CN1891328B - Low concentration adsorbable constituent variable-pressure adsorption and separation method - Google Patents

Low concentration adsorbable constituent variable-pressure adsorption and separation method Download PDF

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Publication number
CN1891328B
CN1891328B CN200610078714XA CN200610078714A CN1891328B CN 1891328 B CN1891328 B CN 1891328B CN 200610078714X A CN200610078714X A CN 200610078714XA CN 200610078714 A CN200610078714 A CN 200610078714A CN 1891328 B CN1891328 B CN 1891328B
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gas
concentration
adsorption
available
raw material
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CN1891328A (en
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杨皓
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals

Abstract

This invention discloses a method for concentrating a gas component with a low concentration which is easy to adsorb, and a method using serial adsorption. A mixture gas containing the easy adsorption components as effective gas components with the concentration of 4-20% is used as a raw material gas. The easy adsorption components include one or more of carbon dioxide, carbon monoxide, methane, ethane, propane, butane, ethylene, acetylene, nitrogen, oxygen, argon gas, helium gas and sulphur dioxide. The raw material gas includes flue gas, grate gas, carbon C low pressure flash gas, cracking gas discharging gas, and the discharging gas containing the above absorption components. The method for concentrating the effective gas concentration is characterized by using a pressure swing adsorption gas separation process and comprising the following steps: the raw material gas pressure being 0.02-0.4 MPa, using a multi-state pressure swing adsorption process to concentrate the effective gas: reducing the gas effective concentration to 40-70% of the raw material concentration at an adsorption outlet in the first stage; reducing the gas effective concentration to 40-70% 2 of the raw material concentration 1 at the adsorption outlet in the second stage; reducing the gas effective concentration to 40-70% 3 of the raw material concentration at the adsorption outlet in the third stage; and the like, according to the recovery requirement, at least using two stages, and at most using five stages; using pumpout gas at the stage or next stage as a substitution gas to replace an adsorption tower, thereby improving the effective gas concentration in the pumpout gas; using the pumpout gas at the stage as the raw material gas of the last stage or the more last stage; the effective gas concentration of the first stage pumpout gas capable of being 150-500 % of the effective concentration of the raw material gas.

Description

A kind of low concentration adsorbable contituent variable-pressure adsorption and separation method
One, technical field
The present invention relates to the gas separation field, is a kind of method of using part component in the pressure swing adsorption separating gas mixture.
Two, background technology
For the technology of flue gas recovery carbon dioxide component, the method for usually using is hydrometallurgic recovery.Owing to need huge equipment and more operation energy consumption, therefore, often have to utilize other carbonated gases to replace flue gas, need investment much to be used for constructing device equally.
For the technology of cracking gas recovery ethylene component, the method for usually using is that alternating temperature absorption is reclaimed.Since need huge equipment and more operation energy consumption, therefore, many users, directly the ethene waste gas that contains with low concentration, low-pressure directly burns, and has reduced the value of ethene in the cracking gas.
Use light concentration gas as industrial chemicals, general because the active ingredient branch forces down, and the reaction motive force is little, is unfavorable for the raising of utilization rate of equipment and installations, therefore, must be by improving gas concentration or improving gas pressure and realize that the active ingredient dividing potential drop improves.The light concentration gas compression certainly will consume a large amount of idle works, therefore, improves gas concentration, becomes a valid approach.
Pressure swing adsorption is used to put forward the concentration carbon dioxide technology all has application in a lot of environments for use, and still, unstripped gas concentration is generally all more than 20%.This is owing to carbon dioxide in the unstripped gas is low excessively, if unstripped gas is brought up to very high pressure, certainly will waste the very high energy.Therefore the recycling of low concentration of carbon dioxide 4~15% is considered to a kind of uneconomic behavior always.
Three, summary of the invention
A kind ofly contain easy absorbed component and be called unstripped gas as the gaseous mixture of available gas constituent concentration 4~20%, easily absorbed component comprises carbon dioxide, carbon monoxide, methane, ethane, propane, butane, ethene, acetylene, nitrogen, oxygen, argon gas, helium, sulfur dioxide, in the hydrogen sulfide one or more, unstripped gas comprises flue gas, stove gas, the carbon third low pressure flash gas, cracking gas is dropped a hint, and other contains above-mentioned easy absorbed component and drops a hint, in order to reclaim low concentration available gas composition, the present invention utilizes the strategy of plural serial stage absorption, is used for improving gas reclaiming rate.
In order to reduce energy consumption, can use lower adsorptive pressure.Before using pressure swing absorption process recovery low concentration available gas, must guarantee raw gas pressure 0.02~0.4MPa (table), through preliminary treatment, remove the component that boiling point is higher than available gas.
To contain low concentration available gas gaseous mixture and under lower pressure 0.02~0.4MPa, send into adsorption tower, in first order adsorption tower, it is attached that available gas is adsorbed agent, and the first order absorption effluent gases lower than unstripped gas available gas concentration directly sent into second level adsorption tower; In the adsorption tower of the second level, available gas is adsorbed agent absorption, and directly sends into third level adsorption tower than the lower second level absorption effluent gases of first order absorption effluent gases available gas concentration; In third level adsorption tower, available gas is adsorbed agent absorption, and directly sends into fourth stage adsorption tower than the lower third level absorption effluent gases of second level absorption effluent gases available gas concentration; The rest may be inferred, can be according to the requirement of the rate of recovery, and adsorption tower progression is secondary at least, can reach Pyatyi at most.
The utilization desorb adsorption tower of finding time.
Use the corresponding levels or next stage the reflux non-available gas gas of displacement adsorption tower dead space of stripping gas of finding time, improve the adsorption tower available gas concentration in the stripping gas of finding time thus.
Next stage can be found time gas as upper level or more the unstripped gas of upper level be mixed into adsorption tower.
Like this, the gas available gas concentration of finding time of the first order can reach 150~500% of unstripped gas available gas concentration.
The pressure swing adsorption technique that the present invention is alleged can be that 2~12 adsorption towers are formed each level.
Four, the specific embodiment
Embodiment 1: certain flue gas available gas gas concentration lwevel 6% needs to improve more than the gas concentration lwevel to 14%.
(1) be 0.12MPa (table) through being compressed to pressure,, remove the low-boiling composition of ratio available gas in the unstripped gas through preliminary clearning, such as, sulfur dioxide, hydrogen sulfide, coal tar, benzene and derivative thereof, or the like; (2) use three grades of pressure-changed adsorption concentrating technologies: first order imported raw material gas available gas concentration 6%, first order adsorption tower effluent gases available gas concentration 4.2%, first order exhaust available gas concentration 15%; Second level imported raw material gas is first order adsorption tower effluent gases, available gas concentration 4.2%, and second level adsorption tower effluent gases available gas concentration 3.0%, second level exhaust available gas concentration 10% is returned the first order as displacement gas; Third level imported raw material gas is second level adsorption tower effluent gases, available gas concentration 3.0%, and third level adsorption tower effluent gases available gas concentration 2.0%, third level exhaust available gas concentration 6% is returned the first order as unstripped gas.
As product gas, available gas concentration reaches about 15% by first order exhaust extension.
Embodiment 2: certain flue gas available gas concentration 12% needs to improve more than the concentration to 35%.
(1) be 0.15MPa (table) through being compressed to pressure,, remove the low-boiling composition of ratio available gas in the unstripped gas through preliminary clearning, such as, sulfur dioxide, hydrogen sulfide, coal tar, benzene and derivative thereof, or the like; (2) use level Four pressure-changed adsorption concentrating technology: first order imported raw material gas available gas concentration 12%, first order adsorption tower effluent gases available gas concentration 8.4%, first order exhaust available gas concentration 35%; Second level imported raw material gas is first order adsorption tower effluent gases, available gas concentration 8.4%, and second level adsorption tower effluent gases available gas concentration 6.0%, second level exhaust available gas concentration 16% is returned the first order as displacement gas; Third level imported raw material gas is second level adsorption tower effluent gases, available gas concentration 6.0%, and third level adsorption tower effluent gases available gas concentration 4.4%, third level exhaust available gas concentration 12% is returned the first order as unstripped gas; Fourth stage imported raw material gas is third level adsorption tower effluent gases, available gas concentration 4.4%, and fourth stage adsorption tower effluent gases available gas concentration 3.2%, third level exhaust available gas concentration 8% is returned the second level as unstripped gas.
As product gas, available gas concentration reaches about 35% by first order exhaust extension.
Embodiment 3: certain stove gas carbon monoxide gas concentration 8% needs to improve more than the concentration to 50%.
(1) be 0.05MPa (table) through being compressed to pressure,, remove the low-boiling composition of ratio available gas in the unstripped gas through preliminary clearning, such as, carbon dioxide, sulfur dioxide, hydrogen sulfide, coal tar, benzene and derivative thereof, or the like; (2) use secondary pressure-changed adsorption concentrating technology: first order imported raw material gas available gas concentration 8%, first order adsorption tower effluent gases available gas concentration 6%, first order exhaust available gas concentration 51%; Second level imported raw material gas is first order adsorption tower effluent gases, available gas concentration 6%, and second level adsorption tower effluent gases available gas concentration 4.4%, second level exhaust available gas concentration 15% is returned the first order as displacement gas.
As product gas, available gas concentration reaches about 51% by first order exhaust extension.
Embodiment 4: certain cracking ethylene gas concentration 4% of dropping a hint needs to improve more than the concentration to 88%.
(1) pressure of this gas own is 0.15MPa (table), through preliminary clearning, removes the low-boiling composition of ratio available gas in the unstripped gas, such as, senior rare hydrocarbon or the like; (2) use secondary pressure-changed adsorption concentrating technology: first order imported raw material gas available gas concentration 4%, first order adsorption tower effluent gases available gas concentration 3%, first order exhaust available gas concentration 20%; Second level imported raw material gas is first order adsorption tower effluent gases, available gas concentration 3%, and second level adsorption tower effluent gases available gas concentration 2%, second level exhaust available gas concentration 10% is returned the first order as displacement gas.
As intermediate products gas, available gas concentration reaches about 18% by first order exhaust extension.
Use for the second time this patent, continue to improve ethylene concentration to qualified 88%.
(1) improving the intermediate products gas pressure is 0.35MPa (table); (2) use secondary pressure-changed adsorption concentrating technology: first order imported raw material gas available gas concentration 20%, first order adsorption tower effluent gases available gas concentration 8%, first order exhaust available gas concentration 88%; Second level imported raw material gas is first order adsorption tower effluent gases, available gas concentration 8%, and second level adsorption tower effluent gases available gas concentration 4%, second level exhaust available gas concentration 44% is returned the first order as displacement gas.
Absorption effluent gases in the second level is as the first order unstripped gas that uses for the first time patent device.
As intermediate products gas, available gas concentration reaches 88% by first order exhaust extension.
This patent reclaims carbon monoxide through actual the use at flue gas recovery carbon dioxide, cracking gas recovery ethene, synthetic ammonia copper gas washing, and effect is fairly obvious, effectively reduces the energy consumption in the gas removal process, has saved cost.

Claims (1)

1. low concentration adsorbable contituent variable-pressure adsorption and separation method, it is characterized in that this method adopts the gaseous mixture of available gas constituent concentration 4~20% to be called unstripped gas, described available gas composition is easy absorbed component, easily absorbed component is a carbon dioxide, carbon monoxide, methane, ethane, propane, butane, ethene, acetylene, nitrogen, oxygen, argon gas, helium, sulfur dioxide, in the hydrogen sulfide one or more, unstripped gas is a flue gas, stove gas, the carbon third low pressure flash gas, cracking gas is dropped a hint or other contains above-mentioned easy absorbed component and drops a hint, this method is used adsorption gas separating technology, and the following step of process: (1) raw gas pressure 0.02~0.4MPa; Use the stage variable pressure absorbing process to carry dense available gas: the first order, absorption exit gas available gas concentration is reduced to 40~70% of unstripped gas concentration; The second level, absorption exit gas available gas concentration is reduced to (40~70%) of unstripped gas concentration 2The third level, absorption exit gas available gas concentration is reduced to (40~70%) of unstripped gas concentration 3The rest may be inferred, and according to rate of recovery needs, minimum use secondary can only use Pyatyi at most; (2) gas of finding time that uses the corresponding levels or next stage is replaced adsorption tower as substitution gas, improves the available gas concentration in the gas of finding time thus; (3) with the gas of finding time of the corresponding levels as the upper level or the unstripped gas of upper level more; (4) the find time available gas concentration of gas of the first order reaches 150~500% of unstripped gas available gas concentration.
CN200610078714XA 2006-05-10 2006-05-10 Low concentration adsorbable constituent variable-pressure adsorption and separation method Expired - Fee Related CN1891328B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101503335A (en) * 2009-02-17 2009-08-12 杨皓 Method for concentrating methane by gas pressure swing adsorption of low concentration methane
CN104415643A (en) * 2013-08-20 2015-03-18 中国石油化工股份有限公司 Method for selectively removing H2S from gas flow containing CO2
CN108392948A (en) * 2018-03-21 2018-08-14 山东京博石油化工有限公司 A kind of purifying technique and device of hydrogen sulfide
CN108545697A (en) * 2018-04-27 2018-09-18 杨皓 A kind of Water gas shift/WGS gas manufacture ammonia synthesis gas technique
CN111140862A (en) * 2019-12-27 2020-05-12 安徽海德化工科技有限公司 High-purity n-butane production device
CN113735079B (en) * 2020-12-31 2023-10-27 李保军 Method and production device for extracting ultra-high purity helium at normal temperature

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1069708A (en) * 1991-08-24 1993-03-10 化学工业部西南化工研究院 From ammonia factory conversion gas, remove the pressure swing adsorption technique of carbonic acid gas
CN1071851A (en) * 1992-12-03 1993-05-12 黄家鹄 Produce the gas separation method by pressure swing adsorption of two kinds of high-purities and high yield product gas simultaneously
US5409684A (en) * 1992-06-10 1995-04-25 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process and installation for the combined production of synthetic ammonia and pure hydrogen
CN1215626A (en) * 1997-10-24 1999-05-05 化学工业部西南化工研究设计院 Pressure swing adsorption process for separating carbon monooxide from carbon monooxide contg. mixed gas
CN1344580A (en) * 2000-09-29 2002-04-17 陈胜飞 Pressure swing adsorption method and apparatus for separating gases
CN1347747A (en) * 2001-07-31 2002-05-08 成都天立化工科技有限公司 Two-sectional variable pressure adsorption and decarbonizing process of recovering hydrogen and nitrogen gas for urea production

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1069708A (en) * 1991-08-24 1993-03-10 化学工业部西南化工研究院 From ammonia factory conversion gas, remove the pressure swing adsorption technique of carbonic acid gas
US5409684A (en) * 1992-06-10 1995-04-25 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process and installation for the combined production of synthetic ammonia and pure hydrogen
CN1071851A (en) * 1992-12-03 1993-05-12 黄家鹄 Produce the gas separation method by pressure swing adsorption of two kinds of high-purities and high yield product gas simultaneously
CN1215626A (en) * 1997-10-24 1999-05-05 化学工业部西南化工研究设计院 Pressure swing adsorption process for separating carbon monooxide from carbon monooxide contg. mixed gas
CN1344580A (en) * 2000-09-29 2002-04-17 陈胜飞 Pressure swing adsorption method and apparatus for separating gases
CN1347747A (en) * 2001-07-31 2002-05-08 成都天立化工科技有限公司 Two-sectional variable pressure adsorption and decarbonizing process of recovering hydrogen and nitrogen gas for urea production

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