CN107998822A - The method of Pressure Swing Adsorption methane - Google Patents

The method of Pressure Swing Adsorption methane Download PDF

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Publication number
CN107998822A
CN107998822A CN201711376950.4A CN201711376950A CN107998822A CN 107998822 A CN107998822 A CN 107998822A CN 201711376950 A CN201711376950 A CN 201711376950A CN 107998822 A CN107998822 A CN 107998822A
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gas
methane
unstripped gas
pressure
adsorption tower
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Chinese (zh)
Inventor
胡耀明
汤历斌
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Chizhou Shanli Molecular Sieve Co Ltd
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Chizhou Shanli Molecular Sieve Co Ltd
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Priority to CN201711376950.4A priority Critical patent/CN107998822A/en
Publication of CN107998822A publication Critical patent/CN107998822A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B01D2256/245—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/108—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Of Gases By Adsorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention relates to a kind of method of Pressure Swing Adsorption methane, purifies the methane in unstripped gas using pressure-swing absorption apparatus, the pressure-swing absorption apparatus includes at least two adsorption tower, adsorbent is housed in the adsorption tower；The unstripped gas includes methane, nitrogen and other gases, and the wherein volumn concentration of methane is more than 50%, and the volumn concentration of nitrogen is less than 40%；Include the following steps：Each adsorption tower undergoes absorption phase, presses stage and desorption phase successively.The method of above-mentioned Pressure Swing Adsorption methane, purifies the methane in unstripped gas using pressure-swing absorption apparatus, by the way that unstripped gas is heated to 40 120 DEG C, can improve the adsorption efficiency of nitrogen, and can guarantee that certain adsorption capacity and separative efficiency.

Description

The method of Pressure Swing Adsorption methane
Technical field
The present invention relates to the purification technique field of admixture of gas, more particularly to a kind of Pressure Swing Adsorption methane Method.
Background technology
Carbon molecular sieve can be used in the separation of methane/nitrogen as adsorbent adsorbing and removing nitrogen.Carbon molecular sieve is speed Divergence type molecular sieve is spent, the different rate of adsorption carrys out separating-purifying gas over a molecular sieve by gas.Conventional pressure-variable adsorption The higher running temperature of device can reduce performance of the adsorbent, therefore would generally maintain unstrpped gas as far as possible in room temperature or low temperature.
Carbon molecular sieve absorption nitrogen performance is temperature dependent, variation of ambient temperature, and apparatus and process performance is unstable.Temperature is low When, carbon molecular sieve absorption nitrogen speed is low cannot to give full play to carbon molecular sieve performance, cause carbon molecular sieve dosage big, carbon molecular sieve Yield is not high, and equipment investment and use cost are high.
Therefore, the prior art could be improved.
The content of the invention
Based on this, the object of the present invention is to provide a kind of method of Pressure Swing Adsorption methane.
Specific technical solution is as follows：
A kind of method of Pressure Swing Adsorption methane, the methane in unstripped gas, the change are purified using pressure-swing absorption apparatus Pressure adsorbent equipment includes at least two adsorption tower, and adsorbent is housed in the adsorption tower；The unstripped gas include methane, nitrogen and The volumn concentration of other gases, wherein methane is more than 50%, and the volumn concentration of nitrogen is less than 40%；Including following step Suddenly：
Each adsorption tower undergoes absorption phase, presses stage and desorption phase successively：
(1) absorption phase：The unstripped gas is heated to 40-120 DEG C, the arrival end through the adsorption tower is passed through absorption Tower, the unstripped gas pass through the adsorbent, and the nitrogen in the unstripped gas is adsorbed by the adsorbent, and the adsorption tower goes out Mouth end discharge product gas；
(2) stage is pressed：After absorption phase, the adsorption tower is by the port of export with another in desorption phase Adsorption tower carries out equal press operation, makes the gas desorption being adsorbed in the adsorbent；
(3) desorption phase：After pressing, the stripping gas desorbed is discharged by the arrival end；
(4) repeat step (1)-(3), the unstripped gas continuously obtain high concentration after the adsorption tower adsorbing separation Product gas.
In wherein some embodiments, the adsorbent is carbon molecular sieve.
In wherein some embodiments, the pore diameter range of the carbon molecular sieve is 0.35-0.39.
In wherein some embodiments, the absorption phase, 40-80 DEG C is heated to by the unstripped gas.
In wherein some embodiments, the absorption phase, 60-70 DEG C is heated to by the unstripped gas.
In wherein some embodiments, the time of the absorption phase is 1.5-2.5min, pressure 0.4-2.0MPa.
In wherein some embodiments, the desorption phase is desorbed for normal pressure or vacuum desorption.
In wherein some embodiments, other described gases be selected from carbon monoxide, carbon dioxide, ethane, propane, hydrogen or One or more in oxygen.
In wherein some embodiments, the unstripped gas is selected from coal bed gas, oil gas or biogas.
The method of above-mentioned Pressure Swing Adsorption methane, using pressure-swing absorption apparatus purify unstripped gas in methane, pass through by Unstripped gas is heated to 40-120 DEG C, can improve the adsorption efficiency of nitrogen, and can guarantee that certain adsorption capacity and separative efficiency.
The adsorbent that above-mentioned pressure-swing absorption apparatus uses is speed type adsorbent (carbon molecular sieve), high in adsorption cycle Faster, methane/nitrogen separation is high for absorption nitrogen when warm, to methane purification advantageously.
The time of absorption phase can be dropped to less than 2.5min, nitrogen adsorption by above-mentioned method of purification from existing 4-6min Speed improves, and same treatment amount carbon molecular sieve usage amount reduces more than 30%, while raw material gas recovery rate at least improves 5-20%.
Brief description of the drawings
Fig. 1 is embodiment pressure-swing absorption apparatus schematic diagram.
Description of reference numerals：
101st, raw material gas storage tank；102nd, vacuum buffer tank；103rd, stripping gas surge tank；104th, finished product gas storage tank；105th, inhale Attached tower.
Embodiment
For the ease of understanding the present invention, the present invention will be described more fully below.But the present invention can be with perhaps More different form is realized, however it is not limited to embodiment described herein.On the contrary, the purpose for providing these embodiments is to make Understanding more thorough and comprehensive to the disclosure.
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention The normally understood implication of technical staff is identical.Term used in the description of the invention herein is intended merely to description tool The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases The arbitrary and all combination of the Listed Items of pass.
The method of the Pressure Swing Adsorption methane of the embodiment of the present invention mainly uses pressure-swing absorption apparatus from gas mixing Methane is purified in thing, the unstripped gas available for the present embodiment is as follows：
Component is mainly removed by the PSA of carbon molecular sieve packed bed
Pressure-swing absorption apparatus used by the present embodiment is as shown in Figure 1, including 4 adsorption towers 105, each adsorption tower enters Mouth end (bottom of towe) is equipped with three valves, connects respectively with raw material gas storage tank 101, stripping gas surge tank 103 and vacuum buffer tank 102 Connect, the port of export (tower top) of adsorption tower is equipped with 2 valves, one of them is connected with finished product gas storage tank 104, another valve is used for Press.Carbon molecular sieve (pore diameter range of carbon molecular sieve is 0.35~0.39nm) is filled with adsorption tower, the volume of adsorption tower is 15L*4, carbon molecular sieve amount of fill is 40kg in each adsorption tower.
Embodiment 1
The present embodiment is using methane volumetric content as 70%, and exemplified by nitrogen volume content is 30% unstripped gas, use is above-mentioned The method of pressure-swing absorption apparatus deduction methane, includes the following steps：
Each adsorption tower undergoes absorption phase, presses stage and desorption phase successively：
(1) absorption phase：The unstripped gas is heated to 65 DEG C, the arrival end through the adsorption tower is passed through adsorption tower, institute State unstripped gas and pass through the adsorbent, the nitrogen in the unstripped gas is adsorbed by the adsorbent, the port of export of the adsorption tower Discharge product gas；The absorption phase time is 1min；
(2) stage is pressed：After absorption phase, the adsorption tower is by the port of export with another in desorption phase Adsorption tower carries out equal press operation, makes the gas desorption being adsorbed in the adsorbent；
(3) desorption phase (normal pressure or vacuum)：After pressing, the stripping gas desorbed is arranged by the arrival end Go out；
(4) repeat step (1)-(3), the unstripped gas continuously obtain high concentration after the adsorption tower adsorbing separation Product gas.
The above method, the concentration of methane is 93% in the methane finished product gas of purification, and gas production is 1.7m per hour3。
Embodiment 2
The present embodiment is using methane volumetric content as 70%, and exemplified by nitrogen volume content is 30% unstripped gas, use is above-mentioned The method of pressure-swing absorption apparatus deduction methane, includes the following steps：
Each adsorption tower undergoes absorption phase, presses stage and desorption phase successively：
(1) absorption phase：The unstripped gas is heated to 40 DEG C, the arrival end through the adsorption tower is passed through adsorption tower, institute State unstripped gas and pass through the adsorbent, the nitrogen in the unstripped gas is adsorbed by the adsorbent, the port of export of the adsorption tower Discharge product gas；The absorption phase time is 2min；
(2) stage is pressed：After absorption phase, the adsorption tower is by the port of export with another in vacuum stages Adsorption tower carries out equal press operation, makes the gas desorption being adsorbed in the adsorbent；
(3) desorption phase：After pressing, the stripping gas desorbed is discharged by the arrival end；
(4) repeat step (1)-(3), the unstripped gas continuously obtain high concentration after the adsorption tower adsorbing separation Product gas.
The above method, the concentration of methane is 93% in the methane finished product gas of purification, and gas production is 1.3m per hour3。
Embodiment 3
Using rubbish landfill gas, (methane volumetric content as 70%, nitrogen volume content is exemplified by 30%), uses to the present embodiment The method of above-mentioned pressure-swing absorption apparatus deduction methane, includes the following steps：
Each adsorption tower undergoes absorption phase, presses stage and desorption phase successively：
(1) absorption phase：The unstripped gas is heated to 100 DEG C, the arrival end through the adsorption tower is passed through adsorption tower, institute State unstripped gas and pass through the adsorbent, the nitrogen in the unstripped gas is adsorbed by the adsorbent, the port of export of the adsorption tower Discharge product gas；The absorption phase time is 30s；
(2) stage is pressed：After absorption phase, the adsorption tower is by the port of export with another in vacuum stages Adsorption tower carries out equal press operation, makes the gas desorption being adsorbed in the adsorbent；
(3) desorption phase：After pressing, the stripping gas desorbed is discharged by the arrival end；
(4) repeat step (1)-(3), the unstripped gas continuously obtain high concentration after the adsorption tower adsorbing separation Product gas.
The above method, the concentration of methane is 93% in the methane finished product gas of purification, and gas production is 1.9m per hour3.Contrast Example 1
The present embodiment is using methane volumetric content as 70%, and exemplified by nitrogen volume content is 30% unstripped gas, use is above-mentioned The method of pressure-swing absorption apparatus deduction methane, includes the following steps：
Each adsorption tower undergoes absorption phase, presses stage and desorption phase successively：
(1) absorption phase：The arrival end of the unstripped gas (25 DEG C of room temperature) through the adsorption tower is passed through adsorption tower, it is described Unstripped gas passes through the adsorbent, and the nitrogen in the unstripped gas is adsorbed by the adsorbent, the port of export row of the adsorption tower Go out product gas；The absorption phase time is 4min；
(2) stage is pressed：After absorption phase, the adsorption tower is by the port of export with another in vacuum stages Adsorption tower carries out equal press operation, makes the gas desorption being adsorbed in the adsorbent；
(3) desorption phase：After pressing, the stripping gas desorbed is discharged by the arrival end；
(4) repeat step (1)-(3), the unstripped gas continuously obtain high concentration after the adsorption tower adsorbing separation Product gas.
The above method, the concentration of methane is 93% in the methane finished product gas of purification, and gas production is 1.0m per hour3。
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, its description is more specific and detailed, but simultaneously Cannot therefore it be construed as limiting the scope of the patent.It should be pointed out that come for those of ordinary skill in the art Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (9)

  1. A kind of 1. method of Pressure Swing Adsorption methane, it is characterised in that the first in unstripped gas is purified using pressure-swing absorption apparatus Alkane, the pressure-swing absorption apparatus include at least two adsorption tower, adsorbent are housed in the adsorption tower；The unstripped gas includes first Alkane, nitrogen and other gases, the wherein volumn concentration of methane are more than 50%, the volumn concentration of nitrogen be less than 40%；Include the following steps：
    Each adsorption tower undergoes absorption phase, presses stage and desorption phase successively：
    (1) absorption phase：The unstripped gas is heated to 40-120 DEG C, the arrival end through the adsorption tower is passed through adsorption tower, institute State unstripped gas and pass through the adsorbent, the nitrogen in the unstripped gas is adsorbed by the adsorbent, the port of export of the adsorption tower Discharge product gas；
    (2) stage is pressed：After absorption phase, which passes through the port of export and another absorption in desorption phase Tower carries out equal press operation, makes the gas desorption being adsorbed in the adsorbent；
    (3) desorption phase：After pressing, the stripping gas desorbed is discharged by the arrival end；
    (4) repeat step (1)-(3), the unstripped gas continuously obtain the production of high concentration after the adsorption tower adsorbing separation Product gas.
  2. 2. the method for Pressure Swing Adsorption methane according to claim 1, it is characterised in that the adsorbent is carbon molecules Sieve.
  3. 3. the method for Pressure Swing Adsorption methane according to claim 2, it is characterised in that the aperture of the carbon molecular sieve Scope is 0.35-0.39nm.
  4. 4. the method for Pressure Swing Adsorption methane according to claim 1, it is characterised in that the absorption phase, by institute State unstripped gas and be heated to 40-80 DEG C.
  5. 5. the method for Pressure Swing Adsorption methane according to claim 1, it is characterised in that the absorption phase, by institute State unstripped gas and be heated to 60-70 DEG C.
  6. 6. the method for Pressure Swing Adsorption methane according to claim 1, it is characterised in that the time of the absorption phase Less than 2.5min, pressure 0.4-2.0MPa.
  7. 7. according to the method for claim 1-6 any one of them Pressure Swing Adsorption methane, it is characterised in that the desorption rank Section is normal pressure desorption or vacuum desorption.
  8. 8. according to the method for claim 1-6 any one of them Pressure Swing Adsorption methane, it is characterised in that other described gas One or more of the body in carbon monoxide, carbon dioxide, ethane, propane, hydrogen or oxygen.
  9. 9. according to the method for claim 1-6 any one of them Pressure Swing Adsorption methane, it is characterised in that the unstripped gas Selected from coal bed gas, oil gas, rubbish landfill gas or aerobic fermentation gas.
CN201711376950.4A 2017-12-19 2017-12-19 The method of Pressure Swing Adsorption methane Pending CN107998822A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110773125A (en) * 2019-11-08 2020-02-11 四川大学 Organic modified molecular sieve and preparation method and application thereof
CN112516748A (en) * 2020-11-10 2021-03-19 华南理工大学 Liquid carbon dioxide spray type pressure-variable temperature-control adsorption tower

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101628198A (en) * 2009-08-26 2010-01-20 同济大学 Pressure-swing adsorption method of directly enriching methane from coal bed gas

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101628198A (en) * 2009-08-26 2010-01-20 同济大学 Pressure-swing adsorption method of directly enriching methane from coal bed gas

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110773125A (en) * 2019-11-08 2020-02-11 四川大学 Organic modified molecular sieve and preparation method and application thereof
CN110773125B (en) * 2019-11-08 2021-06-04 四川大学 Organic modified molecular sieve and preparation method and application thereof
CN112516748A (en) * 2020-11-10 2021-03-19 华南理工大学 Liquid carbon dioxide spray type pressure-variable temperature-control adsorption tower
CN112516748B (en) * 2020-11-10 2021-10-26 华南理工大学 Liquid carbon dioxide spray type pressure-variable temperature-control adsorption tower

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