CN101732947B - Method for safe adsorption and enrichment of gas with low concentration - Google Patents
Method for safe adsorption and enrichment of gas with low concentration Download PDFInfo
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- CN101732947B CN101732947B CN 201010034206 CN201010034206A CN101732947B CN 101732947 B CN101732947 B CN 101732947B CN 201010034206 CN201010034206 CN 201010034206 CN 201010034206 A CN201010034206 A CN 201010034206A CN 101732947 B CN101732947 B CN 101732947B
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Abstract
The invention provides a method for the safe adsorption and enrichment of gas with low concentration. By a pressure swing adsorption method, a product of the gas is obtained from a desorption stage. In order to ensure the safety in the adsorption process, methane and oxygen gas are adsorbed simultaneously in the adsorption process, and the volume fractions of the methane and the oxygen gas are ensured within a safe range, wherein the volume fraction of the methane is below 5%, and the volume fraction of the oxygen gas is below 9.47%. In the invention, an adsorbent used in an adsorption tower is a mixed adsorbent which is mainly used for adsorbing the methane and the oxygen gas. In the invention, the adsorption pressure is controlled within 0.9MPa. The invention can enrich and utilize the drawn gas with low concentration in a coal mine and can also reduce the discharge of greenhouse gases.
Description
Technical field
The invention belongs to the PSA Gas Separation Technology field, especially relate to a kind of method of light concentration mash gas safety enrichment, be used for safe enrichment and the utilization of colliery drawing-off gas.
Background technology
The content of methane is generally 20～45% in the coal bed gas, and 2000 meters in China is approximately 300,000～35 tcms with interior shallow-layer coal bed gas resource amount, and is similar with the total resources of natural gas, occupies the third place in the world.At present, the coal bed gas that China discharges because mining every year accounts for 1/3 of world's coal mining discharging coal bed gas total amount more than 130 billion cubic meters, rank first in the world.China's " safety regulations in coal mine " regulation, the methane volume fraction must not be lower than 30% during gas utilization, and volume fraction is lower than 25% coal bed gas and must not utilizes.The at present industrial way processing methane volume fraction of burning destruction or diffusing that often adopts is lower than 25% coal bed gas, has not only wasted a large amount of high-grade energies, and has caused the discharging of greenhouse gases.Therefore, how with the methane gas separating and concentrating of low concentration, become the major issue of cbm development.
Gas explosion is one of the major casualty in colliery.The volume fraction of methane and oxygen has explosivity in certain scope, generally adopt in the world the explosive range of Coward triangle pair fuel gas to differentiate.Patent 200810101910.3,200810101907.1,200810101908.6 discloses the methane explosion triangle schematic diagram after the expansion shown in Figure 1, among the figure whole concentration range is divided into explosibility district and non-blast area.Wherein the zone in the triangle L ' NV ' is the zone that can blast, and its mid point V is the critical explosion point, and its coordinate is (5.18,9.47).Straight line NVV ' is the UEL of methane under the different oxygen purities, and corresponding methane and oxygen purity close and be: Y=1.181X
O2-6.0.Straight line L ' LN is the LEL of methane under the different oxygen purities, and corresponding methane and oxygen purity close and be: Y=5.344-0.0713X
O2
Separating coal bed gas with Deep Cooling Method, can to obtain volume fraction be methane gas more than 95%.But need gas is added high pressure in the deep cooling process, and the aerial UEL of methane increases along with the increase of pressure, the UEL of methane has brought up to 42.5% when coal bed gas pressure reaches 2.5Mpa.In order to guarantee the safety of separation process, need to carry out in advance deoxidation treatment when Deep Cooling Method is separated gas, and the content of oxygen is very high in the low concentration gas, oxygen purity then needs to increase a large amount of investments greater than 14.7% to low concentration gas qi exhaustion oxygen.Chinese patent 200810101910.3,200810101907.1,200810101908.6 discloses a kind of method for the coalbed methane containing oxygen cryogenic separation, the volume fraction of this separation method control methane, oxygen, nitrogen ternary gas and and operating process in temperature guarantee to be positioned at outside the explosion triangle all the time in the separation process.Separation by deep refrigeration operating process more complicated, equipment investment and energy consumption are all larger, only have scale to reach and just are fit to after sizable degree use.At present, Deep Cooling Method is not yet being seen plant-scale application example aspect the low concentration gas separation.Membrane separation process is simple, easy to operate, with low cost, non-secondary pollution, but the effect that film separates is strong to the masking technique dependence, and film itself may exist easily and silt up, fragile, the problem such as service life is short, and technical also have the larger space of improving.Aspect the film separation, the large-scale membrane separation process that relates to methane in the mist still is in the development phase, and particularly the CH4/N2 system is not also having successful report aspect the film separation.
Pressure-variable adsorption is owing to the advantages such as investment is little, and operating cost is low are being paid close attention to aspect the gas separation field widely.Patent CN85103557A has described a kind of technology of pressure-swing adsorption concentration coal mine gas, take active carbon as adsorbent, is can be with more than the methane concentrate to 95% under the condition of 0.5-1.0MPa at adsorptive pressure.Adopting this technology to build up China's first set processing coal bed gas tolerance in Jiaozhuo, Henan mineral bureau is 1.2 ten thousand m
3The concentrated commerical test device in/sky is successfully with the CH in the coal bed gas
4Volume fraction brings up to 63.9% from 30.4%, increase displacement step after, can further improve 99.4%.Because adsorptive pressure is large, and has potential safety hazard in adsorption process, this technology is not promoted.The low concentration gas oxygen content is high, uses in the pressure-variable adsorption separation process that any gas all can't guarantee to avoid in the operating process explosion triangle in the single adsorption agent adsorption gas gas, and the enrichment for low concentration gas both at home and abroad all lacks research.The method that the present invention mixes by adsorbent, pro rata absorption mist guarantees the safe operation of pressure-variable adsorption separation process.
Summary of the invention
In order to solve the deficiency that enters easily the gas explosion limit in the pressure-variable adsorption enrichment gas process, the invention provides the method for a kind of low concentration gas (the methane volume fraction is less than 30%) safe adsorption and enrichment.The method can safety be more than the low-concentration methane gas concentrate to 30% 20% or more with volume fraction, and the rate of recovery is above 80%.
The technical solution adopted for the present invention to solve the technical problems is: propose a kind of method of safe adsorption and enrichment of gas with low concentration, realize the enrichment of low-concentration methane gas by the method for Vacuum Pressure Swing Adsorption.The adsorbent that loads in the adsorption tower in the described vacuum pressure swing absorption process is mixed adsorbent.Described mixed adsorbent is the adsorbent of main adsorption of oxygen and the adsorbent of main adsorbed methane gas.The adsorbent of described main adsorption of oxygen is carbon molecular sieve, zeolite molecular sieve and MOF (metal-organic framework materials), and the adsorbent of described main adsorbed methane is active carbon, zeolite molecular sieve and MOF.The mixed proportion of described mixing and absorption adsorbent is: the scope of the adsorbent mass of the adsorbent mass of main adsorption of oxygen/main adsorbed methane is 9: 1～1: 2.
Described pressure-changing process flow mainly comprise boost, adsorb, all pressure, depressurization desorption, cleaning five steps.Described pressure swing adsorption technique parameter is as follows: adsorptive pressure is controlled within 0.1MPa～0.9MPa, and depressurization desorption pressure is controlled within 0.01MPa～0.1MPa.In the described pressure-swing absorption process, low-concentration methane gas under high pressure flows into adsorption tower, the pro rata adsorbed methane of mixed adsorbent and oxygen, and the gas that is not adsorbed flows out from the exhaust end of adsorption tower.Methane volume fraction and oxygen purity reduce simultaneously at the absorption mass-transfer zone in the adsorption process, and the methane volume fraction required to remain on below 5% when gas flowed out from exhaust end, and oxygen purity requires to remain on below 9.47%.
The invention has the beneficial effects as follows:
1) uses mixed adsorbent simultaneously adsorbed methane and oxygen, can guarantee the safe operation of separation process;
By the method extracting low-concentration gas of pressure-variable adsorption, its initial cost is low, and operating cost is low, flexible and convenient operation;
2) contain partial oxidation in the stripping gas, can reduce the air of sneaking into when gas product uses, improve the quality of gas product;
3) the present invention can make drawing-off gas be fully utilized, and reduces the methane gas discharging to the pollution of environment, has great economy and environment meaning.
Description of drawings
Fig. 1 is the methane explosion triangle schematic diagram after the expansion;
Fig. 2 is process chart of the present invention.
The specific embodiment
The present invention is further described below in conjunction with drawings and Examples.
An embodiment of the method for safe adsorption and enrichment of gas with low concentration of the present invention as shown in Figure 2, unstripped gas flows into adsorption towers 3 by compressor 1 compression through air inlet surge tank 2 and control valve 4.Behind the methane and oxygen in the adsorbent absorption unstripped gas in the adsorption tower 3, discharging gas flows out from the exhaust end of adsorption tower, enters atmosphere behind throttling 5 of flowing through successively, control valve 4, check valve 6, exhaust surge tank 7, the flow control valve 8.After absorption finished, gas product was extracted out from adsorption tower 3 by vavuum pump 9.
The low-concentration methane gas component is as follows in the present embodiment: the methane volume fraction is 20%, and oxygen purity is 16.8%, and the nitrogen volume fraction is 64.2%.Mixed adsorbent is the mixed adsorbent of active carbon and carbon molecular sieve in the present embodiment, and carbon molecular sieve is 3.6: 1 with the ratio of quality of activated carbon.Technological parameter is as follows in the present embodiment: the highest adsorptive pressure is 320kPa (absolute pressure) after the compressed machine compression of unstripped gas, minimum parsing pressure 25 kPa (absolute pressure).Stripping gas and discharging gas constituent are as follows in the present embodiment:
Stripping gas methane volume fraction: 33.1%
Stripping gas oxygen purity: 21%
Discharging gas methane volume fraction: 2.9%
Discharging gas oxygen purity: 8.9%
Stripping gas and discharging gas all not in explosive range, have been realized the safe operation of adsorption separation process in this case study on implementation.
Claims (5)
1. the method for a safe adsorption and enrichment of gas with low concentration, realize the enrichment of low-concentration methane gas by the method for Vacuum Pressure Swing Adsorption, it is characterized in that: the method for described Vacuum Pressure Swing Adsorption adopts the mixed adsorbent of main adsorbed methane and main adsorption of oxygen, and methane and oxygen are adsorbed simultaneously; The methane volume fraction is lower than 5% in the discharging gas that its adsorption tower exhaust end is discharged, oxygen purity is lower than 9.47%, realize the safe separating of described low-concentration methane gas, the scope of the adsorbent mass of the adsorbent mass of main adsorption of oxygen/main adsorbed methane is 9: 1～1: 2.
2. safe adsorption and enrichment of gas with low concentration method according to claim 1, it is characterized in that: the pressure-swing absorption apparatus of safe adsorption and enrichment of gas with low concentration comprises at least 2 adsorption towers.
3. safe adsorption and enrichment of gas with low concentration method according to claim 2, it is characterized in that: the adsorbent of described main adsorbed methane is active carbon, zeolite molecular sieve and MOF thrin, and the adsorbent of described main adsorption of oxygen is carbon molecular sieve.
4. safe adsorption and enrichment of gas with low concentration method according to claim 1, it is characterized in that: the employed adsorptive pressure of described safe adsorption and enrichment method is controlled in 0.1MPa～0.9MPa scope, and depressurization desorption pressure is controlled in 0.01MPa～0.1MPa scope.
5. each described safe adsorption and enrichment of gas with low concentration method according to claim 1-4, it is characterized in that: described low concentration gas is that the methane volume fraction is 20%, and oxygen purity is 16.8%, and the nitrogen volume fraction is 64.2%; Described mixed adsorbent adopts active carbon and carbon molecular sieve, and carbon molecular sieve is 3.6: 1 with the ratio of quality of activated carbon; Adsorptive pressure is up to 320kPa, and depressurization desorption pressure is minimum to be 25kPa; Obtain at last stripping gas and the discharging gas of following constituent:
Stripping gas methane volume fraction: 33.1%;
Stripping gas oxygen purity: 21%;
Discharging gas methane volume fraction: 2.9%;
Discharging gas oxygen purity: 8.9%.
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| CN101732947B true CN101732947B (en) | 2013-05-01 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102389685B (en) * | 2011-10-11 | 2014-04-09 | 北京科技大学 | Coal mine methane gas enriching method comprising step of pumping at exhaust end of adsorption tower |
| CN105312026B (en) * | 2014-07-09 | 2017-10-31 | 江苏瑞丰科技实业有限公司 | Normal temperature methane efficient absorption material |
| CN105201546B (en) * | 2015-09-21 | 2017-05-17 | 河南理工大学 | Device and method for improving gas extraction concentration |
| CN106669636B (en) * | 2015-11-11 | 2019-08-27 | 中国科学院大连化学物理研究所 | A kind of ordered structure adsorbent and its application |
| CN110368803B (en) * | 2019-07-22 | 2021-10-22 | 煤科集团沈阳研究院有限公司 | Gas absorbent and preparation method and application thereof |
| CN111258192A (en) * | 2020-02-11 | 2020-06-09 | Tcl华星光电技术有限公司 | Photoresist stripping device and photoresist stripping method |
Citations (4)
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|---|---|---|---|---|
| US5229089A (en) * | 1991-11-06 | 1993-07-20 | The Boc Group, Inc. | Recovery of flammable materials from gas streams |
| EP0722764A2 (en) * | 1995-01-23 | 1996-07-24 | The Boc Group, Inc. | Recovery of hydrocarbons from gas streams |
| CN101503335A (en) * | 2009-02-17 | 2009-08-12 | 杨皓 | Method for concentrating methane by gas pressure swing adsorption of low concentration methane |
| CN101596391A (en) * | 2009-06-05 | 2009-12-09 | 安徽理工大学 | The pressure swing adsorption and staged concentrated method of a kind of low concentration gas |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5229089A (en) * | 1991-11-06 | 1993-07-20 | The Boc Group, Inc. | Recovery of flammable materials from gas streams |
| EP0722764A2 (en) * | 1995-01-23 | 1996-07-24 | The Boc Group, Inc. | Recovery of hydrocarbons from gas streams |
| CN101503335A (en) * | 2009-02-17 | 2009-08-12 | 杨皓 | Method for concentrating methane by gas pressure swing adsorption of low concentration methane |
| CN101596391A (en) * | 2009-06-05 | 2009-12-09 | 安徽理工大学 | The pressure swing adsorption and staged concentrated method of a kind of low concentration gas |
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