto circulate between adsorption tower and adsorption-desorption tower;
2) the saturated or absorption of absorption is reached close to after saturated at described adsorption-desorption medium, admixture of gas in adsorption-desorption tower and/or fresh adsorption-desorption medium are moved in adsorption tower, and absorption is proceeded to the described adsorbed gas in admixture of gas, saturated for absorption or absorption are moved in adsorption-desorption tower close to saturated adsorption-desorption medium from adsorption tower simultaneously, and by more than the adsorption-desorption dielectric heating in adsorption-desorption tower to adsorbed gas desorption temperature, thus desorption is carried out to the described adsorbed gas be adsorbed in adsorption-desorption medium;
3) gas after desorption is shifted out outside system as product gas;
4) admixture of gas going out adsorbed gas through adsorbing separation is shifted out outside system.
2. method according to claim 1, wherein said adsorption-desorption medium is zeolite.
3. method according to claim 1, wherein to adsorption-desorption dielectric heating by passing into desorption gas to realize in adsorption-desorption tower.
4. method according to claim 3, wherein product gas is back in described adsorption-desorption tower as desorption gas at least partially.
5. method according to claim 4, the product gas wherein refluxed accounts for 10 ~ 60 (volume) % of product gas total amount.
6. method according to claim 5, the product gas wherein refluxed is heated to more than desorption temperature being back to before in described adsorption-desorption tower.
7. method according to claim 1, wherein makes described product gas further by least one cyclone cluster, pneumatic filter, drier and/or gas compressor, thus forms the higher product gas of purity.
8. method according to claim 1, wherein said fresh adsorption-desorption medium is the adsorption-desorption medium from regenerating through gas desorption in adsorption-desorption tower.
9. method according to claim 1, wherein circulation above-mentioned steps 1)-4).
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