WO2016186293A1 - Agent réducteur scr, procédé de préparation de celui-ci, et système scr - Google Patents

Agent réducteur scr, procédé de préparation de celui-ci, et système scr Download PDF

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Publication number
WO2016186293A1
WO2016186293A1 PCT/KR2016/000713 KR2016000713W WO2016186293A1 WO 2016186293 A1 WO2016186293 A1 WO 2016186293A1 KR 2016000713 W KR2016000713 W KR 2016000713W WO 2016186293 A1 WO2016186293 A1 WO 2016186293A1
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WO
WIPO (PCT)
Prior art keywords
scr
reducing agent
urea water
urea
hydrogen
Prior art date
Application number
PCT/KR2016/000713
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English (en)
Korean (ko)
Inventor
안기주
이장환
Original Assignee
주식회사 에스엔케이중공업
안기주
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from KR1020160007807A external-priority patent/KR101692548B1/ko
Application filed by 주식회사 에스엔케이중공업, 안기주 filed Critical 주식회사 에스엔케이중공업
Publication of WO2016186293A1 publication Critical patent/WO2016186293A1/fr

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to an SCR reducing agent, a method for producing the same, and an SCR system, and more particularly, to an SCR reducing agent, a method for preparing the same, and an SCR system capable of maximizing NOx removal efficiency while reducing the size of the SCR. .
  • marine SCR has the same basic principle of reducing terrestrial SCR and NO x , but it has many problems in applying it to a ship because its surrounding environment is very different from that of SCR on land.
  • Ships should be installed in a limited area and space, unlike onshore denitrification equipment. Moreover, it is very sensitive to weight, so when installed on existing ships, the weight axis of the ship should never be tilted or changed due to the weight of the denitrification equipment.
  • the present invention been made in view of the above problems, an object the present to invention this resolution is nitrogen while reducing the size of the SCR oxide (NO x) removal method efficient manufacturing SCR reducing agent thereof to maximize and SCR system To provide.
  • the present invention provides an SCR reducing agent including an urea water, wherein the urea water includes urea water and a hydrogen bubble.
  • the urea water of the SCR reducing agent of the present invention may include 1 ⁇ 10 6 ⁇ 2 ⁇ 10 9 ( ⁇ 1%) of hydrogen bubbles per 1 ml of urea water.
  • the average particle diameter of the hydrogen bubble of the SCR reducing agent of the present invention may be 1 ⁇ 100 ⁇ m.
  • the urea water of the SCR reducing agent of the present invention may include urea and water in a volume ratio of 22 to 55: 100.
  • the present invention provides a marine SCR containing the aforementioned reducing agent.
  • SCR includes the aforementioned reducing agent, and with respect to 100% by weight of the exhaust gas introduced into the SCR, the reducing agent It provides an SCR system in which 2 to 6% by weight is added.
  • the SCR driving pressure of the SCR system of the present invention may be 1.5 bar ⁇ 8.0 bar.
  • the present invention comprises the steps of injecting urea water into a reservoir in which the nozzle is formed a plurality of micropores; And forming a hydrogen bubble by injecting hydrogen gas at a pressure greater than the internal pressure of the reservoir inside the nozzle to prepare a hydrogen bubble, thereby preparing an activated urea water mixed with the hydrogen bubble and urea water. do.
  • the internal pressure of the reservoir of the SCR reducing agent manufacturing method of the present invention is 0.5bar ⁇ 1.5bar, the pressure injected into the nozzle may be 2bar ⁇ 10bar.
  • the size of the micropores of the SCR reducing agent manufacturing method of the present invention may be 1 ⁇ 100 ⁇ m.
  • the number of activated urea of the SCR reducing agent manufacturing method of the present invention includes 1 ⁇ 10 6 ⁇ 2 ⁇ 10 9 ( ⁇ 1%) hydrogen bubble per 1 ml of urea water can do.
  • the average particle diameter of the hydrogen bubble of the SCR reducing agent manufacturing method of the present invention may be 1 ⁇ 100 ⁇ m.
  • the SCR reducing agent of the present invention a method of manufacturing the same and the SCR system can maximize the removal efficiency of nitrogen oxide (NO x ) while reducing the size of the SCR
  • the SCR system of the present invention is a large transportation of transport equipment such as automobiles, ships, etc. It is suitable for applications in equipment and SCR systems in power plants.
  • 1A to 1E are test reports measured by the Korea Marine Equipment Research Institute, and the measurement of ammonia concentration after treating the exhaust gas with the SCR system using the urea water of Comparative Example 1 and the activated urea water of Example 1 is shown. The result is.
  • Conventional SCR contains ammonia and urea water.
  • a reducing agent such as an alcohol or a hydrocarbon compound was used to react with NO x in the exhaust gas introduced into the marine SCR as shown in Scheme 1 to convert nitrogen into water and nitrogen oxide, which are harmless to the environment.
  • ships should be installed in a limited area and space, unlike onshore denitrification equipment. Moreover, it is very sensitive to weight, so when installed on existing ships, the weight axis of the ship should never be tilted or changed due to the weight of the denitrification equipment.
  • the present invention as an SCR reducing agent, by introducing an activated urea (urea water) containing urea water and hydrogen bubbles (Hydrogen bubble), while reducing the size of the SCR while maximizing the NOx removal efficiency SCR
  • an activated urea urea water
  • hydrogen bubbles Hydro bubbles
  • the urea water in the activated urea water component is a form in which urea and water are mixed, and may include urea and water in a volume ratio of 22 to 50: 100, preferably 24 to 45: 100. If the volume ratio of urea and water included in the urea water is out of the above-described range, a problem may occur that the urea becomes solid after a certain period of time, thereby forming a mixture of urea and water.
  • the hydrogen bubble (Hydrogen bubble) of the activated urea water component serves to activate the urea water
  • the average particle diameter of the hydrogen bubble may be 1 ⁇ 100 ⁇ m, preferably 3 ⁇ 50 ⁇ m. If the average particle diameter of the hydrogen bubble is less than 1 ⁇ m there is a problem that the bubble can be easily absorbed or disappeared by the water pressure, if it exceeds 100 ⁇ m there may be a problem of bubble floating, satisfies the above range It is desirable to maximize the effect of the present invention.
  • the number of activated urea is 1 ⁇ 10 6 ⁇ 2 ⁇ 10 9 ( ⁇ 1%) hydrogen bubble, preferably 5 ⁇ 10 6 ⁇ 1.2 ⁇ 10 9 ( ⁇ 1%) per 1 ml of urea, More preferably 1 ⁇ 10 7 to 1 ⁇ 10 9 ( ⁇ 1%). If the number of activated urea is less than 1 ⁇ 10 6 hydrogen bubbles per 1 mL of urea, there may be a problem that the activation is too weak, and if more than 2 ⁇ 10 9 is included, the activation is too excessive. As described above, the chemical reaction may be promoted, and since there are technical difficulties in maintaining and generating 2 ⁇ 10 9 hydrogen bubbles in urea water, it is preferable to include hydrogen bubbles within the above range.
  • the present invention can be used as a reducing agent of the SCR reducing agent or the SCR for power plants, the SCR reducing agent mentioned above, it can provide a marine SCR, SCR for power plants using the same.
  • the present invention provides an SCR system for reducing nitrogen oxide (NO x ) contained in the exhaust gas
  • the SCR system of the present invention includes the aforementioned SCR reducing agent.
  • the SCR reducing agent may be added in an amount of 2 to 6% by weight, preferably 3 to 5% by weight, based on 100% by weight of the exhaust gas introduced into the SCR. If the concentration is less than%, the reduction of nitrogen oxides may be significantly reduced, and even if the concentration is more than 6 wt%, the improvement of nitrogen oxide removal performance is insufficient, which may result in an uneconomical problem.
  • the driving pressure of the marine SCR may be 1.5bar ⁇ 8.0bar, preferably 2.0bar ⁇ 6.0bar, if the driving pressure is less than 1.5bar urea water is ejected in the fine spray form Difficult to mix well with the exhaust gas may occur. If it exceeds 8.0 bar, hydrogen bubble formation is reduced, and problems with the pressure nozzle may occur.
  • the ammonia conversion rate of the contained nitrogen oxides of the exhaust gas is about 5% to 30%, preferably about 6% to 25%, more preferably 8% to 15% than the conventional SCR system. It may be higher by%.
  • step (1) urea water is introduced into a reservoir having a nozzle in which a plurality of micropores are formed.
  • the nozzle forms a hydrogen bubble and serves to supply hydrogen bubbles produced to the urea water contained in the reservoir, and the size of the micropores formed in the nozzle is 1 to 100 ⁇ m, preferably 1 to 30 ⁇ m. More preferably 1.5 to 10 ⁇ m. If the size of the micropores is less than 1 ⁇ m, the bubble may not only form a long time, but may also cause a problem in that hydrogen bubbles may not be formed. Since it may not be resident and may cause a bubble to break up due to the surface, it is preferable that the micropore size of the nozzle satisfies the above range.
  • step (2) of the manufacturing method of the SCR reducing agent of the present invention hydrogen gas is injected into the nozzle at a pressure greater than the internal pressure of the reservoir to form a hydrogen bubble, and the formed hydrogen bubble is mixed with urea water to form an active urea water. Is switched.
  • hydrogen gas to which a predetermined size of pressure is applied grows in the micropores of the nozzle, and the grown hydrogen bubble is desorbed from the micropores and mixed with the urea water.
  • the average particle diameter of the formed hydrogen bubble may be 1 ⁇ 100 ⁇ m, preferably 3 ⁇ 50 ⁇ m. If the average particle diameter of the minority bubble is less than 1 ⁇ m there may be a problem that the bubble can be easily absorbed or disappeared by the water pressure, if it exceeds 100 ⁇ m may be a problem of bubble injury, the above range It is desirable to maximize the effect of the present invention.
  • the internal pressure of the reservoir may be 0.5 bar to 1.5 bar, preferably 0.7 bar to 1.3 bar, and the pressure injected into the nozzle may be 2.0 bar to 10.0 bar, preferably 3.0 bar to 5.0 bar.
  • the internal pressure of the reservoir is 0.5 to 1.5 bar, if the pressure is less than 2.0 bar in the hydrogen gas injection nozzle for forming the hydrogen bubble, there may be a problem that hydrogen bubbles may not be formed, and 10.0. If it exceeds bar, it may be a problem that the pores of the nozzle is destroyed, it is preferable to satisfy the above range.
  • the activated urea water prepared by mixing hydrogen bubble with urea water is 1 ⁇ 10 6 to 2 ⁇ 10 9 ( ⁇ 1%) of hydrogen bubbles per 1 ml of urea water, preferably 5 ⁇ 10 6 to 1.2 ⁇
  • Hydrogen gas may be injected into the urea water through the nozzle to include 10 9 ( ⁇ 1%), more preferably 1 ⁇ 10 7 to 1 ⁇ 10 9 ( ⁇ 1%). If the number of activated urea is less than 1 ⁇ 10 6 hydrogen bubbles per 1 ml of urea, activation may be too low, leading to a problem of reduced reactivity, and more than 2 ⁇ 10 9 to remove nitrogen oxides. Since the increase effect is inadequate, inefficient, and the cost increases and technical difficulties exist, it is preferable to satisfy the above range.
  • Example 1 SCR reducing agent (activation The number of elements Manufacturing
  • hydrogen gas was introduced through the nozzle at a pressure of 3.7 to 3.9 bar to prepare activated urea water containing 2.55 ⁇ 10 8 ( ⁇ 1%) of hydrogen bubbles per 1 mL of urea water. And the particle size of hydrogen bubble was about 3 micrometers-12 micrometers.
  • Activated urea water was prepared in the same manner as in Example 1, but the hydrogen gas was injected into the nozzle at a pressure of 4.3 to 4.5 bar, and the activated water contained 3.74 ⁇ 10 8 ( ⁇ 1%) of hydrogen bubbles per 1 mL of urea water. Urea water was prepared.
  • Activated urea water was prepared in the same manner as in Example 1, except that 0.97 ⁇ 10 9 ( ⁇ 1%) of hydrogen bubbles were added per 1 ml of urea water by adding hydrogen gas at a nozzle internal pressure of 8.5 to 8.7 bar. Urea water was prepared.
  • An activated urea solution was prepared in the same manner as in Example 1, but the activation pressure including 1.65 ⁇ 10 8 ( ⁇ 1%) of hydrogen bubbles per 1 ml of urea water by adding hydrogen gas at a nozzle internal pressure of 3.0 to 3.2 bar. Urea water was prepared.
  • Example 2 An activated urea solution was prepared in the same manner as in Example 1, but the activation pressure including 5.6 ⁇ 10 6 ( ⁇ 1%) of hydrogen bubbles per 1 ml of urea was added by introducing hydrogen gas at a nozzle internal pressure of 2.3 to 2.5 bar. Urea water was prepared. Compared with Example 4, the number of hydrogen bubbles in the urea water tended to decrease significantly due to the decrease in the pressure inside the nozzle.
  • Activation urea water was prepared in the same manner as in Example 1, but the urea water containing 1.0 ⁇ 10 9 ( ⁇ 1%) of hydrogen bubbles per ml of urea was added by introducing hydrogen gas at a nozzle internal pressure of 10.5 bar. was prepared, and compared with Example 3, even if the pressure inside the nozzle was increased, there was almost no increase in the number of hydrogen bubbles.
  • Equation 1 the sum of theoretical NH 3 and theoretical HCNO concentrations is 1000 ppm ( ⁇ 5 ppm).
  • test report mentioning the specific method of measuring the ammonia concentration by requesting the urea water of Comparative Example 1 and the urea water of Example 1 from Korea Marine Equipment Research Institute is shown in FIGS. 1A to 1E.
  • the present invention can reduce the emissions of nitrogen oxides by providing a SCR reducing agent and SCR reduction apparatus incorporating the same, SCR reducing agent applied to transport equipment such as automobiles, ships, nitrogen gas exhaust plant and thermal power plant.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

La présente invention concerne un agent réducteur SCR, un procédé de préparation associé, et un système SCR et, plus spécifiquement, un agent réducteur SCR capable de maximiser l'efficacité d'élimination des oxydes d'azote (NOx) tout en réduisant le volume du système SCR, un procédé de préparation associé, et un système SCR correspondant.
PCT/KR2016/000713 2015-05-21 2016-01-22 Agent réducteur scr, procédé de préparation de celui-ci, et système scr WO2016186293A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20150070934 2015-05-21
KR10-2015-0070934 2015-05-21
KR10-2016-0007807 2016-01-21
KR1020160007807A KR101692548B1 (ko) 2015-05-21 2016-01-21 Scr 환원제, 이의 제조방법 및 scr 시스템

Publications (1)

Publication Number Publication Date
WO2016186293A1 true WO2016186293A1 (fr) 2016-11-24

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080299016A1 (en) * 2007-05-31 2008-12-04 Siemens Power Generation, Inc. System and method for selective catalytic reduction of nitrogen oxides in combustion exhaust gases
KR20110117323A (ko) * 2010-04-21 2011-10-27 희성촉매 주식회사 암모니아 분해 모듈을 가지는 디젤엔진 배기가스 배출장치
JP2014037788A (ja) * 2012-08-13 2014-02-27 Isuzu Motors Ltd 排ガスの後処理装置と、それを搭載する内燃機関
KR20140046651A (ko) * 2012-10-09 2014-04-21 현대중공업 주식회사 선박용 대형 엔진의 탈질장치
WO2014159859A1 (fr) * 2013-03-14 2014-10-02 Tenneco Automotive Operating Company Inc. Système d'échappement pour moteurs bi-carburant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080299016A1 (en) * 2007-05-31 2008-12-04 Siemens Power Generation, Inc. System and method for selective catalytic reduction of nitrogen oxides in combustion exhaust gases
KR20110117323A (ko) * 2010-04-21 2011-10-27 희성촉매 주식회사 암모니아 분해 모듈을 가지는 디젤엔진 배기가스 배출장치
JP2014037788A (ja) * 2012-08-13 2014-02-27 Isuzu Motors Ltd 排ガスの後処理装置と、それを搭載する内燃機関
KR20140046651A (ko) * 2012-10-09 2014-04-21 현대중공업 주식회사 선박용 대형 엔진의 탈질장치
WO2014159859A1 (fr) * 2013-03-14 2014-10-02 Tenneco Automotive Operating Company Inc. Système d'échappement pour moteurs bi-carburant

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