WO2015102136A1 - Procédé économe en énergie pour retirer un gaz acide par prétraitement au moyen d'eau ammoniaquée - Google Patents

Procédé économe en énergie pour retirer un gaz acide par prétraitement au moyen d'eau ammoniaquée Download PDF

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Publication number
WO2015102136A1
WO2015102136A1 PCT/KR2014/000086 KR2014000086W WO2015102136A1 WO 2015102136 A1 WO2015102136 A1 WO 2015102136A1 KR 2014000086 W KR2014000086 W KR 2014000086W WO 2015102136 A1 WO2015102136 A1 WO 2015102136A1
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Prior art keywords
tower
gas
absorbent
absorption tower
acid gas
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Ceased
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PCT/KR2014/000086
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English (en)
Korean (ko)
Inventor
강기준
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Amtpacific Co Ltd
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Amtpacific Co Ltd
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Priority to PCT/KR2014/000086 priority Critical patent/WO2015102136A1/fr
Publication of WO2015102136A1 publication Critical patent/WO2015102136A1/fr
Anticipated expiration legal-status Critical
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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
    • B01D53/14—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 absorption
    • B01D53/1431—Pretreatment by other processes
    • 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
    • B01D53/14—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 absorption
    • B01D53/1406—Multiple stage absorption
    • 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
    • B01D53/14—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 absorption
    • B01D53/1456—Removing acid components
    • B01D53/1462—Removing mixtures of hydrogen sulfide and carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • B01D2252/102—Ammonia
    • 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

Definitions

  • the present invention is a process for removing acid gas from a gas source containing an acid gas, such as natural gas, pre-combustion gas, post-combustion gas, syngas or reactor exhaust gas, more specifically natural gas, pre-combustion gas, post-combustion
  • an acid gas such as natural gas, pre-combustion gas, post-combustion gas, syngas or reactor exhaust gas, more specifically natural gas, pre-combustion gas, post-combustion
  • the present invention relates to a method for removing acid gas through pretreatment with ammonia water from gas, syngas, reactor exhaust gas and the like.
  • absorbents are used in combination with additives to remove acid gases.
  • absorbents should use medium pressure steam (3.0 kg / cm 2 G to 5.0 kg / cm 2 G) because the regeneration temperature is about 120 °C to 140 °C when removing the absorbed acid gas.
  • the selectivity of the absorbent to absorb acid gas is in the order of carbon dioxide (CO 2 )-> inorganic sulfur compound (H 2 S)-> organic sulfur compound (COS).
  • the absorbent absorbs the highest amount of carbon dioxide in the gas and then absorbs the inorganic sulfur compound and the organic sulfur compound. Therefore, a large amount of the absorbent has to be circulated to remove the inorganic sulfur compound and the organic sulfur compound. It consumes energy.
  • Korean Patent No. 0572286 discloses a method of removing acid gas components such as carbon dioxide and inorganic sulfur compounds from a gas by using a specific absorption medium, it does not disclose an efficient removal process of acid gas through ammonia water pretreatment.
  • the present invention was created in order to solve the problems as described above, by using ammonia water to remove the acidic gas to reduce the use of the medium pressure steam, and pre-treatment by ammonia water to increase the energy efficiency using waste heat generated in the process
  • the purpose is to provide a method for removing energy-saving acid gas.
  • the present invention provides a method for removing an acid gas included in a gas source selected from natural gas, pre-combustion gas, post-combustion gas, syngas, or reactor exhaust gas, wherein the gas source is a first absorbent including ammonia water. Processing by introducing into an absorption tower (first step); And a step (second step) of flowing the upper exhaust gas of the first absorption tower into a second absorption tower using a second absorbent (second step), thereby providing an energy saving acid gas removing method. .
  • the energy saving acid gas removing method according to the present invention provides the following effects.
  • the energy generated in the process of removing acidic gas using the second absorbent can be used as the energy of the process of removing acidic gas using ammonia water, which further reduces energy in the acidic gas removal process using ammonia. can do.
  • 1 is an acid gas removal process using a conventional second absorbent.
  • Figure 3 is an acid gas removal process through another embodiment of the present invention.
  • Figure 4 is an acid gas removal process through another embodiment of the present invention.
  • first absorption tower 400 first stripping tower
  • the present invention provides a method for removing an acid gas included in a gas source selected from natural gas, pre-combustion gas, post-combustion gas, syngas, or reactor exhaust gas, wherein the gas source is a first absorbent including ammonia water. Processing by introducing into an absorption tower (first step); And a step (second step) of introducing the upper exhaust gas of the first absorption tower into the second absorption tower using the second absorbent (second step), and energy saving type acid by pretreatment with ammonia water. Provide a method for degassing.
  • the first step may include introducing the gas source into a first absorption tower including ammonia water as a first absorbent to absorb acid gas into ammonia; Transferring the upper exhaust gas of the first absorption tower to a second absorption tower; Exchanging the lower discharge solution of the first absorption tower with the lower discharge solution of the first stripping tower and then introducing the lower discharge solution into the first stripping tower; Removing the acid gas absorbed by the ammonia from the first stripping column and discharging the acid gas upwardly; Heat-exchanging the lower discharge solution of the first stripping tower with the lower discharge solution of the first absorption tower and cooling the liquid to flow into the upper portion of the first absorption tower; Introducing ammonia water obtained by washing with water in the upper portion of the first absorption tower and ammonia water obtained by washing with water in the upper portion of the first stripping column to a concentration tower; And discharging the concentrated ammonia from the top of the concentration tower.
  • the second step the step of introducing the upper exhaust gas of the first absorption tower into the second absorption tower; Discharging the gas source remaining after absorbing the acidic gas into the second absorbent in the second absorption tower; Exchanging the lower discharge solution of the second absorption tower with the lower discharge solution of the second stripping tower and then introducing the liquid into the second stripping tower; Removing the acid gas absorbed by the second absorbent from the second stripping tower and discharging the acid gas upwardly;
  • the lower discharge solution of the second stripping tower may include heat exchange with the lower discharge solution of the second absorption tower and then cooled to flow into the upper portion of the second absorption tower.
  • the energy-saving acid gas removal method the step of introducing the gas source into the first absorption tower containing ammonia water as the first absorbent to absorb the acid gas in the first absorbent; Introducing a lower discharge solution of the first absorption tower into a first stripping tower; Removing the acid gas absorbed by the first absorbent from the first stripping tower and discharging the acid gas to an upper portion of the first stripping tower; Absorbing the remaining acid gas into the second absorbent by introducing the upper discharge solution of the first absorbent into the second absorbent including the second absorbent; Removing the acid gas absorbed by the second absorbent from the second stripping tower and discharging the acid gas to an upper portion of the second stripping tower; And heat-exchanging the lower discharge solution of the second stripping column with the lower discharge solution of the first absorption tower and then introducing the lower discharge solution into the first stripping tower.
  • the acid gas may be any one or a combination of two or more selected from the group consisting of carbon dioxide, inorganic sulfur compounds and organic sulfur compounds.
  • the gas source is introduced into a first absorption tower including ammonia water as a first absorbent to absorb the acid gas to ammonia; Exchanging the lower discharge solution of the first absorption tower with the lower discharge solution of the first stripping tower and then introducing the lower discharge solution into the first stripping tower; Removing the acid gas absorbed by the ammonia from the first stripping column and discharging the acid gas upwardly; Heat-exchanging the lower discharge solution of the first stripping tower with the lower discharge solution of the first absorption tower and cooling the liquid to flow into the upper portion of the first absorption tower; Introducing ammonia water obtained by washing with water in the upper portion of the first absorption tower and ammonia water obtained by washing with water in the upper portion of the first stripping column to a concentration tower; Discharging the concentrated ammonia from the top of the concentration tower; Introducing a lower discharge solution of the concentration tower into a first absorption tower; Introducing an upper discharge gas of the first absorption tower into a second absorption tower
  • the first discharge tower bottom discharge solution flowing into the first stripping column is heat-exchanged with the bottom discharge solution of the first stripping tower, and then heat exchanged once more with the bottom discharge solution of the second stripping tower To the first stripping column.
  • the second absorbent may be selected from the group consisting of amine compounds, calcium absorbents and sodium absorbents.
  • ammonia water introduced into the concentration tower may be introduced into the concentration tower by exchanging heat again with the lower discharge solution of the second stripping column.
  • the first absorption tower and the first stripping tower using ammonia water may be provided with a washing unit for absorbing and recovering the lost ammonia as water, by cooling the water discharged to the lower portion of the concentration tower to enter the washing unit ammonia Can be used for absorption.
  • the water discharged to the bottom of the concentration tower may be used after cooling the heat exchanged with the solution washed in the upper portion of the first absorption tower and the first stripping tower.
  • the energy saving type acid gas removal method through pretreatment with ammonia water according to the present invention will be described in more detail with one embodiment of removing acid gas from bunker-C oil.
  • the composition of the gas discharged from the reactor is as follows.
  • an acidic gas is introduced into the absorption tower 100 using diisopropanolamine (DIPA) at 39% by weight (wt%) using the gas having the composition 10.
  • DIPA diisopropanolamine
  • Carbon dioxide, inorganic sulfur compound, organic sulfur compound must be removed before synthesis gas can be used in reaction process. Sulfur compounds, in particular, have an adverse effect on the catalyst in the reaction process and should be removed below 1 vol ppm.
  • the selectivity for the second absorbent 32 to absorb the acidic gas 25 is in the order of carbon dioxide-> inorganic sulfur compound-> organic sulfur compound. Therefore, diisopropanolamine as the second absorbent absorbs the most carbon dioxide in the gas and then the inorganic sulfur compound and the organic sulfur compound.
  • the amount (kg) of the absorbent (30,32) to be circulated to remove the inorganic sulfur compound and organic sulfur compound is about 3.5 times the amount of the synthesis gas (Nm 3 ), which consumes a lot of energy in the absorption-regeneration process. .
  • the amount of absorbent consumed to absorb carbon dioxide and inorganic sulfur compounds per 1 Nm 3 of syngas is 3.48 kg as shown in the following formula,
  • the amount of absorbent consumed to absorb the organic sulfur compound per 1 Nm 3 of the synthesis gas is 0.02 kg as shown in the following formula,
  • the exhaust gas of the synthesis gas production reactor is first introduced 40 into the first absorption tower 300 using ammonia water using low temperature energy as an absorbent to first remove carbon dioxide and inorganic sulfur compounds. .
  • Synthesis gas 45 discharged to the upper portion of the absorption tower using ammonia water as the absorbent contains an organic sulfur compound, so that the second absorbent is introduced into the second absorption tower 100 to remove the organic sulfur compound.
  • Theoretical circulation amount of the absorbent for reducing the organic sulfur compound to 30 vol ppm or less is 0.02 kg / synthetic gas 1 Nm 3
  • the theoretical absorbent circulation amount for the organic sulfur compound to 1 vol ppm or less is 0.4 kg / synthetic gas 1 Nm 3 .
  • the amount of medium pressure steam used to reduce the organic sulfur compound to 1 vol ppm or less is about 220 kg x 0.4 kg / 3.5 kg, thus about 25 kg per 1000 Nm 3 of syngas.
  • This medium pressure steam amount is about 11% compared to using only the second absorbent as the absorbent.
  • the amount of low pressure steam can also be reduced.
  • the concentration of ammonia in the ammonia water flowing into the first absorption tower is preferably from 2% by weight to 25% by weight. If the concentration of ammonia is too low, the amount of ammonia water used is too high. If the concentration of ammonia is too high, the amount of ammonia that is volatilized and lost in the process may be high, and excessive freezing energy must be used to reduce this volatilization. to be.
  • 1 is a process chart of a conventional acid gas removal method.
  • FIG. 2 is a process chart of a method for removing acid gas through pretreatment with ammonia water according to an embodiment of the present invention
  • FIG. 3 is a process diagram of an energy saving method according to another embodiment of the process diagram shown in FIG. 2.
  • 4 is a flowchart illustrating another embodiment of the energy saving method of the flowchart illustrated in FIG. 3.
  • the same reference numerals as those shown in Figs. 1, 2, 3, and 4 are the same members having the same configuration and function, and thus repetitive description thereof will be omitted.
  • first absorption tower 300 and the first stripping tower 400 may further include a washing unit at the top, re-boilers (203, 403, 503) of the stripping tower (200, 400) and concentration tower (500) ) Using steam (98) and in the condenser (204, 404, 504) with cooling water (97).
  • the coolers 102, 302, and 502 use the coolant 97 to cool.
  • a gas source 40 selected from natural gas, pre-combustion gas, post-combustion gas, syngas, or reactor exhaust gas flows into the first absorption tower 300 using ammonia water as an absorbent.
  • the acid gas is collected in ammonia water and discharged (50) to the lower portion of the first absorption tower 300 is introduced into the first stripping tower (400).
  • the acid gas collected in the ammonia water in the first stripping tower 400 is discharged through the upper part of the first stripping column 55, and after the acid gas is removed, the ammonia water is discharged into the lower portion of the first stripping column 60 to obtain the first gas. It is introduced into the absorption tower 300 (60, 61, 62).
  • the solution 54 washed in the first stripping tower upper washing unit is introduced into the concentration tower 500 with the solution 44 washed in the first absorption tower upper washing unit 70, and concentrated ammonia Discharge 75.
  • the concentrated tower bottom discharge solution 80 is circulated and introduced into the upper washing part of the first absorption tower 300 and the upper washing part of the first stripping tower 400.
  • the upper exhaust gas 45 of the first absorption tower 300 is introduced into the second absorption tower 100 using the second absorbent.
  • the organic sulfur compound is collected in the second absorbent and flows into the second stripping tower 200 through the lower portion of the second absorption tower 100 (20, 21).
  • the second absorbent and the organic sulfur compound are discharged to the lower 30 and the upper 25 of the second stripping tower 200, respectively.
  • the organic sulfur compound is discharged to the upper portion 25 of the second stripping tower 200, and the second absorbent is discharged to the lower portion 30 of the second stripping tower 200. Inflow 32 to the top of 100).
  • the second stripping tower bottom discharge solution 30, 31 and the first absorption tower bottom discharge solution 50, 51, 53 are heat-exchanged through the heat exchanger 601 to be generated in the second stripping tower 400. Using waste heat saves energy.
  • the ammonia water 44 obtained by washing the waste heat generated in the second stripping tower 200 with water at the top of the first absorption tower and the ammonia water obtained by washing with water at the top of the first stripping tower (54). ) Is introduced into the enrichment tower 500, so the heat is exchanged through the heat exchanger 701 to use waste heat generated in the second stripping tower, thereby saving energy.
  • the second absorbent is monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), methyldiethanolamine (MDEA), diisopropanolamine (Diisopropanolamine; DIPA), Diglycolamine (DGA), aminomethylpropanol (AMP), piperidine ethanol (PE) potassium hydroxide (KOH) and sodium hydroxide (NaOH)
  • MEA monoethanolamine
  • DEA diethanolamine
  • TEA methyldiethanolamine
  • MDEA diisopropanolamine
  • DIPA Diglycolamine
  • AMP aminomethylpropanol
  • PE potassium hydroxide
  • NaOH sodium hydroxide
  • An amine compound which is one or a combination of two or more selected from the group consisting of, calcium-based absorbents such as limestone and slaked lime, sodium-based absorbents such as sodium carbonate (Na 2 CO 3 ) or sodium hydrogen carbonate (NaHCO 3 ), and the like can be used. It is not limited

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

La présente invention concerne un procédé économe en énergie pour retirer un gaz acide par prétraitement au moyen d'eau ammoniaquée, et, plus spécifiquement un procédé économe en énergie pour retirer, par un prétraitement au moyen d'eau ammoniaquée, un gaz acide contenu dans une source de gaz choisie parmi un gaz naturel, un gaz pré-combustion, un gaz post-combustion, un gaz de synthèse et un gaz évacué par un réacteur, le procédé comprenant les étapes suivantes : traitement de la source de gaz par introduction de la source de gaz dans une première tour d'absorption contenant de l'eau ammoniaquée comme premier absorbant (première étape) ; et traitement d'un gaz d'évacuation supérieure de la tour d'absorption par introduction du gaz d'évacuation supérieure dans une seconde tour d'absorption (seconde étape). Selon le procédé de retrait d'un gaz acide, il est possible : de retirer la plus grand partie du dioxyde de carbone à l'avance par un prétraitement à l'eau ammoniaquée ; d'économiser de l'énergie en utilisant la chaleur dégagée pendant le procédé ; de réutiliser l'eau ammoniaquée dans une colonne d'enrichissement ; et de réduire et de simplifier un procédé de production de dioxyde de carbone et un procédé de production de soufre après le retrait du gaz acide, par exemple à partir d'un gaz acide, en séparant et en évacuant un composé soufré inorganique et un composé soufré organique.
PCT/KR2014/000086 2014-01-06 2014-01-06 Procédé économe en énergie pour retirer un gaz acide par prétraitement au moyen d'eau ammoniaquée Ceased WO2015102136A1 (fr)

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PCT/KR2014/000086 WO2015102136A1 (fr) 2014-01-06 2014-01-06 Procédé économe en énergie pour retirer un gaz acide par prétraitement au moyen d'eau ammoniaquée

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107697931A (zh) * 2017-10-31 2018-02-16 四川锌鸿科技有限公司 一种多级逆向循环吸氨工艺
CN115259259A (zh) * 2022-07-18 2022-11-01 陕西未来能源化工有限公司 一种变换冷凝液处理系统及工艺

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KR101190725B1 (ko) * 2010-07-14 2012-10-12 한국전력공사 산성가스 분리회수 장치
KR20130047470A (ko) * 2011-10-31 2013-05-08 한국에너지기술연구원 암모니아수 흡수용액을 사용하는 개선된 이산화탄소 포집 방법 및 이를 구현하는 장치

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KR100703999B1 (ko) * 2006-02-24 2007-04-04 한국에너지기술연구원 암모니아수를 이용한 혼합가스에서 이산화탄소 회수 방법및 장치
KR20110091684A (ko) * 2008-10-21 2011-08-12 우데 게엠베하 가스의 세정을 위한 수성 암모니아 용액 및 아민으로 구성되는 세정 용액 및 이의 사용
KR20120096575A (ko) * 2009-12-17 2012-08-30 알스톰 테크놀러지 리미티드 가스 스트림으로부터 ｃｏ₂의 제거를 추종하는 암모니아 제거
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KR20130047470A (ko) * 2011-10-31 2013-05-08 한국에너지기술연구원 암모니아수 흡수용액을 사용하는 개선된 이산화탄소 포집 방법 및 이를 구현하는 장치

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107697931A (zh) * 2017-10-31 2018-02-16 四川锌鸿科技有限公司 一种多级逆向循环吸氨工艺
CN107697931B (zh) * 2017-10-31 2020-06-30 四川锌鸿科技有限公司 一种多级逆向循环吸氨工艺
CN115259259A (zh) * 2022-07-18 2022-11-01 陕西未来能源化工有限公司 一种变换冷凝液处理系统及工艺

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