CN103861422A - New technique for concentrating methane in oxygen-containing coal bed gas - Google Patents

New technique for concentrating methane in oxygen-containing coal bed gas Download PDF

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Publication number
CN103861422A
CN103861422A CN201410049993.1A CN201410049993A CN103861422A CN 103861422 A CN103861422 A CN 103861422A CN 201410049993 A CN201410049993 A CN 201410049993A CN 103861422 A CN103861422 A CN 103861422A
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gas
methane
concentrate
concentration
bed gas
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CN103861422B (en
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余兰金
兰治淮
刘清源
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SICHUAN DKT ENERGY TECHNOLOGY Co Ltd
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SICHUAN DKT ENERGY TECHNOLOGY Co Ltd
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Abstract

The invention discloses a new technique for concentrating methane in oxygen-containing coal bed gas. Different adsorbents and different technological processes are adopted according to different concentrations of methane in the oxygen-containing coal bed gas, when concentration of methane in the oxygen-containing coal bed gas is low, a three-stage technological process is adopted, namely a first stage of low pressure methane enrichment technological process, a second stage of pressurized adsorption deoxygenation technological process, and a third stage of methane concentration technological process; when the concentration of the methane in the oxygen-containing coal bed gas is high, a two-stage technological process is adopted, namely a first stage of pressurized adsorption deoxygenation technological process and a second stage of methane concentration technological process, and 2-12 towers are arranged during an adsorption process. By adopting the new technique for concentrating the methane in the oxygen-containing coal bed gas, concentration of CH4 in the oxygen-containing coal bed gas can be increased to be more than 90%, O2 content can be reduced to be less than 0.5%, and a corresponding multi-stage concentrating way and a corresponding adsorbent are adopted in a concentrating process, so that technical defects in the prior art that PSA (polysulfone amide) is adopted for concentrating CH4 in the oxygen-containing coal bed gas are overcome.

Description

A kind of concentrate is containing the new process of methane in oxygen coal-bed gas gas
Technical field
The present invention relates to gas separation technique field, particularly relate to the new process of a kind of concentrate containing methane in oxygen coal-bed gas gas.
Background technology
For the concentrate of coal-bed gas gas, in document, there is the report of multiple situation, think the most practical with pressure swing adsorption method (PSA) in all multi-methods, the domestic You Duojia unit that carries out correlative study:
One, in Ministry of Education's coal bed gas concentrate emphasis science and technology item task of bearing in University Of Chongqing, mainly with CH 4/ N 2-active carbon is research system, carries out the selection of adsorbent, and they think with regard to the PSA extracting and concentrating technology of coal-bed gas gas, no matter from studying or should being used for, all lack very much at present, should strengthen the dynamics of scientific research and through engineering approaches;
Its two, in University Of Tianjin's High Pressure Absorption laboratory, draw high surface activity carbon, specific area reaches 3000m2/g, CH 4with N 2separation reach 20.13, but due to the original performance that is hard to keep of the active carbon after its moulding, also there is larger difficulty for industrial;
Its three, in Institutes Of Technology Of Taiyuan to CH 4/ N 2adsorbing separation test in, employing be carbon molecular sieve (CMS), with this adsorbent separation of C H 4/ N 2though, CH 4/ N 2separation wants large compared with active carbon, but still undesirable, and CMS price is high, wants cheapness and obtains high concentration CH 4still have difficulties.
In the research and development of above-mentioned coal-bed gas gas, domestic is mostly to make adsorbent with active carbon, Patents has: " CN85103557 ", " CN101096907A ", " CN101096908 " proposed to adopt active carbon to make the PSA concentrate CH of adsorbent 4process.Because CH 4/ N 2separation too little, as the products C H of strong adsorbent component 4to obtain from stripping gas, CH 4concentrate multiple not high, the more important thing is in process that safety and product quality can not get sufficient assurance in actual production, thereby cannot be used for actual production without effectively deoxidation.And abroad at CH 4/ N 2the adsorbent separating mostly is CMS, mainly for high concentration CH 4casing-head gas (CH 4> 70%), through concentrated CH 4can be higher than 90%; For intermediate concentration CH 4rubbish landfill gas (CH 4in 60% left and right), also there is good effect, and have commercialization example.But the relevant report separating containing oxygen coal-bed gas gas PSA for low concentration (< 30%) is little, and for device in Gas, deoxidation has people to propose Production by Catalytic Combustion Process deoxidation method (CN02113628.9), coke combustion method (CN02113627.0), although these methods deoxidation in advance, but to consume a large amount of methane in combustion process, and generate the CO2 of some, increase follow-up cleaning procedure, because said method causes the drawback that investment is large, methane production is low, have very large difficulty for reality.This reflects coal-bed gas gas from a side, particularly the CH of low concentration coal-bed gas gas 4concentrate, exists larger difficulty.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides the new process of a kind of concentrate containing methane in oxygen coal-bed gas gas, to solve existing PSA concentrate containing CH in oxygen coal-bed gas gas 4technological deficiency, according to different material concentration and requirement, adopt the adsorbent adapting to, the PSA technology of adapt efficient, low consumption is provided.
The technical solution adopted in the present invention is: a kind of concentrate is containing the new process of methane in oxygen coal-bed gas gas, according to containing methane concentration difference in oxygen coal-bed gas gas, adopt different adsorbents, organize different flow processs, it is characterized in that: when described methane in gas concentration is low, adopt three sections of flow processs, first paragraph is low-pressure methane enrichment, second segment is pressurization absorption deoxidation, and the 3rd section is concentrate methane; When described methane concentration is high, adopt two sections of flow processs, first paragraph is pressurization absorption deoxidation, and second segment is concentrate methane, and adsorption process is made up of 2 ~ 12 towers, and by above-mentioned technique, energy will be containing CH in oxygen coal-bed gas gas 4concentrate is to > 90%, O 2content drops to below 0.5%.
As preferably, described adsorbent is active carbon class, molecular sieve, silica type.
As preferably, CH in described device in Gas 4when concentration < 30%, adopt three sections of flow processs, first paragraph, by low pressure adsorption and enrichment methane, obtains guaranteeing the intermediate products of compressing secure, and boost to≤3.0 M Pa.G of these intermediate products enter de-O 2, N 2second segment absorption deoxidation process, never adsorb in gas phase and obtain the deoxidation device in Gas that methane content is higher, directly enter the 3rd section of concentrate methane process, obtain CH 4the gas product of concentration > 90%, O2 < 0.5%.
As preferably, CH in described device in Gas 4when concentration > 30%, adopt two sections of flow processs, first paragraph, for absorption deoxidation, adsorptive pressure is≤3.0MPa.G, adopts absorption O 2, N 2adsorbent, never in adsorbed gas, obtain O 2the intermediate products gas of < 1%, this intermediate products gas can directly enter second segment concentrate methane process, obtains CH 4concentration > 90%, O 2the gas product of < 0.5%.
As preferably, product or other high concentration methane that described facility reclaims mix with the unstripped gas of methane concentration < 30%, make to mix CH in rear unstripped gas 4concentration > 30%, now adopts two sections of flow processs.
As preferably, described concentrate methane section adopts pressure swing adsorption method or separation by deep refrigeration.
As preferably, in described PSA adsorption process, the proceedings of adsorption tower is the absorption of single tower, single tower desorb, each adsorption tower only once adsorbs respectively in a cycle period, all pressure drops, along putting, inverse put, flushing, vacuum desorption, all voltage rises, final rise.
Compared with prior art, the invention has the beneficial effects as follows: by adopting the extracting and concentrating technology of segmented, first in the situation that can meet compressing secure, pressurization deoxidation, the safety of assurance device in Gas separation of methane; Secondly can be to the O that contains of various concentration 2coal-bed gas gas carries out CH 4concentrate, concentrate CH 4concentration > 90%.Consume low, safe and reliable; Then realize and efficiently remove CH 4middle O 2, make O in gas product 2content is down to below 0.5%, can meet the de-O of the degree of depth 2requirement (with the de-O of catalytic combustion 2method, the de-O of coke burning 2method is compared, and this method does not additionally consume CH 4, the CO that methane production height does not also produce because of burning 2, H 2, CO, reduced purification process, simplify flow process, reduce investment and operating cost, improve methane yield); Last the present invention has fully demonstrated PSA method advantage: equipment is simple, automaticity is high, safe and reliable, operating cost is low, CH 4yield high.
Accompanying drawing explanation
Fig. 1 is the pressure-changing process flow figure of low concentration oxygen-containing mash gas of the present invention enrichment or concentrated methane.
Fig. 2 is PSA deoxidation concentrate CH4 process chart of the present invention.
Fig. 3 is two sections of procedural style extracting and concentrating technology flow charts that the present invention mentions.
Fig. 4 is three sections of procedural style extracting and concentrating technology flow charts that the present invention mentions.
In figure: 1,2,3,4,5-surge tank, 9-compressor 8-vavuum pump, 11 ~ 56,110 ~ 117-sequencing valve, 120 ~ 129-stop valve, 181 ~ 185-adsorption tower.
The specific embodiment
Below in conjunction with accompanying drawing, the present invention is further described.
embodiment 1, as shown in Figure 1, the methane content of coal mine mash gas is 12% to flow process, and adsorptive pressure is 0.02MPa.G, and 40 ℃ of adsorption temps are equipped with absorption CH in adsorption tower 4adsorbent, this pressure-swing absorption apparatus adopts safety devices related to the present invention to carry out, explosion-suppressing material has been loaded at the vacant place of adsorption tower, pipeline has filled the explosion-suppressing material that accounts for conduit volume 1%.Pressure swing adsorption technique as shown in Figure 1, adopts the VPSA flow process that single tower adsorbs, twice is all pressed.Device in Gas through compressor compresses enters by 181~185 5 pressure swing adsorption systems that adsorption tower forms.Below take adsorption tower 181 as example is to CH 4the technical process of recovery system is illustrated in conjunction with Fig. 1.
1, absorption A:
Raw material device in Gas enters air inlet surge tank 5, the bottom inflow through sequencing valve 11 from adsorption tower 181, be controlled at~0.02MPa.G of adsorption column pressure, the selected CH that is adsorbed in of methane in device in Gas 4on adsorbent, a small amount of CH 4and other components discharge through sequencing valve 14, stop valve 128 from absorption tower top as adsorbed gas not, enter then emptying of tail gas buffer 4.This step completes separating completely of methane and other components.In the time that adsorption tower 181 discharges in gas that methane concentration reaches 0.81%, close sequencing valve 14,11, adsorption step A finishes.
2, equal pressure drop D1:
After absorption A step finishes, open sequencing valve 15,112, stop valve 126, make 181 adsorption towers and surge tank 3 all be depressed into two tower pressure tank balances.After all pressure finishes, close 15,112 sequencing valves
3, equal pressure drop D2:
After all pressure drop D1 finishes, open sequencing valve 16,46, make 181 adsorption towers and 184 adsorption towers all be depressed into two pressure tower balances.After all pressure finishes, close 16,46 sequencing valves.
4, along putting P:
After all pressure drop D2 finishes, open sequencing valve 16,110, stop valve 124, gas in 181 adsorption towers, along the step-down of absorption direction, in the time that tower internal pressure is down to 0.02 MPa.G, is closed to 16,110 sequencing valves.Enter its recovery system along venting, after pressurization as unstripped gas reuse.
5, gas product displacement Z:
Along after putting P and finishing, open sequencing valve 12,16,111, stop valve 125, close sequencing valve 117,13, displacement gas enters adsorption tower 181 from sequencing valve 12, replace along absorption direction, displace implication and flow out adsorption tower 181 through sequencing valve 16,111, stop valve 125.Displace in implication methane concentration higher, enter its recovery system, after pressurization as unstripped gas reuse.After replacement completion, close sequencing valve 12,16,111.
6, vacuumize V:
After gas product replacement completion, open sequencing valve 13,117, stop valve 122, through surge tank 2, extracted out by vavuum pump 8, vacuumize after end, close sequencing valve 13,117.
7, isolation I:
Vacuumize after end, the sequencing valve 11~16 of adsorption tower 181, all in closed condition, waits pending next step.
8, equal voltage rise E2:
After isolation I finishes, open sequencing valve 16, 36, the gas that utilizes the equal pressure drop E2 of adsorption tower 183 to discharge boosts to completing the adsorption tower vacuumizing, to two pressure tower balances.After all pressure finishes, close sequencing valve 16,36.
9, equal voltage rise E1:
After all voltage rise E2 finishes, open sequencing valve 15,112, utilize the gas in surge tank 3 to boost to adsorption tower 181, to two pressure tower balances.After all pressure finishes, close sequencing valve 15,112.
10, the FR that finally boosts:
After all voltage rise E1 finishes, open sequencing valve 15,113, stop valve 127,128, utilize the gas in surge tank 4 to boost to adsorption tower 181, in the time that adsorption tower 181 pressure approach adsorptive pressure, close sequencing valve 15,113.
Complete after above-mentioned steps, adsorption tower 181 has completed the cycling of one-period.The circulation step of other four adsorption towers 182~185 is identical with adsorption tower 181, just mutually staggering in time, to guarantee having an at any time adsorption tower adsorbing the operation of A step, thereby guarantees the continuous operation of methane adsorbent equipment.
So far, the technical process of the present embodiment all finishes.It is 40% methane gas that the present embodiment can obtain methane content, and methane yield is 95.2%, security of system.
embodiment 2,as shown in Figure 2, the methane content of coal mine mash gas is 40% to flow process, and adsorptive pressure is 0.7 MPa.G, and 30 ℃ of adsorption temps are equipped with de-O in adsorption tower 2adsorbent.This pressure-swing absorption apparatus adopts safety devices related to the present invention to carry out, and explosion-suppressing material has been loaded at the vacant place of adsorption tower, and pipeline has filled the explosion-suppressing material that accounts for conduit volume 1%.Pressure swing adsorption technique as shown in Figure 1, adopts the VPSA flow process that single tower adsorbs, twice is all pressed.Device in Gas through compressor compresses enters by 181~185 5 pressure swing adsorption systems that adsorption tower forms.Below as an example of adsorption tower 181 example to gas qi exhaustion O 2, N 2the technical process of recovery system is illustrated in conjunction with Fig. 2.
1, absorption A:
Raw material device in Gas enters air inlet surge tank 5, the bottom inflow through sequencing valve 11 from adsorption tower 181, be controlled at~0.7MPa.G of adsorption column pressure, the O in device in Gas 2, N 2selected being adsorbed on adsorbent, CH 4and other components are discharged through sequencing valve 14, stop valve 128 from absorption tower top as adsorbed gas not on a small quantity, enter tail gas buffer 4, are re-used as product and send.This step has realized O 2, N 2absorption, improved the concentration of methane, make separating completely of methane and other components.When adsorption tower 181 is discharged O in gas 2when concentration reaches 1.0V%, close sequencing valve 14,11, adsorption step A finishes.
2, equal pressure drop D1:
After absorption A step finishes, open sequencing valve 15,112, stop valve 126, adsorption tower 181 is all depressed into two pressure tower balances with surge tank 3.After all pressure finishes, close sequencing valve 15,112.
3, equal pressure drop D2:
After all pressure drop D1 finishes, open sequencing valve 16,46, adsorption tower 181 is all depressed into two pressure tower balances with adsorption tower 184.After all pressure finishes, close sequencing valve 16,46.
4, along putting P:
After all pressure drop D2 finishes, open sequencing valve 16,110, stop valve 124, interior adsorption tower 181 gas, along the step-down of absorption direction, in the time that tower internal pressure is down to 0.02 MPa.G, is closed to sequencing valve 16,110.Enter its recovery system along venting, after pressurization as unstripped gas reuse.
5, vacuumize V:
Along after putting P and finishing, open sequencing valve 13,117, stop valve 122, through surge tank 2, extracted out by vavuum pump 8, vacuumize after end, close sequencing valve 13,117.
6, isolation I:
Vacuumize after end, the sequencing valve 11~16 of adsorption tower 181, all in closed condition, waits pending next step.
7, equal voltage rise E2:
After isolation I finishes, open sequencing valve 16,36, the gas that utilizes 183 equal pressure drop E2 to discharge boosts to completing the adsorption tower vacuumizing, to two pressure tower balances.After all pressure finishes, close sequencing valve 16,36.
8, equal voltage rise E1:
After all voltage rise E2 finishes, open sequencing valve 15,112, utilize the gas in surge tank 3 to boost to adsorption tower 181, to two pressure tower balances.After all pressure finishes, close sequencing valve 15,112.
9, the FR that finally boosts:
After all voltage rise E1 finishes, open sequencing valve 15,113, stop valve 127,128, utilize the gas in surge tank 4 to boost to adsorption tower 181, in the time that adsorption column pressure approaches adsorptive pressure, close sequencing valve 15,113.
Complete after above-mentioned steps, adsorption tower 181 has completed the cycling of one-period.The circulation step of other four adsorption towers 182~185 is identical with adsorption tower 181, just mutually staggering in time, to guarantee having an at any time adsorption tower adsorbing the operation of A step, thereby guarantees the continuous operation of methane adsorbent equipment.
So far, the technical process of the present embodiment all finishes.The present embodiment can obtain that methane content is 75%, O 2be 1% product methane gas, methane yield is 95.3%, security of system.
example 3, as shown in Figure 1, the methane content of coal-bed gas gas is 75% to flow process, and adsorptive pressure is 1.0 MPa.G, and 40 ℃ of adsorption temps adopt single tower absorption, and absorption CH is housed in adsorption tower 4adsorbent.This PSA device also adopts safety devices related to the present invention to carry out, and explosion-suppressing material has been loaded at the vacant place of adsorption tower, and pipeline has filled the explosion-suppressing material that accounts for conduit volume 1%.The enforcement of PSA technical process is as example 1.
This example can obtain CH 4content 95 %, O 2the product of content < 0.5%, methane yield is 99.5%.
example 4,as shown in Figure 3, the methane content of coal-bed gas gas is 45% to flow process, and adsorptive pressure is 1.0 MPa.G, and 30 ℃ of adsorption temps adopt two sections of flow processs, and first paragraph is equipped with absorption O 2adsorbent.Second segment is equipped with absorption CH4 adsorbent.This PSA device also adopts safety devices related to the present invention to carry out, and explosion-suppressing material has been loaded at the vacant place of adsorption tower, and pipeline has filled the explosion-suppressing material that accounts for conduit volume 1%.Pressure swing adsorption technique as shown in Figure 3, the enforcement of PSA technical process, first paragraph PSA is as example 2, second segment PSA is as example 1.
This example can obtain CH 4content 95.5%, O 2the product of content 0.4%, methane yield is 94.6%.
example 5,as shown in Figure 4, the methane content of coal-bed gas gas is 20% to flow process, and 30 ℃ of adsorption temps adopt three sections of flow processs, and first paragraph is equipped with the adsorbent of absorption CH4, and adsorptive pressure is that 0.1 MPa.G, second segment are equipped with absorption O 2adsorbent, adsorptive pressure is that 1.0 MPa.G, the 3rd section are equipped with absorption CH 4adsorbent, adsorptive pressure is 1.0 MPa.G.This PSA device also adopts safety devices related to the present invention to carry out, and explosion-suppressing material has been loaded at the vacant place of adsorption tower, and pipeline has filled the explosion-suppressing material that accounts for conduit volume 1%.Pressure swing adsorption technique as shown in Figure 4, the enforcement of PSA technical process, first paragraph PSA is as example 1, second segment PSA is if 2, the three sections of PSA of example are as example 1.
This example can obtain CH 4content 95.2%, O 2the product of content 0.5%, methane yield is 91.1%.

Claims (8)

1. a concentrate is containing the new process of methane in oxygen coal-bed gas gas, according to containing methane concentration difference in oxygen coal-bed gas gas, adopt different adsorbents, organize different flow processs, it is characterized in that: when described methane in gas concentration is low, adopt three sections of flow processs, first paragraph is low-pressure methane enrichment, second segment is pressurization absorption deoxidation, and the 3rd section is concentrate methane; When described methane concentration is high, adopt two sections of flow processs, first paragraph is pressurization absorption deoxidation, and second segment is concentrate methane, and adsorption process is made up of 2 ~ 12 towers, and by above-mentioned technique, energy will be containing CH in oxygen coal-bed gas gas 4concentrate is to > 90%, O 2content drops to below 0.5%.
2. a kind of concentrate according to claim 1 is containing the new process of methane in oxygen coal-bed gas gas, and its feature is: described adsorbent is active carbon class, molecular sieve, silica type.
3. the new process containing methane in oxygen coal-bed gas gas according to a kind of concentrate described in claim 1,2, its feature is: CH in described device in Gas 4when concentration < 30%, adopt three sections of flow processs, first paragraph, by low pressure adsorption and enrichment methane, obtains guaranteeing the intermediate products of compressing secure, and boost to≤3.0 M Pa.G of these intermediate products enter de-O 2, N 2second segment absorption deoxidation process, never adsorb in gas phase and obtain the deoxidation device in Gas that methane content is higher, directly enter the 3rd section of concentrate methane process, obtain CH 4the gas product of concentration > 90%, O2 < 0.5%.
4. the new process containing methane in oxygen coal-bed gas gas according to a kind of concentrate described in claim 1,2, its feature is: CH in described device in Gas 4when concentration > 30%, adopt two sections of flow processs, first paragraph, for absorption deoxidation, adsorptive pressure is≤3.0MPa.G, adopts absorption O 2, N 2adsorbent, never in adsorbed gas, obtain O 2the intermediate products gas of < 1%, this intermediate products gas can directly enter second segment concentrate methane process, obtains CH 4concentration > 90%, O 2the gas product of < 0.5%.
5. the new process containing methane in oxygen coal-bed gas gas according to a kind of concentrate described in claim 1,2,4, its feature is: product or other high concentration methane that described facility reclaims mix with the unstripped gas of methane concentration < 30%, make to mix CH in rear unstripped gas 4concentration > 30%, now adopts two sections of flow processs.
6. the new process containing methane in oxygen coal-bed gas gas according to a kind of concentrate described in claim 1,2,3,4,5, its feature is: described concentrate methane section adopts pressure swing adsorption method [U1] separation by deep refrigeration.
7. the new process containing methane in oxygen coal-bed gas gas according to a kind of concentrate described in claim 1,2,3,4,5, its feature is: described concentrate methane section adopts separation by deep refrigeration.
8. the new process containing methane in oxygen coal-bed gas gas according to a kind of concentrate described in claim 1,2,3,4,5,6, its feature is: in described PSA adsorption process, each adsorption tower only adsorbs respectively in a cycle period, all pressure drops, along putting, the process such as inverse put, flushing, vacuum desorption, all voltage rises, final rise.
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CN104436993A (en) * 2014-11-27 2015-03-25 煤炭科学技术研究院有限公司 Concentration separation method for methane in low-concentration gas
CN104479781A (en) * 2014-11-27 2015-04-01 煤炭科学技术研究院有限公司 Method for concentrating and separating methane from gas within explosive limit
CN105199798A (en) * 2015-10-12 2015-12-30 宁波鲍斯能源装备股份有限公司 Low-concentration coal bed gas enriching device
CN105233624A (en) * 2015-10-21 2016-01-13 中国石油化工股份有限公司 Organic gas processing device based on adsorption under pressure and using method thereof
CN106497621A (en) * 2016-12-30 2017-03-15 北京健坤伟华新能源科技有限公司 A kind of biogas pressure-swing absorption apparatus for improving methane recovery
CN108043172A (en) * 2017-12-18 2018-05-18 洛阳健阳科技有限公司 A kind of method of zeolite molecular sieve separation of methane and nitrogen
CN112742172A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Energy gas purification method

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CN112742172A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Energy gas purification method

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