CN102728179A - Pressure-variable adsorption process for concentrating methane from low-concentration coal mine gas - Google Patents

Pressure-variable adsorption process for concentrating methane from low-concentration coal mine gas Download PDF

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CN102728179A
CN102728179A CN2012102465733A CN201210246573A CN102728179A CN 102728179 A CN102728179 A CN 102728179A CN 2012102465733 A CN2012102465733 A CN 2012102465733A CN 201210246573 A CN201210246573 A CN 201210246573A CN 102728179 A CN102728179 A CN 102728179A
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adsorbent bed
pressure
gas
methane
concentration
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张国瑞
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BEIJING XINNUO HAIBO PETROCHEMICAL TECHNOLOGY DEVELOPMENT Co Ltd
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BEIJING XINNUO HAIBO PETROCHEMICAL TECHNOLOGY DEVELOPMENT Co Ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/20Capture or disposal of greenhouse gases of methane
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/40Capture or disposal of greenhouse gases of CO2

Abstract

The invention provides a pressure-variable adsorption process for concentrating low-concentration coal mine gas by normal-pressure adsorption and vacuum desorption. The process adopts at least four adsorption beds, wherein at least one adsorption bed is used for adsorbing at any time, at least one adsorption bed is used for vacuumizing or cleaning under vacuum at any time, and each adsorption bed is sequentially used for adsorbing, pressure-reduced concentrating, pressure-reduced releasing, vacuumizing, cleaning under vacuum, uniform pressure rising, finally charging and the like. According to the process, the low-concentration coal mine gas with methane concentration about 20% is concentrated into the methane gas of which the methane concentration is more than 60%, so that the process is suitable for concentrating the low-concentration coal mine gas on a large scale.

Description

Low concentration coal mine gas pressure-changed adsorption concentrating methane technology
Technical field
The present invention relates to a kind ofly will carry the dense pressure swing adsorption technique of higher methane concentration methane gas that is than the coal mine gas of low methane concentrations.
Background technology
The main component of coal mine gas is methane, also contains a certain amount of nitrogen, oxygen, water, carbon dioxide etc. simultaneously, and what the value utilized was wherein arranged most is methane.China is that coal is contained and big producing country, and the coal mine gas reserves are very abundant, and having developed coal mine gas is a basic power source strategy of country.In order to make good use of coal gas, also in order to reduce the harm that gas causes safety in production in the progress of coal mining, country has proposed the policy of " take out afterwards earlier and adopt, can take out to the greatest extent and take out, urge to take out to use " to utilizing coal mine gas.But because the methane concentration scope has explosion danger at 5~16% low concentration gas, be in security consideration, country's " safety regulations in coal mine " regulation, when the colliery mash gas extraction utilized, methane concentration must not be lower than 30%.Annual national gas pumping amount surpasses 10,000,000,000 m3 at present.In the coal mine gas that extraction goes out; Accounting for total amount, to surpass 70% gas be that concentration is lower than 30% low concentration gas; Can not be had to efflux atmosphere by directly burning utilization after this part gas pumping comes out, this not only causes the waste of precious resources; Because the greenhouse effects of methane are equivalent to 21 times of carbon dioxide, discharging directly into atmosphere can cause significant adverse effect to environment.
Chinese patent CN101096606A has proposed a kind of low concentration coal mine gas normal pressure concentrating method, the extracting and concentrating technology process for absorption, once all pressure drops, vacuumize, adopt 2~5 adsorbent beds, be filled with in 2~3 methane adsorbent efficiently in the adsorbent bed.Concrete technical process mainly comprises, will under normal temperature and<0.05MPa (G) pressure, carry out adsorbing separation from the low concentration gas gas of coal mine gas extracting device, obtains methane content less than 5% emptying gas from the adsorbent bed outlet; Carry out once all pressure drops then; Then adsorbent bed is vacuumized, obtain maximum concentration and reach 60% methane gas.The method that this patent proposes is a kind of normal temperature, a normal pressure desorption under absorption, the vacuum down, neither need the unstripped gas compression be boosted, and also need not use the reflux low concentration gas pressure-changed adsorption concentrating method of displacement of product methane gas.The part but this process comes with some shortcomings.At first; Only carry out once all pressure drops behind the adsorbent bed completion adsorption step in this process and just then vacuumize the recovery methane gas; Certainly will cause dead space in the adsorbent bed retain with adsorbent on the nitrogen etc. of a great deal of that adsorbs be difficult for absorbed component and be not discharged from, the result is the methane gas that is difficult to obtain higher concentration; Secondly, only adopt 2~5 adsorbent beds in this process, be difficult to arrange many absorbing process, this is unfavorable for improving the treatment scale of actual industrial device.The treatment scale that general low concentration coal mine gas concentration unit requires is all bigger, and extensive treating apparatus requires treating capacity at 2000~10000Nm 3/ h, in addition higher, have only the pressure-changed adsorption concentrating technology of 2~5 adsorbent beds to be difficult to satisfy such scale requirement.
Summary of the invention
The objective of the invention is to propose a kind of extracting low-concentration coal mine gas, to obtain the pressure swing adsorption technique of higher methane concentration methane gas.
Another object of the present invention is to propose a kind of pressure swing adsorption technique that is suitable for the extracting low-concentration coal mine gas of fairly large treating apparatus.
The objective of the invention is to realize like this; Adopt the pressure swing adsorption technique of normal pressure absorption vacuum desorption to handle the low concentration coal mine gas; The adsorbent bed that comprises 4 and 4 above quantity in the technology; Whenever have at least 1 adsorbent bed to be in adsorption step, whenever have at least 1 adsorbent bed to be in and vacuumize step or vacuum cleaned step, every adsorbent bed experiences following operating procedure successively:
A. adsorption step---the coal mine gas than low methane concentrations that extraction equipment in coal seam is discharged is introduced adsorbent bed from the adsorbent bed inlet; Under normal temperature, normal pressure, pass through in the adsorbent bed process; Easy absorbed component such as the methane in the gas, moisture, carbon dioxide are adsorbed the adsorbents adsorb of filling in the bed and get off; Nitrogen in the gas, oxygen etc. are difficult for absorbed component and then pass adsorbent bed and discharge from adsorbent bed outlet as purified gas, when the absorption forward position of adsorbent bed is about to penetrate adsorbent bed, stop absorption;
B. the step-down concentration step---adsorbent bed pressure is progressively reduced to first vacuum pressure, and the rich nitrogen carrier of oxygen of discharge low methane concentrations is concentrated the methane in the adsorbent bed;
C. the step-down release steps---adsorbent bed is communicated with the adsorbent bed that is in step e, makes adsorbent bed pressure progressively reduce to second vacuum pressure, make the methane in the adsorbent bed obtain further concentrating, the gas that discharges in the step-down process is as the purgative gas of step e;
D. vacuumize step---adsorbent bed is vacuumized with vaccum-pumping equipment from the adsorbent bed entrance side; Make adsorbent bed pressure progressively reduce to the 3rd vacuum pressure; Be adsorbed on easy absorbed component such as methane on the adsorbent bed, moisture, carbon dioxide progressively desorption get off, obtain the methane gas of higher methane concentration from the vaccum-pumping equipment outlet;
E. vacuum cleaned step---the adsorbent bed outlet is communicated with the adsorbent bed that is in step c; When continuation vacuumizes adsorbent bed; With purgative gas adsorbent bed is carried out reverse vacuum cleaned; Make adsorbent bed pressure progressively reduce to the 4th vacuum pressure; Utilize vaccum-pumping equipment to reduce the acting in conjunction that stagnation pressure and purgative gas reduce dividing potential drop, further will be adsorbed on easy absorbed component desorptions such as methane on the adsorbent bed, moisture, carbon dioxide and get off, export the methane gas that continues to obtain higher methane concentration from vaccum-pumping equipment;
F. equal voltage rise step---the adsorbent bed outlet is communicated with the adsorbent bed that is in equal voltage drop step or other pans of other higher operating pressure, makes adsorbent bed obtain part and boost;
G. fill step eventually---the purified gas of step a is introduced adsorbent bed from the adsorbent bed outlet, adsorbent bed is pressurized to the normal pressure adsorptive pressure;
H. circulation step a~step g.
The said low concentration coal mine gas of the present invention; Or be called the low concentration coal bed gas; Mainly refer to components such as main component methane that the extraction of coal mine gas extraction equipment goes out, nitrogen, oxygen, moisture, carbon dioxide; Wherein the methane concentration scope is 1~60% low concentration coal mine gas, and especially to be difficult to by the methane concentration scope of directly utilizing be 5~40% low concentration coal mine gas because of the explosion danger reason; Or other forms the mist similar with coal mine gas with the methane concentration scope.
Adsorption step of the present invention carries out at normal temperatures and pressures.Here the normal pressure of saying refer to gas discharge in mine equipment outlet a little more than atmospheric gas pressure; Usually at 100~160kPa (A); This pressure is enough to make unstrpped gas to overcome bed resistance to fall and pass adsorbent bed and finally enter atmosphere, and needn't utilize other special equipment that boosts that extraction equipment exit gas is further boosted.Said normal temperature refers to the temperature of extraction equipment exit gas, usually 10~40.About ℃.
According to the inventor's research, the adsorbent that is fit to pressure-changed adsorption concentrating low concentration coal mine gas technology of the present invention is that active carbon is or/and molecular sieve; Be moisture and the carbon dioxide in the effective elimination low concentration coal mine gas, also can load a certain amount of silica gel or activated alumina at the adsorbent bed entrance point, adsorbent bed remainder filling active carbon is or/and molecular sieve.
After adsorption step finishes, reduce adsorbent bed pressure through the step-down concentration step, discharge retain in the dead space in the adsorbent bed with adsorbent on the rich nitrogen carrier of oxygen that adsorbs, to concentrate the methane in the adsorbent bed.The inventor has carried out preliminary test research to low-concentration methane qi exhaustion additive process; With the methane of low methane concentrations and the mist of nitrogen is feeding gas, after the absorption of adsorbent bed normal pressure is saturated, stops absorption; Reduce adsorbent bed pressure, analyze the methane concentration of the rich nitrogen carrier of oxygen of discharging.Result of the test shows that along with the reduction of pressure, the methane concentration of discharging gas raises gradually; At the step-down process initial stage, the methane concentration of discharging gas is relatively low, and the speed that concentration raises also relatively slowly when being depressurized to certain pressure, being discharged gases methane concentration and begun to raise with fast speed.Result of the test also shows, the feeding gas of different methane concentrations, and after the saturated absorption of normal pressure, it also is different that step-down process discharge gases methane concentration begins quick elevated pressure.The feeding gas methane concentration is high more, and discharging gases methane concentration, to begin quick elevated pressure also high more.
The pressure of adsorbent bed was defined as first vacuum pressure when inventor finished step-down concentration step b.
The step-down concentration step can optionally adopt following two preferred versions.
Preferred version one: adsorbent bed or other pans of the equal voltage rise step of adsorbent bed and other are communicated with, through 1~5 equal pressure drop step by step, adsorbent bed are depressurized to first vacuum pressure, discharge the rich nitrogen carrier of oxygen in the adsorbent bed.
Preferred version two: form with vacuumizing to return step by step step by step by 1~3 equal pressure drop.Be exactly that first adsorbent bed or other pans with the equal voltage rise step of adsorbent bed and other are communicated with, through 1~3 equal pressure drop step by step, the rich nitrogen carrier of oxygen of discharge section; Then vacuumize and return step by step operation, with vacuumizing Returning equipment adsorbent bed is vacuumized exactly, make adsorbent bed be depressurized to first vacuum pressure, the rich nitrogen carrier of oxygen that vaccum-pumping equipment is exported enters feeding line to be mixed with unstripped gas.
The scope of first vacuum pressure changes with feed gas methane concentration and the product methane gas methane concentration that requires to obtain.According to preliminary test research, the scope of preferred first vacuum pressure is 15~60kPa (A).
The pressure of adsorbent bed was defined as second vacuum pressure when the present invention finished step-down release steps c, and is same, and the scope of second vacuum pressure also changes with feed gas methane concentration and the product methane gas methane concentration that requires to obtain.According to preliminary test research, the scope of preferred second adsorptive pressure is 10~50kPa (A).
The main purpose that vacuumizes steps d is the negative pressure that provides through vaccum-pumping equipment, major part is adsorbed on easy absorbed component desorptions such as methane on the adsorbent, moisture, carbon dioxide and gets off, and obtains the methane gas of higher methane concentration from the vaccum-pumping equipment outlet.The pressure of adsorbent bed is called as the 3rd vacuum pressure when vacuumizing the step end.The 3rd vacuum pressure is low more, and the methane gas methane concentration that obtains is high more, and regeneration of adsorbent beds must be thorough more, but the load of vaccum-pumping equipment is also big more.Preferred the 3rd vacuum pressure scope is 5~25kPa (A).
Vacuum cleaned step e is when the vaccum-pumping equipment continuation vacuumizes adsorbent bed; The relatively low purgative gas of methane concentration of discharging with the step-down release steps carries out reverse vacuum cleaned to adsorbent bed; To obtain lower methane dividing potential drop in the adsorbent bed; Further will be adsorbed on easy absorbed component desorptions such as methane on the adsorbent bed, moisture, carbon dioxide and get off, be that adsorbent obtains regenerating more completely.The pressure of adsorbent bed is called as the 4th vacuum pressure when vacuumizing the cleaning step end.Preferred the 4th vacuum pressure scope is 3~20kPa (A).
Vacuumize step and vacuum cleaned step and comprise a single order pumped vacuum systems of carrying out vacuum pumping continuously at least; When the pressure-swing absorption apparatus treatment scale bigger; Or evacuated pressure requires when relatively lower; The load of pumped vacuum systems is often bigger; Cause the size of vaccum-pumping equipment, pumped vacuum systems pipeline and valve also to increase thereupon, at this moment can adopt two or more to carry out the multistage pumped vacuum systems of vacuum pumping continuously.
In above-mentioned low concentration coal mine gas pressure-changed adsorption concentrating methane technology, whenever have at least 1 adsorbent bed to be in adsorption step, so that guarantee to handle continuously the low concentration coal mine gas.When treatment scale was bigger, the adsorbent bed that possibly have more than 2 even 2 was in adsorption step simultaneously.For making full use of the ability of vaccum-pumping equipment, whenever also there is at least 1 adsorbent bed to be in and vacuumizes step or vacuum cleaned step simultaneously.Except at least 1 adsorbent bed being in adsorption step be in vacuumize or at least 1 adsorbent bed of vacuum cleaned step, other has at least 2 adsorbent beds to be in step-down concentration step, step-down release steps, equal steps such as voltage rise step, pressurising step.Therefore, comprise at least 4 adsorbent beds in the technology of the present invention.
Adopted the step-down concentration step of fully discharging rich nitrogen carrier of oxygen just because of the present invention; Methane in the adsorbent bed is concentrated; Dividing potential drop effect with the purgative gas that utilizes relatively low methane concentration; Both improved the methane concentration that reclaims the purgative gas part, and made the methane that adsorbs on the adsorbent obtain desorption more completely again, adsorbent bed is better regenerated.Consequently can obtain the methane gas of higher methane concentration on the one hand, can effectively reduce the methane concentration of absorption back emission purification gas on the other hand.Simultaneously, just because of adopting many adsorbent beds to adsorb simultaneously and multistage evacuation process in the technology of the present invention, make the pressure-swing absorption apparatus of fairly large extracting low-concentration coal mine gas be achieved.
Below in conjunction with accompanying drawing and embodiment the said low concentration coal mine gas of the present invention pressure-changed adsorption concentrating methane technology is further specified.It is emphasized that following embodiment just in order to help to understand better the present invention, can not be understood that it is the restriction to claim of the present invention.
Description of drawings
Fig. 1 is a 6-1-3-1 low concentration coal mine gas pressure-changed adsorption concentrating process flow diagram.
Fig. 2 is that the 5-1-2-1 band vacuumizes the low concentration coal mine gas pressure-changed adsorption concentrating process flow diagram that returns.
Fig. 3 is the fairly large low concentration coal mine gas pressure-changed adsorption concentrating process flow diagram of 8-2-3-2.
The specific embodiment
Embodiment 1
Shown in Figure 1 is 6-1-3-1 low concentration coal mine gas pressure-changed adsorption concentrating process flow diagram.The meaning of " 6-1-3-1 " representative is, comprises 6 adsorbent beds in the flow process, wherein has 1 to be in adsorption step, comprises 3 times and all presses 1 rank pumped vacuum systems.
From the low concentration gas of gas discharge in mine equipment, methane concentration 20%, flow 3000Nm 3/ h, 30 ℃ of temperature, pressure 150kPa (A) gets into the pressure-changed adsorption concentrating device along the direction shown in the arrow (1).Be provided with the adsorbent bed that 6 numberings are respectively A, B, C, D, E, F in the device, what adsorbent bed lower floor loaded is silica gel, and what loaded on the upper strata is active carbon.Table the-1st, adsorbent bed work schedule table:
Table-1 embodiment 1 adsorbent bed work schedule table
1 2 3 4 5 6 7 8 9 10 11 12
A A A 1D 2D 3D DP V VP 3R 2R 1R FR
B 1R FR A A 1D 2D 3D DP V VP 3R 2R
C 3R 2R 1R FR A A 1D 2D 3D DP V VP
D V VP 3R 2R 1R FR A A 1D 2D 3D DP
E 3D DP V VP 3R 2R 1R FR A A 1D 2D
F 1D 2D 3D DP V VP 3R 2R 1R FR A A
In the table: the A-adsorption step; Step all falls in 1D-one; Step all falls in 2D-two; Step all falls in 3D-three; DP-step-down release steps; V-vacuumizes step; VP-vacuum cleaned step; 3R-three all rises step; 2R-two all rises step; 1R-one all rises step; FR-fills step eventually.
Whole transformation adsorption cycle is divided into 12 periods.Below be that example is explained whole pressure swing adsorption technique process with the A adsorbent bed.
Supposed for the 1st, the 2nd period, adsorbent bed (A) is in adsorption step (A).At this moment; Adsorbent bed (A) imported valve (V1A) and outlet valve (V3A) are opened, all the other valve closings (below the undeclared valve of opening promptly be the valve of closing), and charging gas is introduced adsorbent bed from the adsorbent bed inlet; In passing the adsorbent bed process; Easy absorbed component such as the methane that wherein absorption affinity is stronger, water, carbon dioxide are adsorbed agent and absorb, and the more weak nitrogen of absorption affinity, oxygen etc. are difficult for absorbed component and then pass adsorbent bed, enter atmosphere as purified gas from adsorbent bed (A) outlet.When the approaching outlet in the methane absorption forward position of adsorbent bed absorption, according to setting adsorption time parameter handover operation, (A) carries out following regenerative operation to adsorbent bed.The average methane concentration that adsorbent bed in the whole adsorption process (A) is discharged purified gas is about 4%.
The the 3rd~the 5th period, adsorbent bed (A) is in the step-down concentration step.The step-down concentration step of present embodiment adopts the technology of preferred version one, is made up of step by step 3 equal pressure drops.At first carry out one of the 3rd period and all fall (1D), open valve (V4A) and valve (V4C), with adsorbent bed (A) be in the adsorbent bed C that all rises and be communicated with, adsorbent bed (A) realization one is all fallen; Carry out two of the 4th period then and all fall (2D), open valve (V4A) and valve (V4D), with adsorbent bed (A) be in two adsorbent beds (D) that all rise and be communicated with, adsorbent bed (A) realization two is all fallen; Then carry out three of the 5th period and all fall (3D), open valve (V5A) and valve (V5E), with adsorbent bed (A) be in three adsorbent beds (E) that all rise and be communicated with, adsorbent bed (A) realization three is all fallen.Through after above-mentioned 3 equal pressure drops, adsorbent bed pressure is reduced to first vacuum pressure about 35kPa (A).
The 6th period, adsorbent bed (A) is in step-down release steps (DP).Open valve (V5A) and valve (V6F); Adsorbent bed (A) is communicated with the adsorbent bed that is in the vacuum cleaned step (F); Valve (V8) is the valve of manually limiting the quantity of, the adsorbent bed pressure when can manual adjustment cleaning tolerance with the end of step-down release steps with this valve, i.e. second vacuum pressure.Adsorbent bed pressure when present embodiment step-down release steps finishes is about 30kPa (A).
The 7th period, adsorbent bed (A) is in and vacuumizes step (V).Open valve (V2A), adsorbent bed (A) is vacuumized, adsorbent bed pressure is evacuated to the 3rd vacuum pressure about 15kPa (A) with vavuum pump (4).In the vacuum; Reduction along with pressure; Easy absorbed component such as the methane that adsorbs on the adsorbent, moisture, carbon dioxide are progressively got off by desorption, obtain the higher methane gas of concentration and after vavuum pump boosts, enter gas holder (not drawing among the figure) along the direction shown in the arrow (3).
The 8th period, adsorbent bed (A) is in vacuum cleaned step (VP).Open valve (V6A) and valve (V5B); When vavuum pump (4) continues to vacuumize to adsorbent bed (A); The purgative gas of discharging with adsorbent bed (B) carries out reverse vacuum cleaned through valve (V5B), valve (V8) and valve (V6A) to adsorbent bed, makes adsorbent bed pressure progressively reduce to the 4th vacuum pressure about 10kPa (A).The higher methane gas of the concentration that vacuum cleaned step vacuum pump outlet obtains also enters gas holder and reclaims.
In the present embodiment, vacuumize the average methane concentration of mixing methane gas that step and vacuum cleaned step obtain more than 55%.
The the 9th~the 11st period, adsorbent bed (A) is in equal voltage rise step.3 equal voltage drop step of 3 respectively corresponding other adsorbent beds of equal voltage rise step of present embodiment.At first carrying out three of the 9th period all rises (3R), opens valve (V5A) and valve (V5C), with adsorbent bed (A) be in the three adsorbent bed C that all fall and be communicated with, make all liters of adsorbent bed (A) realization three; Carrying out two of the 10th period then all rises (2R), opens valve (V4A) and valve (V4D), with adsorbent bed (A) be in two adsorbent beds (D) that all fall and be communicated with, make all liters of adsorbent bed (A) realization two; Then carrying out one of the 11st period all rises (1R), opens valve (V4A) and valve (V4E), with adsorbent bed (A) be in the adsorbent bed (E) that all falls and be communicated with, make all liters of adsorbent bed (A) realization one.
The 12nd period, adsorbent bed (A) is in and fills step (FR) eventually.Open valve (V3A), adsorbent bed (A) is pressurized to atmospheric pressure with the purified gas that discharges.
So far, adsorption cycle of adsorbent bed (A) finishes, and then circulation gets into next adsorption cycle.
Adsorbent bed (B), adsorbent bed (C), adsorbent bed (D), adsorbent bed (E), adsorbent bed (F) under the logic control of PLC, according to the sequential step shown in the table-1 handover operation successively, are realized the continuous of whole adsorption/desorption process also in an identical manner.
Embodiment 2
Shown in Figure 2 is that the 5-1-2-1 band vacuumizes the low concentration coal mine gas pressure-changed adsorption concentrating process flow diagram that returns.The meaning of " 5-1-2-1 " representative is, comprises 5 adsorbent beds in the flow process, wherein has 1 to be in adsorption step, comprises 2 times and all presses 1 rank pumped vacuum systems.
From the low concentration gas of gas discharge in mine equipment, methane concentration 15%, flow 2000Nm 3/ h, 30 ℃ of temperature, pressure 150kPa (A) gets into the pressure-changed adsorption concentrating device along the direction shown in the arrow (1).Be provided with the adsorbent bed that 5 numberings are respectively A, B, C, D, E in the device, filling is active carbon in the adsorbent bed.Table the-2nd, adsorbent bed work schedule table:
Table-2 embodiment 2 adsorbent bed work schedule tables
Period 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
A A A A A 1D 1D 2D 2D VC DP V V V VP 2R 2R 1R 1R FR FR
B 1R 1R FR FR A A A A 1D 1D 2D 2D VC DP V V V VP 2R 2R
C V VP 2R 2R 1R 1R FR FR A A A A 1D 1D 2D 2D VC DP V V
D VC DP V V V VP 2R 2R 1R 1R FR FR A A A A 1D 1D 2D 2D
E 1D 1D 2D 2D VC DP V V V VP 2R 2R 1R 1R FR FR A A A A
In the table: the A-adsorption step; Step all falls in 1D-one; Step all falls in 2D-two; VC-vacuumizes and returns step; DP-step-down release steps; V-vacuumizes step; VP-vacuum cleaned step; 2R-two all rises step; 1R-one all rises step; FR-fills step eventually.
Whole transformation adsorption cycle is divided into 20 periods.Below be that example is explained whole pressure swing adsorption technique process with the A adsorbent bed.
Supposed for the 1st~the 4th period, adsorbent bed (A) is in adsorption step (A), at this moment; Adsorbent bed (A) imported valve (V1A) and outlet valve (V3A) are opened; Charging gas is introduced adsorbent bed from the adsorbent bed inlet, and in passing the adsorbent bed process, easy absorbed component such as the methane that wherein absorption affinity is stronger, water, carbon dioxide are adsorbed agent and absorb; The more weak nitrogen of absorption affinity, oxygen etc. are difficult for absorbed component and then pass adsorbent bed, enter atmosphere as purified gas from adsorbent bed (A) outlet.When the approaching outlet in the methane absorption forward position of adsorbent bed, according to setting adsorption time parameter handover operation, (A) carries out following regenerative operation to adsorbent bed.The average methane concentration that adsorbent bed in the whole adsorption process (A) is discharged purified gas is about 3%.
The the 5th~the 9th period, adsorbent bed (A) is in the step-down concentration step.The step-down concentration step of present embodiment adopts the technology of preferred version two, comprises 2 equal pressure drops and returns (VC) step by step with vacuumizing step by step.At first carry out one of the 5th, the 6th period and all fall (1D), open valve (V4A) and valve (V4C), with adsorbent bed (A) be in the adsorbent bed C that all rises and be communicated with, adsorbent bed (A) realization one is all fallen; Carry out two of the 7th, the 8th period then and all fall (2D), open valve (V4A) and valve (V4D), with adsorbent bed (A) be in two adsorbent beds (D) that all rise and be communicated with, adsorbent bed (A) realization two is all fallen; Then open valve (V5A) and valve (V9); With circulating vacuum pump (6) adsorbent bed (A) is vacuumized; Make adsorbent bed be depressurized to first vacuum pressure about 25kPa (A), the rich nitrogen carrier of oxygen of circulating vacuum pump (6) outlet is entered feeding line mix with unstripped gas.Circulation gas tank (5) in the flow process is to establish for the service efficiency that improves circulating vacuum pump (6), and purpose is to vacuumize in nothing to return (V ℃) when operating step by step, utilizes the idle capacity of circulating vacuum pump (6) that circulation gas tank (5) is vacuumized.
The 10th period, adsorbent bed (A) is in step-down release steps (DP).Open valve (V5A) and valve (V6E), adsorbent bed (A) is communicated with the adsorbent bed that is in the vacuum cleaned step (E), the adsorbent bed pressure when cleaning tolerance and the end of step-down release steps, i.e. second vacuum pressure through the valve of manually limiting the quantity of (V8) manual adjustment.Adsorbent bed pressure when present embodiment step-down release steps finishes is about 20kPa (A).
The the 11st~the 13rd period, adsorbent bed (A) is in and vacuumizes step (V).Open valve (V2A), adsorbent bed (A) is vacuumized, adsorbent bed pressure is evacuated to the 3rd vacuum pressure about 10kPa (A) with vavuum pump (4).In the vacuum; Reduction along with pressure; Easy absorbed component such as the methane that adsorbs on the adsorbent, moisture, carbon dioxide are progressively got off by desorption, obtain the higher methane gas of concentration and after vavuum pump boosts, enter gas holder (not drawing among the figure) along the direction shown in the arrow (3).
The 14th period, adsorbent bed (A) is in vacuum cleaned step (VP).Open valve (V6A) and valve (V5B); When vavuum pump (4) continues to vacuumize to adsorbent bed (A), with the purgative gas that adsorbent bed (B) provides, process valve (V8); Adsorbent bed is carried out reverse vacuum cleaned, make adsorbent bed pressure progressively reduce to the 4th vacuum pressure about 7kPa (A).The higher methane gas of the concentration that vacuum cleaned step vacuum pump outlet obtains also enters gas holder and reclaims.
In the present embodiment, vacuumize the average methane concentration of mixing methane gas that step and vacuum cleaned step obtain more than 55%.
The the 15th~the 18th period, adsorbent bed (A) is in equal voltage rise step.2 equal voltage drop step of 2 respectively corresponding other adsorbent beds of equal voltage rise step of present embodiment.At first carrying out two of the 15th, the 16th period all rises (2R), opens valve (V4A) and valve (V4C), with adsorbent bed (A) be in the two adsorbent bed C that all fall and be communicated with, make all liters of adsorbent bed (A) realization two; Carrying out one of the 17th, the 18th period then all rises (1R), opens valve (V4A) and valve (V4D), with adsorbent bed (A) be in the adsorbent bed (D) that all falls and be communicated with, make all liters of adsorbent bed (A) realization one.
19th, the 20th period, adsorbent bed (A) is in and fills step (FR) eventually.Open valve (V3A), adsorbent bed (A) is pressurized to atmospheric pressure with the purified gas that discharges.
So far, adsorption cycle of adsorbent bed (A) finishes, and then circulation gets into next adsorption cycle.
Adsorbent bed (B), adsorbent bed (C), adsorbent bed (D), adsorbent bed (E) under the logic control of PLC, according to the sequential step shown in the table-2 handover operation successively, are realized the continuous of whole adsorption/desorption process also in an identical manner.
Embodiment 3
Shown in Figure 3 is 8-2-3-2 low concentration coal mine gas pressure-changed adsorption concentrating process flow diagram.The meaning of " 8-2-3-2 " representative is, comprises 8 adsorbent beds in the flow process, wherein has 2 to be in adsorption step, comprises 3 times and all presses 2 rank pumped vacuum systems.
From the low concentration gas of gas discharge in mine equipment, methane concentration 20%, flow 6000Nm 3/ h, 30 ℃ of temperature, pressure 150kPa (A) gets into the pressure-changed adsorption concentrating device along the direction shown in the arrow (1).Be provided with the adsorbent bed that 8 numberings are respectively A, B, C, D, E, F, G, H in the device, what adsorbent bed lower floor loaded is activated alumina, and what loaded on the upper strata is active carbon.Table the-3rd, adsorbent bed work schedule table:
Table-3 embodiment 3 adsorbent bed work schedule tables
Figure BSA00000750048900091
In the table: the A-adsorption step; Step all falls in 1D-one; Step all falls in 2D-two; Step all falls in 3D-three; DP-step-down release steps; V-vacuumizes step; VP-vacuum cleaned step; 3R-three all rises step; 2R-two all rises step; 1R-one all rises step; FR-fills step eventually.
Whole transformation adsorption cycle is divided into 16 periods.Below be that example is explained whole pressure swing adsorption technique process with the A adsorbent bed.
Supposed for the 1st~the 4th period, adsorbent bed (A) is in adsorption step (A).Adsorbent bed (A) imported valve (V1A) and outlet valve (V3A) are opened; Low methane concentrations charging gas is introduced adsorbent bed from the adsorbent bed inlet; In passing the adsorbent bed process; Easy absorbed component such as the methane that wherein absorption affinity is stronger, water, carbon dioxide are adsorbed agent and absorb, and the more weak nitrogen of absorption affinity, oxygen etc. are difficult for absorbed component and then pass adsorbent bed, enter atmosphere as purified gas from adsorbent bed (A) outlet.When the approaching outlet in the methane absorption forward position of adsorbent bed, according to setting adsorption time parameter handover operation, (A) carries out following regenerative operation to adsorbent bed.The average methane concentration that adsorbent bed in the whole adsorption process (A) is discharged purified gas is about 4%.
In the present embodiment, in the 1st~the 4th period, adsorbent bed (A) is when being in adsorption step, and the 1st and the 2nd period, adsorbent bed (H) also is in adsorption step, and the 3rd and the 4th period was changed to adsorbent bed (B) and also is in adsorption step.Whenever all there is the parallel connection simultaneously of two adsorbent beds to be in adsorption step.This has not only effectively reduced the volume and the diameter of every adsorbent bed, has also effectively satisfied the requirement of adsorption dynamics adsorption kinetics to the adsorbent bed air speed simultaneously.
The the 5th~the 7th period, adsorbent bed (A) is in the step-down concentration step.The step-down concentration step of present embodiment adopts the technology of preferred version one, is made up of 3 equal pressure drops.At first carry out one of the 5th period and all fall (1D), open valve (V4A) and valve (V4D), with adsorbent bed (A) be in the adsorbent bed (D) that all rises and be communicated with, adsorbent bed (A) realization one is all fallen; Carry out two of the 6th period then and all fall (2D), open valve (V4A) and valve (V4E), with adsorbent bed (A) be in two adsorbent beds (E) that all rise and be communicated with, adsorbent bed (A) realization two is all fallen; Then carry out three of the 7th period and all fall (3D), open valve (V5A) and valve (V5F), with adsorbent bed (A) be in three adsorbent beds (F) that all rise and be communicated with, adsorbent bed (A) realization three is all fallen.Through after above-mentioned 3 equal pressure drops, adsorbent bed pressure is reduced to first vacuum pressure about 35kPa (A).
The 8th period, adsorbent bed (A) is in step-down release steps (DP).Open valve (V5A) and valve (V6G), adsorbent bed (A) is communicated with the adsorbent bed that is in the vacuum cleaned step (G), the adsorbent bed pressure when cleaning tolerance and the end of step-down release steps, i.e. second vacuum pressure through the valve of manually limiting the quantity of (V8) adjustment.Adsorbent bed pressure when present embodiment step-down release steps finishes is about 30kPa (A).
Present embodiment adopts the second order evacuation process, is exactly two pumped vacuum systems independently separately, respectively the different adsorption bed is carried out vacuum pumping simultaneously.Given two pumped vacuum systems with the whole sharing of load that vacuumizes like this, made equipment, pipeline and the valve of each pumped vacuum systems diminish, and can adopt the vaccum-pumping equipment of different types according to situation separately.
The the 9th~the 11st period, adsorbent bed (A) is in and vacuumizes step (V).The the 9th and the 10th period wherein; Vacuumize (the 9th, the 10th period second pumped vacuum systems is vacuumizing adsorbent bed (H)) with first pumped vacuum systems; Open valve (V2A); With vavuum pump (4/1) adsorbent bed (A) is vacuumized, obtain the higher methane gas of concentration and after vavuum pump boosts, enter gas holder (not drawing among the figure) along the direction shown in the arrow (3) with vacuumizing.Followed for the 11st period; Conversion vacuumizes (the 11st, the 12nd period first pumped vacuum systems is vacuumizing adsorbent bed (B)) with second pumped vacuum systems; Open valve (V7A); With vavuum pump (4/2) adsorbent bed (A) is proceeded to vacuumize, vavuum pump (4/2) outlet is obtained the higher methane gas of concentration also enter gas holder.At this moment adsorbent bed pressure is evacuated to the 3rd vacuum pressure about 10kPa (A).
The 12nd period, adsorbent bed (A) is in vacuum cleaned step (VP).Open valve (V6A) and valve (V5C), when vavuum pump (4/2) continues to vacuumize to adsorbent bed (A), adsorbent bed A is carried out reverse vacuum cleaned, make adsorbent bed pressure progressively reduce to the 4th vacuum pressure about 7kPa (A) with the purgative gas of adsorbent bed (C).The higher methane gas of the concentration that vacuum cleaned step vacuum pump outlet obtains also enters gas holder and reclaims.
In the present embodiment, vacuumize the average methane concentration of mixing methane gas that step and vacuum cleaned step obtain from two vacuum pump outlets more than 65%.
The the 13rd~the 15th period, adsorbent bed (A) is in equal voltage rise step.3 equal voltage drop step of 3 respectively corresponding other adsorbent beds of equal voltage rise step of present embodiment.At first carrying out three of the 13rd period all rises (3R), opens valve (V5A) and valve (V5D), with adsorbent bed (A) be in the three adsorbent bed D that all fall and be communicated with, make all liters of adsorbent bed (A) realization three; Carrying out two of the 14th period then all rises (2R), opens valve (V4A) and valve (V4E), with adsorbent bed (A) be in two adsorbent beds (E) that all fall and be communicated with, make all liters of adsorbent bed (A) realization two; Then carrying out one of the 15th period all rises (1R), opens valve (V4A) and valve (V4F), with adsorbent bed (A) be in the adsorbent bed (F) that all falls and be communicated with, make all liters of adsorbent bed (A) realization one.
The 16th period, adsorbent bed (A) is in and fills step (FR) eventually.Open valve (V3A), adsorbent bed (A) is pressurized to atmospheric pressure with the purified gas that discharges.
So far, adsorption cycle of adsorbent bed (A) finishes, and then circulation gets into next adsorption cycle.
Adsorbent bed (B), adsorbent bed (C), adsorbent bed (D), adsorbent bed (E), adsorbent bed (F), adsorbent bed (G), adsorbent bed (H) are also in an identical manner; Under the logic control of PLC; According to the sequential step shown in the table-3 handover operation successively, realize the continuous of whole adsorption/desorption process.

Claims (11)

1. the pressure swing adsorption technique of normal pressure absorption vacuum desorption extracting low-concentration coal mine gas; It is characterized in that: the adsorbent bed that comprises 4 and 4 above quantity; Whenever have at least 1 adsorbent bed to be in adsorption step; Whenever have at least 1 adsorbent bed to be in and vacuumize step or vacuum cleaned step, every adsorbent bed experiences following operating procedure successively:
A. adsorption step---the coal mine gas than low methane concentrations that extraction equipment in coal seam is discharged is introduced adsorbent bed from the adsorbent bed inlet; Under normal temperature, normal pressure, pass through in the adsorbent bed process; Easy absorbed component such as the methane in the gas, moisture, carbon dioxide are adsorbed the adsorbents adsorb of filling in the bed and get off; Nitrogen in the gas, oxygen etc. are difficult for absorbed component and then pass adsorbent bed and discharge from adsorbent bed outlet as purified gas, when the absorption forward position of adsorbent bed is about to penetrate adsorbent bed, stop absorption;
B. the step-down concentration step---adsorbent bed pressure is progressively reduced to first vacuum pressure, and the rich nitrogen carrier of oxygen of discharge low methane concentrations is concentrated the methane in the adsorbent bed;
C. the step-down release steps---adsorbent bed is communicated with the adsorbent bed that is in step e, makes adsorbent bed pressure progressively reduce to second vacuum pressure, make the methane in the adsorbent bed obtain further concentrating, the gas that discharges in the step-down process is as the purgative gas of step e;
D. vacuumize step---adsorbent bed is vacuumized with vaccum-pumping equipment from the adsorbent bed entrance side; Make adsorbent bed pressure progressively reduce to the 3rd vacuum pressure; Be adsorbed on easy absorbed component such as methane on the adsorbent bed, moisture, carbon dioxide progressively desorption get off, obtain the methane gas of higher methane concentration from the vaccum-pumping equipment outlet;
E. vacuum cleaned step---the adsorbent bed outlet is communicated with the adsorbent bed that is in step c; When continuation vacuumizes adsorbent bed; With purgative gas adsorbent bed is carried out reverse vacuum cleaned; Make adsorbent bed pressure progressively reduce to the 4th vacuum pressure; Utilize vaccum-pumping equipment to reduce the acting in conjunction that stagnation pressure and purgative gas reduce dividing potential drop, further will be adsorbed on easy absorbed component desorptions such as methane on the adsorbent bed, moisture, carbon dioxide and get off, export the methane gas that continues to obtain higher methane concentration from vaccum-pumping equipment;
F. equal voltage rise step---the adsorbent bed outlet is communicated with the adsorbent bed that is in equal voltage drop step or other pans of other higher operating pressure, makes adsorbent bed obtain part and boost;
G. fill step eventually---the purified gas of step a is introduced adsorbent bed from the adsorbent bed outlet, adsorbent bed is pressurized to the normal pressure adsorptive pressure;
H. circulation step a~step g.
2. technological process according to claim 1 is characterized in that: the methane concentration scope of low concentration coal mine gas is 1~60%.
3. according to claim 1 and 2 described technological processes, it is characterized in that: the methane concentration scope of low concentration coal mine gas is 5~40%.
4. technological process according to claim 1 is characterized in that: the adsorbent bed feed gas pressure is 100~160kPa (A) (cutting off), and temperature is 10~40 ℃.
5. technological process according to claim 1 is characterized in that: the adsorbent of filling is an active carbon or/and molecular sieve in the adsorbent bed, or silica gel or activated alumina and active carbon are or/and the multiple-hearth of molecular sieve.
6. technological process according to claim 1; It is characterized in that: the concrete technology of step-down concentration step is that the adsorbent bed of the equal voltage rise step of adsorbent bed and other or other pans are communicated with; Through 1~5 equal pressure drop step by step; Adsorbent bed is depressurized to first vacuum pressure, discharges the rich nitrogen carrier of oxygen in the adsorbent bed.
7. technological process according to claim 1 is characterized in that: the concrete technology of step-down concentration step is that first adsorbent bed or other pans with the equal voltage rise step of adsorbent bed and other are communicated with, through 1~3 equal pressure drop step by step, and the rich nitrogen carrier of oxygen of discharge section; Then vacuumize and return step by step operation, with vacuumizing Returning equipment adsorbent bed is vacuumized, make adsorbent bed be depressurized to first vacuum pressure, the rich nitrogen carrier of oxygen that vaccum-pumping equipment is exported enters feeding line to be mixed with unstripped gas.
8. according to claim 1,6,7 described technological processes, it is characterized in that: the first vacuum pressure scope is 15~60kPa (A).
9. technological process according to claim 1 is characterized in that: the second vacuum pressure scope is 10~50kPa (A).
10. technological process according to claim 1 is characterized in that: the 3rd vacuum pressure scope is 5~25kPa (A).
11. technological process according to claim 1 is characterized in that: the 4th vacuum pressure scope is 3~20kPa (A).
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CN105879571A (en) * 2014-12-10 2016-08-24 北京信诺海博石化科技发展有限公司 Oil gas recycling technology for treating large amount of oil gas through adsorption method
CN106693608A (en) * 2016-12-13 2017-05-24 中国石油化工股份有限公司 Refinery dry gas separating and recycling process
CN109971521A (en) * 2019-04-04 2019-07-05 煤炭科学技术研究院有限公司 A kind of method of methane concentration separation in low concentration coal-bed gas
CN110052114A (en) * 2019-05-24 2019-07-26 成都华西化工科技股份有限公司 A kind of vacuum pressure swing adsorption system of band backwash
CN111773882A (en) * 2020-07-28 2020-10-16 中国矿业大学 Micro-positive pressure vacuum pressure swing adsorption system and method for safely concentrating low-concentration gas

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CN104587795A (en) * 2014-12-10 2015-05-06 北京信诺海博石化科技发展有限公司 Oil and gas recovery process for treating large quantity of oil and gas by using adsorption method
CN105879571A (en) * 2014-12-10 2016-08-24 北京信诺海博石化科技发展有限公司 Oil gas recycling technology for treating large amount of oil gas through adsorption method
CN106693608A (en) * 2016-12-13 2017-05-24 中国石油化工股份有限公司 Refinery dry gas separating and recycling process
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CN109971521A (en) * 2019-04-04 2019-07-05 煤炭科学技术研究院有限公司 A kind of method of methane concentration separation in low concentration coal-bed gas
CN109971521B (en) * 2019-04-04 2020-12-11 煤炭科学技术研究院有限公司 Method for concentrating and separating methane in low-concentration coal bed gas
CN110052114A (en) * 2019-05-24 2019-07-26 成都华西化工科技股份有限公司 A kind of vacuum pressure swing adsorption system of band backwash
CN111773882A (en) * 2020-07-28 2020-10-16 中国矿业大学 Micro-positive pressure vacuum pressure swing adsorption system and method for safely concentrating low-concentration gas
CN111773882B (en) * 2020-07-28 2021-08-20 中国矿业大学 Micro-positive pressure vacuum pressure swing adsorption system and method for safely concentrating low-concentration gas

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