CN1300635A - Process for removing CO2 and H2S from biological gas - Google Patents

Process for removing CO2 and H2S from biological gas Download PDF

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Publication number
CN1300635A
CN1300635A CN00134330A CN00134330A CN1300635A CN 1300635 A CN1300635 A CN 1300635A CN 00134330 A CN00134330 A CN 00134330A CN 00134330 A CN00134330 A CN 00134330A CN 1300635 A CN1300635 A CN 1300635A
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absorption tower
biogas
desorber
gas
absorption
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CN00134330A
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CN1137753C (en
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计中坚
郑义
何平
刘洪�
孟祥荣
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Anshan General Design Inst Of Coking Refractory Materials Chinese Metallurgica
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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
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/40Capture or disposal of greenhouse gases of CO2

Abstract

A purified process for removing CD2 and H2S from biologic gas includes such steps as countercurrent contacting between the biologic gas and regenerated poor liquid in absorption tower, absorbing CO2 and H2S by poor liquid to purity said biologic gas and making poor liquid become rich liquid, delivering said rich liquid to desorption tower, heating it by boiler to release CO2 and H2S, exhausting them from tower top, discharging the regenerated poor liquid from tower bottom, and returning the absorption tower for cyclic use of the poor liquid. Its advantages are high absorption performance and purifying effect, less corrosion, low cost and less energy consumption.

Description

CO in the biogas 2, H 2The process for purifying of S
The present invention relates to CO in the biogas that anaerobic processes such as garbage loading embeading biogas (LFG) and sewage, mud, ight soil, straw produce 2, H 2The process for purifying of S.
At present, for CO in the biogas such as landfill biogas 2, H 2The purification of S abroad has and adopts embrane method to separate.Membrane separation process is under certain pressure condition, utilizes variety classes gas to have different infiltration rates to realize the purpose of its separation in the organic polymer film.For biogas, N wherein 2, CH 4Be difficult for infiltration, and CO 2, H 2Easily infiltration, thus realize CH 4With CO 2Separation.The advantage of this technology is: take up an area of and lack, shutting down is easy; Be not subjected to contain in the unstripped gas O 2The influence of amount, and remove CO 2In time, also dewater.But also there is following shortcoming in this technology: a) strict to the preliminary treatment of biogas, otherwise film is easy to be polluted and lost efficacy; B) service life of film limited, the renewal cost costliness of film makes production cost improve; C) film separates needs to carry out under elevated pressures, and needs the multistage pressurization, makes capital construction and operating cost improve; D) film separates CH 4The rate of recovery lower, only 70%.There is employing MEA (MEA) solution to be used for the CO that takes off of biogas as absorbent both at home and abroad 2Process for purifying is though this technology can be removed CO in the biogas effectively 2, H 2S, but this technology has following weak point: the one, the MEA solvent-oil ratio is big, purifies the cost height; The 2nd, absorption liquid has certain corrosivity, so process equipment need be used resistant material, technology investment is increased considerably.Still there is not to adopt the polyamines absorption liquid that contains absorbent MDEA (N methyl glycol amine) to be used for biogas CO both at home and abroad 2, H 2The absorption cleaning technology of S.
In view of the problems referred to above that exist, the purpose of this invention is to provide polyamines solution that a kind of employing contains absorbent MDEA and be CO in the biogas of absorption liquid 2, H 2The physical-chemical process for purifying of S makes effective ingredient CH in the biogas 4Can access more efficiently utilization, it is low to reach its investment and operating cost, CH 4The high purpose of the rate of recovery.
For realizing purpose of the present invention, take following technical measures:
CO in the biogas 2, H 2The process for purifying of S comprises absorption tower 1, desorber 8, reboiler 10, heat exchanger 5, cooler 2,3,6, separator 4,7, rich solution medial launder 13, absorbent storage tank 9, pump 11,12 etc.
1 bottom enters the absorption tower to biogas from the absorption tower, enters the absorption tower by the regeneration lean solution of desorber 8 from top, absorption tower, biogas and regeneration lean solution counter current contacting, CO in the biogas in the absorption tower 2, H 2Impurity such as S are absorbed by liquid absorption; Purified gas comes out from the top, absorption tower, and through cooler 3 coolings, separator 4 separates, and separating back gas becomes purified product gas, and condensate stream is to rich solution medial launder 13; Absorb CO 2, H 2Rich solution behind the impurity such as S comes out from the bottom, absorption tower, enters rich solution medial launder 13, comes out to enter heat exchanger 5 through pump 12 pressurizations from the rich solution medial launder, comes the lean solution heat exchange with desorber in heat exchanger, enters desorber 8 tops after heat exchanger comes out, and sprays into desorber; At the bottom of the tower of desorber, adopt reboiler 10 heating, make the CO in the rich solution 2Deng the impurity desorb, (contain CO from the cat head discharge 2, H 2S tail gas), contain CO 2Tail gas separate the back discharging or recycle through cooler 6 cooling, separator 7, the condensate stream of separation arrives rich solution medial launder 13; Regeneration lean solution after the desorb is come out from desorber 8 bottoms, and through pump 11 pressurizations, the rich solution heat exchange that enters heat exchanger 5 and absorption tower enters condenser 2 coolings again, enters the absorption tower from top, absorption tower again and recycles; Absorbent MDEA by absorbent storage tank 9 sends into pump 11.
Above-mentioned CO 2, H 2The absorption of S can be carried out in normal pressure or compression system.
Above-mentioned regeneration lean solution concentration is the polyamines aqueous solution that contains MDEA30%~50%.
Absorb 55 ℃~90 ℃ of temperature in the above-mentioned absorption tower, gas liquid ratio 40~60 under the normal pressure: 1, and pressurization gas liquid ratio down can reach 100~160: 1.
Desorption temperature is 90 ℃~110 ℃ in the above-mentioned desorber.
The polyamines solution that this process using contains absorbent MDEA is made absorption liquid, is a kind of chemical absorbent with Physical Absorption performance, can effectively remove CO in the biogas 2, H 2Impurity such as S reach the purpose of effective purification.The major advantage of this method is: a) have Physical Absorption and chemical absorbing characteristic concurrently, CO 2Solubility is big therein; B) have a narrow range of temperature between absorption and the regeneration, absorption reaction heat is less, and side reaction is few, and the regeneration hear rate is little; C) stability of solution is good, is difficult for degraded, so solvent-oil ratio is few; D) solution corrosion is little, and equipment can be selected carbon steel for use; E) absorption liquid concentration is higher, so the solution internal circulating load is little, and energy consumption is low; F) absorption liquid steam forces down, and the solvent evaporates loss is few; G) degree of purification height, CO in the purified gas 2Content≤2% (normal pressure absorption) add depress can<0.2%, so this method has small investment, operating cost is low, the characteristics of less energy consumption.
Introduce technology contents of the present invention in detail below in conjunction with drawings and Examples.
Fig. 1 is CO in the biogas 2, H 2S process for purifying flow chart.
Among the figure, CO in the biogas 2, H 2The process for purifying of S comprises absorption tower 1, desorber 8, reboiler 10, heat exchanger 5, cooler 2,3,6, separator 4,7, rich solution medial launder 13, absorbent storage tank 9, pump 11,12 etc.
1 bottom enters the absorption tower to the biogas that transports through air blast from refuse landfill from the absorption tower, column bottom temperature~90 ℃, regeneration lean solution by desorber 8 enters the absorption tower from top, absorption tower, 55 ℃~60 ℃ of tower top temperatures, regeneration lean solution concentration is the polyamines aqueous solution that contains MDEA30%~50%, biogas and regeneration lean solution counter current contacting, CO in the biogas in the absorption tower 2, H 2Impurity such as S are absorbed by liquid absorption, and absorb 55 ℃~90 ℃ of temperature, gas liquid ratio 40~60: 1; Purified gas comes out from the top, absorption tower, and through cooler 3 coolings, separator 4 separates, and separating back gas becomes purified product gas, purified gas CH 4Content>80%, CO 2Content<2%, H 2S<20mg/m 3, CH 4The rate of recovery>95% purifies artifact gas and can be applicable to do motor vehicle fuel (pressurization) or make high quality gas fuel.Condensate stream is to rich solution medial launder 13; Absorb CO 2, H 2Rich solution behind the impurity such as S comes out from the bottom, absorption tower, enters rich solution medial launder 13, comes out to enter heat exchanger 5 through pump 12 pressurizations from the rich solution medial launder, comes the lean solution heat exchange with desorber in heat exchanger, enters desorber 8 tops after heat exchanger comes out, and sprays into desorber; Tower top temperature~90 ℃, column bottom temperature~110 ℃, 90 ℃~110 ℃ of desorption temperatures adopt reboiler 10 heating at the bottom of the tower of desorber, make the CO in the rich solution 2Deng the impurity desorb, (contain CO from the cat head discharge 2, H 2S tail gas), contain CO 2Tail gas separate the back discharging or recycle through cooler 6 cooling, separator 7, the condensate stream of separation arrives rich solution medial launder 13; Regeneration lean solution after the desorb is come out from desorber 8 bottoms, and through pump 11 pressurizations, the rich solution heat exchange that enters heat exchanger 5 and absorption tower enters condenser 2 coolings again, enters the absorption tower from top, absorption tower again and recycles; Absorbent MDEA by absorbent storage tank 9 sends into pump 11.
Embodiment one
Handle unstripped gas (LFG) amount 10,000 m 3/ d, unstripped gas form (%) and are: CH 450%~55%; CO 235%~45%; O 21~2.Absorption liquid concentration 30%~50%; Gas (unstripped gas) liquor ratio 50: 1.Purified gas CH 4Content>80%, CO 2Content<2%, H 2S<20mg/m 3, CH 4The rate of recovery>95%.
The absorption tower: tower top temperature~60 ℃, column bottom temperature~90 ℃, normal pressure absorbs (P=0.12Mpa absolute pressure) down;
Desorber: tower top temperature~90 ℃, column bottom temperature~110 ℃.
Embodiment two
Handle unstripped gas (LFG) amount 15000m 3/ d, unstripped gas form (%) and are: CH 450%~55%; CO 235%~45%; O 21~2.Absorption liquid concentration 30%~50%; Gas (unstripped gas) liquor ratio 150: 1.Purified gas CH 4Content>80%, CO 2Content<1%, H 2S<20mg/m 3, CH 4The rate of recovery>95%.
The absorption tower: tower top temperature~60 ℃, column bottom temperature~90 ℃ add and depress absorption (P=1.5Mpa absolute pressure);
Desorber: tower top temperature~90 ℃, column bottom temperature~110 ℃.

Claims (5)

1. CO in the biogas 2, H 2The process for purifying of S, it is characterized in that: comprise absorption tower (1), desorber (8), reboiler (10), heat exchanger (5), cooler (2), (3), (6), separator (4), (7), rich solution medial launder (13), absorbent storage tank (9), pump (11), (12) etc., (1) bottom enters the absorption tower to biogas from the absorption tower, the regeneration lean solution of being come by desorber (8) enters the absorption tower from top, absorption tower, biogas and regeneration lean solution counter current contacting, CO in the biogas in the absorption tower 2, H 2Impurity such as S are absorbed by liquid absorption; Purified gas comes out from the top, absorption tower, and through cooler (3) cooling, separator (4) separates, and separating back gas becomes purified product gas, and condensate stream is to rich solution medial launder (13); Absorb CO 2, H 2Rich solution behind the impurity such as S comes out from the bottom, absorption tower, enter rich solution medial launder (13), come out to enter heat exchanger (5), in heat exchanger, come the lean solution heat exchange with desorber through pump (12) pressurization from the rich solution medial launder, after heat exchanger comes out, enter desorber (8) top, spray into desorber; At the bottom of the tower of desorber, adopt reboiler (10) heating, make the impurity desorbs such as CO2 in the rich solution, discharge, contain CO from cat head 2Tail gas separate the back discharging or recycle through cooler (6) cooling, separator (7), the condensate stream of separation arrives rich solution medial launder (13); Regeneration lean solution after the desorb is come out from desorber (8) bottom, and through pump (11) pressurization, the rich solution heat exchange that enters heat exchanger (5) and absorption tower enters condenser (2) cooling again, and (1) top enters the absorption tower and recycles from the absorption tower again; The absorbent MDEA that is come by absorbent storage tank (9) sends into pump (11).
2. CO in the biogas according to claim 1 2, H 2The process for purifying of S is characterized in that: the interior CO in absorption tower (1) 2, H 2The absorption of S can be carried out in normal pressure or compression system.
3. CO in the biogas according to claim 1 2, H 2The process for purifying of S is characterized in that: regeneration lean solution concentration is the polyamines aqueous solution that contains MDEA30%~50%.
4. CO in the biogas according to claim 1 2, H 2The process for purifying of S is characterized in that: absorb 55 ℃~90 ℃ of temperature in absorption tower (1), gas liquid ratio 40~60 under the normal pressure: 1, and pressurization gas liquid ratio down can reach 100~160: 1.
5. CO in the biogas according to claim 1 2, H 2The process for purifying of S is characterized in that: 90 ℃~110 ℃ of the interior desorption temperatures of desorber (8).
CNB001343300A 2000-12-19 2000-12-19 Process for removing CO2 and H2S from biological gas Expired - Lifetime CN1137753C (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101856579A (en) * 2010-06-02 2010-10-13 清华大学 Novel energy-saving CO2 trapping process of improved potassium carbonate
CN101108988B (en) * 2007-08-10 2011-03-23 辽宁凯田再生能源环保有限公司 Biogas cleaning equipment and purifying technique thereof
CN102059037A (en) * 2010-11-22 2011-05-18 重庆欣雨压力容器制造有限责任公司 Process for purifying carbon dioxide from tail gas of natural gas
CN101612512B (en) * 2008-06-25 2011-05-25 苏庆泉 Carbon dioxide separating system and separating method
CN102242059A (en) * 2011-04-25 2011-11-16 青岛天人环境股份有限公司 Device and method for preparing automobile fuel gas by utilizing organic wastes
CN101659889B (en) * 2008-08-25 2012-09-26 来铁路 Methane purifying comprehensive utilization technology
CN102802766A (en) * 2009-06-19 2012-11-28 国际壳牌研究有限公司 Process For The Removal Of Carbon Dioxide And/or Hydrogen Sulphide From A Gas
CN102933284A (en) * 2010-04-20 2013-02-13 巴布考克日立株式会社 Exhaust gas treatment system provided with carbon dioxide chemisorption equipment
CN103113945A (en) * 2013-02-01 2013-05-22 王仕华 Marsh gas purification system and marsh gas purification method
CN106318500A (en) * 2015-07-06 2017-01-11 中国石油化工股份有限公司 Biological purifying process of unconventional gas
CN106669365A (en) * 2016-12-15 2017-05-17 西安交通大学 Thermal-electric co-driven CO2 capturing system adopting amine method
CN108348841A (en) * 2015-08-28 2018-07-31 能源科技创新有限责任公司 Method and apparatus for handling biogas
CN111013333A (en) * 2019-12-24 2020-04-17 中国纺织科学研究院有限公司 Method for treating hydrogen sulfide in waste gas generated in viscose fiber production
CN111372671A (en) * 2017-11-30 2020-07-03 株式会社神户制钢所 Gas processing method and gas processing apparatus

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101108988B (en) * 2007-08-10 2011-03-23 辽宁凯田再生能源环保有限公司 Biogas cleaning equipment and purifying technique thereof
CN101612512B (en) * 2008-06-25 2011-05-25 苏庆泉 Carbon dioxide separating system and separating method
CN101659889B (en) * 2008-08-25 2012-09-26 来铁路 Methane purifying comprehensive utilization technology
CN102802766A (en) * 2009-06-19 2012-11-28 国际壳牌研究有限公司 Process For The Removal Of Carbon Dioxide And/or Hydrogen Sulphide From A Gas
CN102933284A (en) * 2010-04-20 2013-02-13 巴布考克日立株式会社 Exhaust gas treatment system provided with carbon dioxide chemisorption equipment
CN101856579A (en) * 2010-06-02 2010-10-13 清华大学 Novel energy-saving CO2 trapping process of improved potassium carbonate
CN102059037A (en) * 2010-11-22 2011-05-18 重庆欣雨压力容器制造有限责任公司 Process for purifying carbon dioxide from tail gas of natural gas
CN102242059A (en) * 2011-04-25 2011-11-16 青岛天人环境股份有限公司 Device and method for preparing automobile fuel gas by utilizing organic wastes
CN103113945A (en) * 2013-02-01 2013-05-22 王仕华 Marsh gas purification system and marsh gas purification method
CN103113945B (en) * 2013-02-01 2015-04-08 王仕华 Marsh gas purification system and marsh gas purification method
CN106318500A (en) * 2015-07-06 2017-01-11 中国石油化工股份有限公司 Biological purifying process of unconventional gas
CN108348841A (en) * 2015-08-28 2018-07-31 能源科技创新有限责任公司 Method and apparatus for handling biogas
CN106669365A (en) * 2016-12-15 2017-05-17 西安交通大学 Thermal-electric co-driven CO2 capturing system adopting amine method
CN111372671A (en) * 2017-11-30 2020-07-03 株式会社神户制钢所 Gas processing method and gas processing apparatus
CN111013333A (en) * 2019-12-24 2020-04-17 中国纺织科学研究院有限公司 Method for treating hydrogen sulfide in waste gas generated in viscose fiber production

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