CN1279006C - Method for purification and recovery of methane from refuse landfill gas - Google Patents

Method for purification and recovery of methane from refuse landfill gas Download PDF

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CN1279006C
CN1279006C CNB2004100812725A CN200410081272A CN1279006C CN 1279006 C CN1279006 C CN 1279006C CN B2004100812725 A CNB2004100812725 A CN B2004100812725A CN 200410081272 A CN200410081272 A CN 200410081272A CN 1279006 C CN1279006 C CN 1279006C
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gas
adsorption
pressure
bed
aluminum oxide
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CN1634813A (en
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李克兵
殷文华
刘丽
王键
武立新
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Southwest Research and Desigin Institute of Chemical Industry
Haohua Chemical Science and Technology Corp Ltd
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Sichuan Tianyi Science and Technology Co Ltd
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    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

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Abstract

In the method of the present invention, garbage landfill gas is treated with the following procedures, such as compression, desulfurization, freezing liquid separation, temperature swing adsorption (TSA) and pressure swing adsorption (PSA), and methane product gas of which the purity is from 80 to 90% and the yield is from 80 to 95% is obtained, wherein in the desulfurization procedure, a special compound desulfurizing agent containing activated carbon and ferric oxide is adopted, the total sulfur is at least 20 mg/m<3> after desulfurization; the temperature of a freezing liquid separation system is from 4 to 10 DEG C, and most of water and high boiling substances are removed; in the TSA, aluminum oxide and silica gel, or aluminum oxide and activated carbon are used as adsorbing agents, the volume mixture ratio of the aluminum oxide to the silica gel (or activated carbon) is 1 to (2 to 10), the aluminum oxide is filled at the inlet end of an adsorbent bed, and the silica gel or the activated carbon is filled at the outlet end of the adsorbent bed; or in the TSA, the volume mixture ratio of aluminum oxide to activated carbon to silica gel which are used as adsorbing agents is 1 to (2 to 10) to (2 to 10); in the PSA, an evacuation and desorption technology is adopted, aluminum oxide and silica gel are used as adsorbing agents, the volume mixture ratio of the aluminum oxide to the silica gel is 1 to (3 to 10), the adsorbent pressure is from 0.2 to 2.5MPa(G), and the evacuation pressure is from-0.09 to-0.05MPa(G). The product gas (methane)is obtained from the adsorption stage. The method is especially suitable for the purification and the recovery of high-purity methane from garbage landfill gas.

Description

From refuse embedded gas, purify the method that reclaims methane
Technical field:
The separating of the present invention and gas mixture, purification are relevant with recovery method, especially with to purify the method that reclaims methane from refuse embedded gas relevant.
Background technology:
Rubbish focuses on landfill yard, waters the fermentation using bacteria agent and covers mucous membrane and earth again, and the gas that produces of degrading in anaerobic process of the organism in the rubbish is called refuse embedded gas (Landfill gas, english abbreviation LFG).The complicated component of LFG, and along with the composition of the stabilization process of rubbish, compaction, rubbish and factor such as characteristic, the geographic hydrology matter of landfill and land-fill method and become, main component is CH 4, N 2, CO 2And H 2O, other trace impurities have more than 140 kinds.The typical case forms table 1:
The typical case of table 1 refuse embedded gas forms
Main component Content v% Minor component
Component Content (V10 -6) Component Content (V10 -6) Component Content (V10 -6)
CH 4 40～50 H 2S 20～100 Ethylene Dichloride 33 Benzene 0.4～2
CO 2 32～40 Thiomethyl alcohol 3～5 Ethylene dichloride 0.25 Vinylbenzene 0～0.5
N 2 2～4 Sulfur alcohol 0.1～0.5 Trieline 2.8 Toluene 4.7～35
H 2O 3～12 Dimethyl sulfide 5～10 Dichlorofluoromethane 0.6 Ethylbenzene 3.5～13
O 2 2～4 Dimethyl disulfide 0.01～0.05 Zellon 6.3 Chlorobenzene 0.1～1.0
CO 0.4～0.6 COS ＜0.5 Methylene dichloride 12.0 Iso-pentane 0～0.1
NH3 1～3 CS2 ＜0.5 Vinylchlorid 1.4 Skellysolve A 0～0.02
The main component of refuse embedded gas is CO 2And CH 4, directly discharging can produce stronger Greenhouse effect, and easy explosion caused accident.And the micro-content organism in the landfill gas can cause serious environmental to pollute.
Refuse embedded gas also is a kind of energy of recyclable utilization, has very high calorific value, about 19MJ/m 3, approaching with the calorific value of town gas.Purify and recycle landfill gas, can turn waste into wealth, improve environmental quality.Because the composition of landfill gas is very complicated, especially contains high boiling sulfide, muriate and other organism, it is big to purify difficulty.The recycling of landfill gas is carried out in more than 500 refuse landfill of existing more than 20 countries in the world at present, its most of refuse landfill is directly to utilize refuse embedded gas to generate electricity for oil engine or burning generation steam heating, and only the small portion landfill gas is used as piped gas after dehydration purifies.
Because town gas or C-1 chemistry processing are higher to the purity requirement of methane, and the main component in the landfill gas is CO 2And CH 4, in order to improve methane concentration, increase the calorific value of purified gas, must remove CO 2The present invention adopts desulfurization, freezing separatory, alternating temperature absorption (being called for short TSA), transformation absorption (being called for short PSA) process integration.TSA adopts special sorbent material and proportioning to remove high boiling substance in the refuse embedded gas, and the sorbent material behind the absorption high boiling substance can regenerate at a lower temperature, and PSA removes most of CO 2Thereby, reach the purpose that concentrates methane.
Countries in the world also in the purifying method of active development refuse embedded gas, because trace impurity is difficult for removing, only limit to adopt liquid phase absorption process (as MDEA) to remove CO at present at present 2The art of this patent adopts absolutely dry method flow process, and Technology is reliable, and flow process is simple, the most components except that methane in the refuse embedded gas can be removed, and comprises removing trace impurity and CO 2, the alternative Sweet natural gas of the methane gas after the purification is as the raw material of C-1 chemistry.
The content of invention:
The purpose of this invention is to provide a kind of method that from refuse embedded gas and similar source of the gas, reclaims methane.
The present invention is achieved in that
Purify the method that reclaims methane in the refuse embedded gas of the present invention, comprise landfill gas is compressed to 0.20～2.5MPaG, the landfill gas desulfurization, landfill gas is refrigerated to 4～10 ℃, remove most of water and high boiling substance and obtain rough purification gas, the rough purification pneumatic transmission is gone into temperature swing adsorption system, send into pressure swing adsorption system after removing most of trace impurity, reclaim methane.
Temperature swing adsorption system is the continuous operation system that two or more adsorption beds are formed, each adsorption bed is once experiencing absorption in the circulation successively, step-down, thermal regeneration, cooling, the step of boosting, the pressure of adsorption step is 0.20～2.5MPaG, temperature is 15～45 ℃, purified gas removes the adsorption bed of pressure swing adsorption system, depressurization step is the reverse normal pressure that is depressurized to, the impurity composition that major part is adsorbed is discharged adsorption bed with the step-down air-flow, the impurity composition that residue is adsorbed is by discharging with resurgent gases with the resurgent gases thermal regeneration, the temperature of thermal regeneration step is 120～300 ℃, the adsorption bed that the cold blowing step adopts the product gas of pressure swing adsorption system stripping gas or product gas or temperature swing adsorption system that firm thermal regeneration is finished carries out cold blowing, make its temperature reduce to adsorption temp, the step of boosting boosts to adsorptive pressure with the purified gas of landfill gas or temperature swing adsorption system adsorption step or the product gas of pressure swing adsorption system to adsorption bed.
Pressure swing adsorption system is the continuous operation system that two or more adsorption beds are formed, each adsorption bed is once experiencing absorption in the circulation successively, at least once all pressure drops, the reverse pressure of putting, find time, at least once all voltage rise reaches the step of finally boosting, adsorption step pressure is 0.2～2.5MPaG, its adsorption temp is 15～45 ℃, the purified gas that contains methane is discharged by adsorption bed product end, reverse putting pressed the most of impurity composition of step by unstripped gas inlet end discharging bed internal adsorption, the reverse resulting pressure of putting pressure is near normal pressure, evacuation step further allows the impurity composition that is adsorbed in the bed desorb, evacuation pressure is-0.05～-0.09MPaG, all voltage rise is an one or many, utilize the gas of the equal pressure drop of other adsorption bed to boost, the step of finally boosting utilizes the product gas of adsorption step gained to boost from adsorption bed product end, make its pressure reach adsorptive pressure, or from the bed feed end adsorption bed is boosted with landfill gas, or simultaneously adsorption bed is boosted from bed raw material gas inlet end and product gas outlet end with the product gas of landfill gas and transformation absorption, until reaching adsorptive pressure.
Temperature swing adsorption system is sorbent used to be aluminum oxide and silica gel or aluminum oxide and gac, its proportioning is 1: 2～10 volume ratios, or aluminum oxide, gac and silica gel, its proportioning is 1: 2～10: 2～10 volume ratios, aluminum oxide is seated in the adsorption bed inlet end, and silica gel, gac are seated in the adsorption bed exit end; Pressure swing adsorption system adopts the desorption technique of finding time, and sorbent material is aluminum oxide and silica gel, and its proportioning is 1: 3～10 volume ratios, and adsorptive pressure is 0.2～2.5MPaG, and evacuation pressure is-0.05～-0.09MPaG, the finished product gas methane is to obtain from absorption phase.
In the desulphurization system, remove organosulfur and inorganic sulfur in the landfill gas with modified activated carbon and iron oxide compound desulfurizer, the proportioning of modified activated carbon and iron oxide compound desulfurizer is: 1: 1～10 volume ratios.
The resurgent gases of alternating temperature absorption is pressure swing adsorption system stripping gas or product gas, or is the product gas of temperature swing adsorption system, or is N 2
The present invention and existing recovery CH 4Method is compared different, mainly shows:
(1) source of the gas is formed difference, and existing recovery methane method is as methane in the patent CN 85 1 03557 B pressure swing adsorption process enrichment coal mine mash gas, methane content only is 20～30% in the coal mine gas, all the other foreign gas N2 50～60%, O2+Ar 12～18%, saturation water; And rubbish is formed complicated (seeing the above table), methane content 40～50%, impurity contains the minor component that thiomethyl alcohol, Ethylene Dichloride, chlorobenzene and penta ethane etc. are difficult for removing, and does not reach the purpose that methane after removing these minor components and making recovery has higher purity and yield with single pressure swing adsorption process and common sorbent material.The present invention adopts compression, desulfurization, freezing separatory, alternating temperature absorption and transformation absorption process combined to be used aluminum oxide and silica gel or aluminum oxide and acticarbon, obtains the methane of purity 80～90%, yield 80～95%.
(2) obtain the stage difference of methane, methane is to obtain product methane from desorption phase in the pressure swing adsorption process enrichment coal mine mash gas, and the present invention obtains product methane from absorption phase.
Because the source of the gas of refuse embedded gas is huge, so this patented method is used to purify refuse embedded gas, has vast market prospect and considerable economic results in society, also help environment protection simultaneously.
The present invention can take off the sulphur in the refuse embedded gas to≤20mg/m 3, all the other trace impurities take off to≤50 * 10-6, methane purity and reach 80～90%, the methane yield reaches 80～95%.
Description of drawings:
Fig. 1 is a FB(flow block) of the present invention.
Embodiment:
Embodiment 1:
The present invention is made of compression, desulfurization, freezing separatory, alternating temperature absorption and transformation absorption technological processs such as (being two).Its flow process is illustrated as Fig. 1:
Particular content of the present invention is described below.
Compression: non-pressurized refuse embedded gas is compressed to the required pressure of subsequent handling, so that overcome enough resistance drops, satisfies the C0 of PSA 2Decreasing ratio and CH 4The requirement of the rate of recovery, compressed landfill gas pressure are 0.2MPa (G) or 1.5MPa (G) or 2.5MPa (G).
Desulfurization: desulfurization process adopts modified activated carbon and iron oxide compound desulfurizer, and its proportioning is 1: 1～10 (volume ratios).Pressure is that the landfill gas of 0.2MPa (G) or 1.8MPa (G) or 2.5MPa (G) is sent into the desulfurization process desulfurization, makes sulphur content≤20mg/m wherein 3, satisfy the requirement of town gas to sulfide.
Freezing separatory: 4-10 ℃ of freezing separatory system operation temperature, purpose is to remove most of water and high boiling substance.
Alternating temperature absorption: it is further to remove larger molecular organicses such as the component that do not remove after rough purification is handled such as benzene, toluene, positive iso-pentane that native system mainly acts on, and makes trace impurity content≤50 * 10-6.TSA is sorbent used to be a kind of in aluminum oxide and silica gel or the gac, and its proportioning is 1: 2～10 (volume ratios), or aluminum oxide, gac and silica gel, and its proportioning is 1: 2～10: 2～10 (volume ratios).
Each adsorption bed in the TSA technology of the present invention experiences following steps successively in once circulating:
(1) refuse embedded gas of absorption (A): pressure 0.2MPa (G) or 1.2MPa (G) or 2.5MPa (G) enters the alternating temperature adsorption bed and adsorbs, remove trace impurity after, purified gas removes the PSA adsorption bed.When impurity reaches normality in Purge gas after, to end unstripped gas, stop absorption, unstripped gas entered cooled another bed of regenerating and adsorbed this moment.
(2) step-down (D): reverse step-down is near normal pressure, and the component that major part is adsorbed is discharged the TSA adsorption bed with the step-down air-flow.
(3) thermal regeneration (H): the product gas of the stripping gas of pressure swing adsorption system or product gas or temperature swing adsorption system or nitrogen are heated to 120 ℃ or 180 ℃ or 250 ℃ or 300 ℃ as resurgent gases or enter the intact adsorption bed of firm absorption through the exit end of adsorption bed and carry out thermal regeneration.
(4) cold blowing (C): the product gas of pressure swing adsorption system stripping gas or product gas or temperature swing adsorption system enters the intact adsorption bed of firm thermal regeneration, and adsorption bed is carried out cold blowing, makes the temperature of adsorption bed reduce to adsorption temp.
(5) (R) boosts: with the purified gas of landfill gas or temperature swing adsorption system adsorption step or the product gas of pressure swing adsorption system adsorption bed is boosted to adsorptive pressure.
Transformation absorption: the effect of native system is a large amount of impurity composition CO that remove in the refuse embedded gas 2Reach other impurity of trace such as benzene, toluene, positive iso-pentane etc., finish recovery methane.
Each adsorption bed in the pressure swing adsorption technique of the present invention experiences following steps successively in once circulating:
(1) absorption (A): the refuse embedded gas that will be have removed trace impurity by TSA is sent into the adsorption bed feed end and is adsorbed adsorptive pressure 0.2MPa (G) or 1.5MPa (G) or 2.5MPa (G), the easy CO absorption of selective adsorption 2Deng impurity composition, be difficult for adsorbed components (as oxygen, nitrogen, methane, CO etc.) and discharge by adsorption bed and from the product end, when impurity reaches normality in Purge gas, stop unstripped gas, stop absorption.
(2) all pressure drops (ED): after the A step, gas in the bed is arranged owing to a bed internal pressure the discharge process constantly descends, so CO from adsorption bed product end 2The impurity composition absorb leading-edge also constantly moves to the product end with adsorption zone, ends gaseous emission when absorb leading-edge moves to the products export end, at this moment, and CO 2The impurity absorption district stays in the bed basically entirely, and expellant gas does not contain CO 2Impurity composition, the good bed that can be used for regenerating boosts.According to the processing power of adsorptive pressure, sorbent material, the situation of bed number, all pressure drop can be finished one or more times, can abbreviate as successively E1D, E2D, E3D, E4D, E5D ...
(3) the reverse pressure (D) of putting: after above-mentioned ED step finished, gas still residual in the adsorption bed was then drained by the feed end of bed, and reverse putting presses final pressure near normal pressure.
(4) (V) finds time: regenerate more thoroughly in order to make the agent of bed internal adsorption, adopt the method vacuumize, further reduce after the D step CO in the bed 2Dividing potential drop, remaining CO 2And other trace impurity component drains from the feed end of bed, this process need make usually bed layer pressure reduce to-0.05MPa (G) or-0.07MPa (G) or-0.09MPa (G).
(5) all voltage rises (ER): this step is corresponding with the ED step, promptly utilizes ED step adsorption bed expellant gas to enter and finishes the adsorption bed that the V step is in vacuum state, and its pressure is progressively raise.This step can be finished one or more times, can abbreviate as successively E1R, E2R, E3R, E4R, E5R ...
(6) (FR) finally boosts: because the ER step can't make adsorption bed pressure reach adsorptive pressure, therefore need the part of the product gas exported with the adsorption bed that is in the A step this adsorption bed to be boosted from the product end, also useful raw materials gas boosts to this adsorption bed or product gas and unstripped gas finally boost to adsorption bed simultaneously from the bed feed end, until reaching adsorptive pressure.
Each adsorption bed all will experience identical step, just diverge mutually on the sequential, carry out continuously to guarantee sepn process.
Embodiment 2:
This example adopts temperature swing adsorption process 2 bed systems, 4 equal pressing systems of secondary of pressure swing adsorption technique.TSA adsorption bed dress aluminum oxide and silica gel, volume ratio is 1: 6, PSA adsorption bed dress aluminum oxide and silica gel, volume ratio is 1: 7.
The compressed machine of forming as table one of refuse embedded gas is compressed to 0.5MPa, enter desulphurization system and carry out desulfurization, desulphurization system adopts two tower series-parallel connection flow processs, sweetening agent modified activated carbon and iron oxide compound desulfurizer, its proportioning is 1: 2 (volume ratio), and sulphur in the refuse embedded gas is taken off to≤20mg/m 3After enter freezing minute liquid system again, freezing separatory system operation temperature is 5 ℃, isolates most of water and high-boiling-point impurity in the refuse embedded gas.The refuse embedded gas of rough purification enters the TSA system of two towers, and the TSA working pressure is 0.45MPa, and loop cycle is 12 hours.Unstripped gas enters adsorption tower from top, and the high hydro carbons in the unstripped gas is adsorbed, and makes trace impurity take off the PSA system that enters four-column process flow to≤50 * 10-6 again.When high hydro carbons is about to penetrate adsorption bed in the adsorption tower, cut off feed valve, open the contrary valve of putting, from the top of tower most of impurity in the tower is discharged the TSA adsorption tower, enter the TSA adsorption tower after the stripping gas of PSA is heated to 130 ℃, adsorption tower is further regenerated, and the TSA adsorption tower after the regeneration is through boosting and entering adsorption step.
The working pressure of PSA system is 0.4MPa (G)～0.45MPa (G), enters the PSA system from the purified gas of temperature swing adsorption system, and purified gas enters adsorption tower from the adsorption tower bottom and adsorbs, low hydrocarbon and CO in the unstripped gas 2Be adsorbed, product methane is drawn the battery limit (BL) from adsorption tower top.The every tower of PSA experiences absorption (A), once all pressure drops (E1D), the equal pressure drop of secondary (E2D) successively, contraryly puts (D), find time (V), the equal voltage rise of secondary (E2R), once all voltage rises (E1R), fill eventually (FR), evacuation pressure be-0.05～-0.09MPa (G), control the CO in the product methane gas 2Concentration is 0.6%.
The methane purity that reclaims in this example reaches 90%, and yield reaches 80%.
Embodiment 3:
This example adopts temperature swing adsorption process 2 bed systems, 6 three equal pressing systems of pressure swing adsorption technique.Attached tower dress aluminum oxide of TSA and gac, volume ratio is 1: 2, attached tower dress aluminum oxide of PSA and silica gel, volume ratio is 1: 9.
The compressed machine of forming as table one of refuse embedded gas is compressed to 0.7MPa (G), enter freezing minute liquid system, freezing separatory system operation temperature is 6 ℃, with most of water and high-boiling-point impurity condensation separation discharging garbage landfill gas wherein, refuse embedded gas enters desulphurization system and carries out desulfurization, sweetening agent is with modified activated carbon and iron oxide compound desulfurizer, and its proportioning is 1: 5 (volume ratio), and sulphur takes off to≤20mg/m 3The refuse embedded gas of rough purification enters the alternating temperature adsorption unit, and the regeneration temperature of TSA system is 240 ℃, trace impurity is taken off to≤50 * 10-6 enter the PSA system again, and evacuation pressure is-0.075MPa the CO in the control product methane gas 2Concentration is 1.0%.The methane purity that reclaims in this example reaches 87%, and yield reaches 85%.
Embodiment 4:
This example adopts temperature swing adsorption process 2 bed systems, 6 three equal pressing systems of pressure swing adsorption technique.The attached tower dress of TSA aluminum oxide, silica gel and gac, volume ratio is 1: 3: 5 or 1: 2: 10 or 1: 10: 2 or 1: 5: 7, attached tower dress aluminum oxide of PSA and silica gel, volume ratio is 1: 3.
The compressed machine of forming as table one of refuse embedded gas is compressed to 0.7MPa, enter freezing minute liquid system, freezing separatory system operation temperature is 6 ℃, with most of water and high-boiling-point impurity condensation separation discharging garbage landfill gas wherein, refuse embedded gas enters desulphurization system and carries out desulfurization, sweetening agent is with modified activated carbon and iron oxide compound desulfurizer, and its proportioning is 1: 5 (volume ratio), and sulphur takes off to≤20mg/m 3The refuse embedded gas of rough purification enters the alternating temperature adsorption unit, and the regeneration temperature of TSA system is 200 ℃, trace impurity is taken off to≤50 * 10-6 enter the PSA system again, and evacuation pressure is-0.075MPa the CO in the control product methane gas 2Concentration is 1.0%.The methane purity that reclaims in this example reaches 87%, and yield reaches 85%.
Embodiment 5:
This example adopts temperature swing adsorption process 3 bed systems, 8 four equal pressing systems of pressure swing adsorption technique.TSA adsorption bed dress aluminum oxide and silica gel, volume ratio is 1: 8, PSA adsorption bed dress aluminum oxide and silica gel, volume ratio is 1: 8.
The compressed machine of forming as table one of refuse embedded gas is compressed to 1.0MPa (G), enters desulphurization system and carries out desulfurization, and sweetening agent is with modified activated carbon and iron oxide compound desulfurizer, and its proportioning is 1: 6 (volume ratio), and sulphur is taken off to≤20mg/m 3Enter freezing minute liquid system, freezing separatory system operation temperature is 4.5 ℃, with most of water and high-boiling-point impurity condensation separation discharging garbage landfill gas wherein, the refuse embedded gas of rough purification enters the TSA system, the regeneration temperature of TSA system is 160 ℃, trace impurity is taken off to≤50 * 10-6 enter the PSA system again, evacuation pressure is-0.09MPa (G).CO in the control product methane gas 2Concentration is 1.0%.The methane purity that reclaims in this example reaches 85%, and yield reaches 90%.
Embodiment 6:
This example adopts temperature swing adsorption process 3 bed systems, 10 five equal pressing systems of pressure swing adsorption technique.TSA adsorption bed dress aluminum oxide and gac, volume ratio is 1: 7.5, PSA adsorption bed dress aluminum oxide and silica gel, volume ratio is 1: 10.
The compressed machine of forming as table one of refuse embedded gas is compressed to 1.0MPa (G), enters desulphurization system and carries out desulfurization, and sweetening agent is with modified activated carbon and iron oxide compound desulfurizer, and its proportioning is 1: 7 (volume ratio), and sulphur is taken off to≤20mg/m 3Enter freezing minute liquid system, freezing separatory system operation temperature is 8 ℃, with most of water and high-boiling-point impurity condensation separation discharging garbage landfill gas wherein, the refuse embedded gas of rough purification enters the TSA system, the regeneration temperature of TSA system is 250 ℃, trace impurity is taken off to≤50 * 10-6 enter the PSA system again, evacuation pressure is-0.08MPa (G) CO in the control product methane gas 2Concentration is 3.0%.The methane purity that reclaims in this example reaches 83%, and yield reaches 92%.
Embodiment 7:
This example adopts temperature swing adsorption process 4 bed systems, 12 five equal pressing systems of pressure swing adsorption technique.TSA adsorption bed dress aluminum oxide and gac, volume ratio is 1: 7, PSA adsorption bed dress aluminum oxide and silica gel, volume ratio is 1: 10.
The compressed machine of forming as table one of refuse embedded gas is compressed to 0.5～1.6MPa (G), enters desulphurization system and carries out desulfurization, and sweetening agent is with modified activated carbon and iron oxide compound desulfurizer, and its proportioning is 1: 8 (volume ratio), and sulphur is taken off to≤20mg/m 3Enter freezing minute liquid system, freezing separatory system operation temperature is 7 ℃, with most of water and high-boiling-point impurity condensation separation discharging garbage landfill gas wherein, the refuse embedded gas of rough purification enters the TSA system, the regeneration temperature of TSA system is 220 ℃, trace impurity is taken off to≤50 * 10-6 enter the PSA system again, evacuation pressure is-0.08MPa (G) CO in the control product methane gas 2Concentration is 3.0%.The methane purity that reclaims in this example reaches 82%, and yield reaches 93%.
Embodiment 8:
This example adopts temperature swing adsorption process 4 bed systems, 14 five equal pressing systems of pressure swing adsorption technique.TSA adsorption bed dress aluminum oxide and gac, volume ratio is 1: 10, PSA adsorption bed dress aluminum oxide and silica gel, volume ratio is 1: 9.5.
The compressed machine of forming as table one of refuse embedded gas is compressed to 1.6MPa, enters desulphurization system and carries out desulfurization, and sweetening agent is with modified activated carbon and iron oxide compound desulfurizer, and its proportioning is 1: 4 (volume ratio), and sulphur is taken off to≤20mg/m 3Enter freezing minute liquid system, freezing separatory system operation temperature is 4 ℃, with most of water and high-boiling-point impurity condensation separation discharging garbage landfill gas wherein, the refuse embedded gas of rough purification enters the TSA system, the regeneration temperature of TSA system is 180 ℃, trace impurity is taken off to≤50 * 10-6 enter the PSA system again, evacuation pressure is-0.08Mpa (G) CO in the control product methane gas 2Concentration is 2.0%.The methane purity that reclaims in this example reaches 80%, and yield reaches 92%.
Embodiment 9:
This example adopts temperature swing adsorption process 4 bed systems, 16 seven equal pressing systems of pressure swing adsorption technique.TSA adsorption bed dress aluminum oxide and gac, volume ratio is 1: 8, PSA adsorption bed dress aluminum oxide and silica gel, volume ratio is 1: 9.
The compressed machine of forming as table one of refuse embedded gas is compressed to 2.4MPa (G), enters desulphurization system and carries out desulfurization, and sweetening agent is with modified activated carbon and iron oxide compound desulfurizer, and its proportioning is 1: 3 (volume ratio), and sulphur is taken off to≤20mg/m 3Enter freezing minute liquid system, freezing separatory system operation temperature is 4 ℃, with most of water and high-boiling-point impurity condensation separation discharging garbage landfill gas wherein, the refuse embedded gas of rough purification enters the TSA system, the regeneration temperature of TSA system is 200 ℃, trace impurity is taken off to≤50 * 10-6 enter the PSA system again, evacuation pressure is-0.08MPa (G) CO in the control product methane gas 2Concentration is 3.0%.The methane purity that reclaims in this example reaches 80%, and yield reaches 95%.

Claims (6)

1, purifies the method that reclaims methane in the refuse embedded gas, it is characterized in that comprising landfill gas is compressed to 0.20～2.5MPaG, the landfill gas desulfurization, landfill gas is refrigerated to 4～10 ℃, remove most of water and high boiling substance and obtain rough purification gas, the rough purification pneumatic transmission is gone into temperature swing adsorption system, send into pressure swing adsorption system after removing most of trace impurity, reclaim methane.
2, method according to claim 1, it is characterized in that temperature swing adsorption system is the continuous operation system that two or more adsorption beds are formed, each adsorption bed is once experiencing absorption in the circulation successively, step-down, thermal regeneration, cooling, the step of boosting, the pressure of adsorption step is 0.20～2.5MPaG, temperature is 15～45 ℃, purified gas removes the adsorption bed of pressure swing adsorption system, depressurization step is the reverse normal pressure that is depressurized to, the impurity composition that major part is adsorbed is discharged adsorption bed with the step-down air-flow, the impurity composition that residue is adsorbed is by discharging with resurgent gases with the resurgent gases thermal regeneration, the temperature of thermal regeneration step is 120～300 ℃, the adsorption bed that the cold blowing step adopts the product gas of pressure swing adsorption system stripping gas or product gas or temperature swing adsorption system that firm thermal regeneration is finished carries out cold blowing, make its temperature reduce to adsorption temp, the step of boosting boosts to adsorptive pressure with the purified gas of landfill gas or temperature swing adsorption system adsorption step or the product gas of pressure swing adsorption system to adsorption bed.
3, method according to claim 1, it is characterized in that pressure swing adsorption system is the continuous operation system that two or more adsorption beds are formed, each adsorption bed is once experiencing absorption in the circulation successively, at least once all pressure drops, the reverse pressure of putting, find time, at least once all voltage rise reaches the step of finally boosting, adsorption step pressure is 0.2～2.5MPaG, its adsorption temp is 15～45 ℃, the purified gas that contains methane is discharged by adsorption bed product end, reverse putting pressed the most of impurity composition of step by unstripped gas inlet end discharging bed internal adsorption, the reverse resulting pressure of putting pressure is near normal pressure, evacuation step further allows the impurity composition that is adsorbed in the bed desorb, evacuation pressure is-0.05～-0.09MPaG, all voltage rise is an one or many, utilize the gas of the equal pressure drop of other adsorption bed to boost, the step of finally boosting utilizes the product gas of adsorption step gained to boost from adsorption bed product end, make its pressure reach adsorptive pressure, or from the bed feed end adsorption bed is boosted with landfill gas, or simultaneously adsorption bed is boosted from bed raw material gas inlet end and product gas outlet end with the product gas of landfill gas and transformation absorption, until reaching adsorptive pressure.
4, according to claim 1 or 2 or 3 described methods, it is characterized in that temperature swing adsorption system sorbent used be aluminum oxide and silica gel or aluminum oxide and gac, its proportioning is 1: 2～10 volume ratios, or aluminum oxide, gac and silica gel, its proportioning is 1: 2～10: 2～10 volume ratios, aluminum oxide is seated in the adsorption bed inlet end, and silica gel, gac are seated in the adsorption bed exit end; Pressure swing adsorption system adopts the desorption technique of finding time, and sorbent material is aluminum oxide and silica gel, and its proportioning is 1: 3～10 volume ratios, and adsorptive pressure is 0.2～2.5MPaG, and evacuation pressure is-0.05～-0.09MPaG, the finished product gas methane is to obtain from absorption phase.
5, method according to claim 1, it is characterized in that in the desulphurization system, remove organosulfur and inorganic sulfur in the landfill gas with modified activated carbon and iron oxide compound desulfurizer, the proportioning of modified activated carbon and iron oxide compound desulfurizer is: 1: 1～10 volume ratios.
6, method according to claim 1 and 2 is characterized in that the resurgent gases of alternating temperature absorption is pressure swing adsorption system stripping gas or product gas, or is the product gas of temperature swing adsorption system, or is N 2
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