KR101175136B1 - Method for renewed activation of the deactivated plate type SCR catalyst - Google Patents
Method for renewed activation of the deactivated plate type SCR catalyst Download PDFInfo
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- KR101175136B1 KR101175136B1 KR1020100035874A KR20100035874A KR101175136B1 KR 101175136 B1 KR101175136 B1 KR 101175136B1 KR 1020100035874 A KR1020100035874 A KR 1020100035874A KR 20100035874 A KR20100035874 A KR 20100035874A KR 101175136 B1 KR101175136 B1 KR 101175136B1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
본 발명은 판형 배연탈질 폐 촉매의 재생방법에 관한 것으로, 보다 상세하게는 활성도가 감소한 이산화티타늄, 바나듐 및 텅스텐을 함유하는 폐탈질 촉매 모듈을 세정장치에서 산 수용액을 세정액으로 사용하는 재생공정에 있어서, 상기 세정액에 철이온의 용출을 억제하여 삼산화황에 의한 설비 부식을 방지할 수 있는 첨가제를 추가로 첨가한 혼합액을 사용하여 재생공정을 가지는 판형 배연탈질 폐촉매의 재생방법에 관한 것이다. The present invention relates to a regeneration method of a plate-type flue gas denitrification waste catalyst, and more particularly, in a regeneration process in which a waste denitrification catalyst module containing titanium dioxide, vanadium, and tungsten having reduced activity is used in a washing apparatus using an acid aqueous solution as a washing liquid. In addition, the present invention relates to a method for regenerating a plate-type flue gas denitrification waste catalyst having a regeneration process using a mixed solution in which iron ions are prevented from being added to the rinse solution to further prevent equipment corrosion caused by sulfur trioxide.
Description
본 발명은 판형 배연탈질 폐촉매의 재생방법에 관한 것으로, 판형선택적 촉매환원 촉매를 케이싱에서 분리없이 직접 세정장치에서 재생하여 철 이온의 용출을 억제하여 삼산화황에 의한 부식을 감소시킬 수 있는 폐촉매의 재생방법에 관한 것이다.
The present invention relates to a method for regenerating a plate-type flue gas denitrification waste catalyst, wherein the plate-type catalytic reduction catalyst can be regenerated in a direct cleaning apparatus without separation in a casing to suppress the leaching of iron ions, thereby reducing corrosion by sulfur trioxide. It relates to a regeneration method.
화력발전소에서 가장 널리 이용되는 질소산화물 제거기술은 암모니아 환원제와 촉매반응에 의하여 질소산화물을 무해한 질소와 물로 분해 제거하는 선택적 촉매환원 기술(Selective Catalytic Reduction, 이하 SCR) 이다. 이에 사용되는 판형 (plate) 촉매는 메탈(스테인레스 스틸) 지지체에 이산화티타늄, 바나듐과 텅스텐을 활성물질로 코팅하여 제조하고 있다. 상기 촉매는 배기가스 중에 포함된 비산회의 피독 및 고형물의 침적 등으로 활성이 지속적으로 떨어져 일정기간이 지나면 그 수명이 끝난다.The most widely used nitrogen oxide removal technology in thermal power plants is Selective Catalytic Reduction (SCR), which decomposes and removes nitrogen oxides into harmless nitrogen and water by catalytic reaction with ammonia reducing agents. Plate catalysts used for this purpose are prepared by coating titanium dioxide, vanadium and tungsten with an active material on a metal (stainless steel) support. The catalyst is continually deactivated due to poisoning of fly ash contained in the exhaust gas and deposition of solids, and thus ends its life after a certain period of time.
종래의 재생방법은 전부 피독물질의 용해능이 알려져 있는 산, 알칼리의 수용액으로 피독물질을 용출 제거하고 활성의 회복을 도모하는 것으로서 메탈재질인 판(plate) 및 케이싱(casing)부식으로 인한 철(Fe)이온의 용출을 억제시키는 방법에 대한 기술은 없다. 용출된 철 이온은 촉매 표면에 침투되어 배기가스 중의 이산화황(SO2)의 산화를 더욱 촉진시켜 다량의 삼산화황(SO3)을 생성시키는데, 이와 같이 생성된 삼산화황은 환원제로 주입된 미반응된 암모니아와 반응하여 암모니아 황산염(NH4HSO4, (NH4)2SO4)을 생성한다. 상기 암모니아 황산염 생성반응을 반응식으로 간단히 표시하면 아래와 같다.The conventional regeneration method is to dissolve and remove the poisoned substance with an aqueous solution of acid and alkali, which is known to be capable of dissolving the poisoned substance, and to recover the activity. The iron due to corrosion of the plate and casing made of metal There is no description of how to inhibit elution of ions. The eluted iron ions penetrate the surface of the catalyst to further promote the oxidation of sulfur dioxide (SO 2 ) in the exhaust gas to produce a large amount of sulfur trioxide (SO 3 ), which is then reacted with the unreacted ammonia injected into the reducing agent. The reaction produces ammonia sulfate (NH 4 HSO 4 , (NH 4 ) 2 SO 4 ). The ammonia sulphate production reaction is briefly expressed as follows.
SO3 + NH3 + H2O → NH4HSO4 (1)SO 3 + NH 3 + H 2 O → NH 4 HSO 4 (1)
SO3 + 2NH3 + H2O → (NH4)2SO4 (2) SO 3 + 2 NH 3 + H 2 O → (NH 4 ) 2 SO 4 (2)
상기와 같은 암모니아 황산염(NH4HSO4, (NH4)2SO4)은 촉매의 수명저하, 전열기 차압증가, 전열기의 부식 등을 발생시키는 문제점이 있다.
The ammonia sulfate as described above (NH 4 HSO 4 , (NH 4 ) 2 SO 4 ) has a problem that decreases the life of the catalyst, increase the differential pressure of the heater, corrosion of the heater.
본 발명은 상기한 바와 같은 종래기술의 문제점을 해결하기 위한 것으로, 판형 SCR 촉매를 케이싱에서 분리 없이 직접 세정장치에서 재생하면서도 철(Fe) 이온의 용출을 억제하여 삼산화황 (SO3)에 의한 설비의 부식을 감소시키는 방법을 제공한다.
The present invention is to solve the problems of the prior art as described above, while reproducing the plate-type SCR catalyst in a direct cleaning device without separation in the casing, while suppressing the elution of iron (Fe) ions to the installation of sulfur trioxide (SO 3 ) It provides a method of reducing corrosion.
상기 목적을 달성하기 위하여 본 발명은,The present invention to achieve the above object,
활성도가 감소한 이산화티타늄, 바나듐 및 텅스텐을 함유하는 폐탈질 촉매 모듈을 세정장치에서 산 수용액을 세정액으로 사용하는 재생공정에 있어서, 상기 세정액에 아민이나 사이오화합물을 추가로 첨가한 혼합액을 사용하여 재생공정을 가지는 판형 배연탈질 폐촉매의 재생방법을 제공한다.In a regeneration process in which a waste denitrification catalyst module containing titanium dioxide, vanadium, and tungsten having reduced activity is used as a cleaning solution in an aqueous cleaning solution, a regeneration is performed using a mixed solution in which an amine or a cio compound is added to the cleaning solution. Provided is a method for regenerating a plate-type flue gas denitrification waste catalyst having a process.
상기 혼합액은 물, 산 및 첨가물의 부피비가 각각 98.93:1.0:0.07 내지 90.4:9:0.6 의 범위내인 것을 만족하는 것을 특징으로 하고, 상기 판형촉매의 판 간격은 7mm인 것이 바람직하다. 또한, 상기 산 수용액은 황산 또는 유기산 수용액인 것을 특징으로 한다.The mixed solution is characterized in that the volume ratio of water, acid and additives is within the range of 98.93: 1.0: 0.07 to 90.4: 9: 0.6, respectively, and the plate spacing of the plate catalyst is preferably 7 mm. In addition, the acid aqueous solution is characterized in that the aqueous solution of sulfuric acid or organic acid.
또한, 본 발명은 활성도가 감소한 이산화티타늄, 바나듐 및 텅스텐을 함유하는 폐탈질 촉매 모듈을 세정장치에서 황산 수용액을 세정액으로 사용하는 재생공정에 있어서, 상기 세정액에 질산을 추가로 첨가한 혼합액을 사용하여 재생공정을 가지는 판형 배연탈질 폐촉매의 재생방법을 제공한다.In addition, the present invention is a waste denitrification catalyst module containing titanium dioxide, vanadium and tungsten having reduced activity in the regeneration process using a sulfuric acid aqueous solution as a cleaning liquid in the cleaning apparatus, using a mixed solution in which nitric acid is further added to the cleaning liquid A method for regenerating a plate-type flue gas denitrification waste catalyst having a regeneration process is provided.
또한, 본 발명은 활성도가 감소한 이산화티타늄, 바나듐 및 텅스텐을 함유하는 폐탈질 촉매 모듈을 세정장치에서 염산 수용액을 세정액으로 사용하는 재생공정에 있어서, 상기 세정액에 아세틸레닉 알코올을 추가로 첨가한 혼합액을 사용하여 재생공정을 가지는 판형 배연탈질 폐촉매의 재생방법을 제공한다.In addition, the present invention is a waste denitrification catalyst module containing titanium dioxide, vanadium and tungsten having reduced activity in the regeneration process using an aqueous hydrochloric acid solution as a cleaning liquid in a washing apparatus, the mixed liquid of the addition of acetylenic alcohol to the cleaning liquid It provides a method for regenerating a plate-type flue gas denitrification waste catalyst having a regeneration process.
또한, 본 발명은 활성도가 감소한 이산화티타늄, 바나듐 및 텅스텐을 함유하는 폐탈질 촉매 모듈을 세정장치에서 수산화나트륨 수용액을 세정액으로 사용하는 재생공정에 있어서, 상기 세정액에 질산 또는 폴리썰파이드 용액을 추가로 첨가한 혼합액을 사용하여 재생공정을 가지는 판형 배연탈질 폐촉매의 재생방법을 제공한다.
The present invention also provides a waste denitrification catalyst module containing titanium dioxide, vanadium and tungsten with reduced activity in a regeneration process using an aqueous sodium hydroxide solution as a cleaning solution, wherein the nitric acid or polysulfide solution is further added to the cleaning solution. Provided is a method for regenerating a plate-type flue gas denitrification waste catalyst having a regeneration process using an added mixed liquid.
본 발명에 따르면, 활성도가 크게 감소한 판형 SCR 폐 촉매를 세정장치에서 산 수용액으로 세정하여 활성기능을 오염 전 촉매상태로 회복시키는 재생공정에서 세정액에 사이오화합물 등을 첨가하여 촉매의 지지체 및 케이싱의 부식을 억제하여 철 (Fe) 이온의 용출을 감소시키는 효과가 있다.
According to the present invention, in the regeneration process of washing the plate-type SCR waste catalyst whose activity is greatly reduced with an aqueous acid solution in the washing apparatus and restoring the active function to the catalyst state before contamination, by adding a cio compound or the like to the washing liquid, It is effective in reducing the dissolution of iron (Fe) ions by inhibiting corrosion.
본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.
따라서, 본 명세서에 기재된 실시예와 도면에 도시된 구성은 본 발명의 가장 바람직한 일 실시예에 불과할 뿐이고, 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다.Therefore, the embodiments described in the specification and the drawings shown in the drawings are only the most preferred embodiment of the present invention, and do not represent all of the technical idea of the present invention, which can be replaced at the time of the present application It should be understood that there may be various equivalents and variations.
본 발명에 따른 암모니아 환원제를 이용하여 배기가스 중의 질소산화물을 제거에 사용하는 판형 (plate)촉매는 메탈(스테인레스 스틸 등) 지지체(support)에 이산화티타늄(TiO2), 바나듐(V) 및 텅스텐(W) 산화물을 코팅한 촉매로서 장기간 사용시 비산회의 피독 및 고형물의 침적등으로 활성이 떨어지면 이들을 산 수용액 및 알카리 수용액을 이용하여 세정하여 활성을 회복시킨다. The plate catalyst used to remove nitrogen oxides in the exhaust gas using the ammonia reducing agent according to the present invention is a titanium (TiO 2 ), vanadium (V) and tungsten ( W) As an oxide-coated catalyst, if activity is reduced due to poisoning of fly ash and deposition of solids during long-term use, they are washed with an aqueous acid solution and an aqueous alkali solution to restore activity.
그러나, 이들 촉매의 지지체 및 케이싱은 세정액인 황산용액 등으로 부식되어 철(Fe)을 용출하고 이는 촉매표면에 침투하여 배기가스 중의 이산화황(SO2)을 삼산화황(SO3)으로 산화시켜 촉매반응기 후단 설비에 많은 문제점을 해결하기 위한 방법으로, 본 발명은 세정액에 아민, 사이오화합물 (thioureas, sulfoxides) 및 아세틸레닉 알코올 등을 첨가하여 재생공정을 거치는 방법에 관한 것이다.However, the support and casing of these catalysts are corroded with sulfuric acid solution, which is a cleaning solution, to elute iron (Fe), which penetrates into the surface of the catalyst and oxidizes sulfur dioxide (SO 2 ) in the exhaust gas to sulfur trioxide (SO 3 ). In order to solve a lot of problems in the installation, the present invention relates to a method of regeneration by adding amine, thioureas, sulfoxides and acetylenic alcohol to the cleaning solution.
본 발명은 상기와 같은 첨가액을 이용하여 종래에 판(plate)형 배연탈질 폐 촉매 재생에 문제가 되었던 철(Fe) 이온 용출을 억제시키면서 활성을 동등하게 회복시킬 수 있는 방법에 관한 것이다. 즉, 활성도가 감소한 이산화티타늄, 바나듐 및 텅스텐을 함유하는 폐탈질 촉매 모듈을 세정장치에서 산 수용액을 세정액으로 사용하는 재생공정에 있어서, 상기 세정액에 아민이나 사이오화합물을 추가로 첨가한 혼합액을 사용하는 것을 특징으로 한다. The present invention relates to a method for recovering activity equally while suppressing the elution of iron (Fe) ions, which has been a problem in the conventional plate-type flue gaseous denitrification waste catalyst regeneration, by using the above additive solution. That is, in the regeneration process in which a waste denitrification catalyst module containing titanium dioxide, vanadium, and tungsten with reduced activity is used as a cleaning solution in an acid solution in a washing apparatus, a mixed solution in which an amine or a cio compound is added to the cleaning solution is used. Characterized in that.
상기에서 언급한 산 수용액은 유기산 또는 무기산의 산 수용액을 사용할 수 있으며, 구체적으로 HCl, HNO3, HF 또는 H2SO4등의 수용액이 있다. 상기 HCl, HNO3, HF 또는 H2SO4의 수용액을 이용하는 경우, 수용액의 농도는 0.1~25 중량%의 범위로 하고, 수용액의 온도는 10~90℃의 범위로 하는 것이 바람직하다. 이는 수용액의 온도가 10℃ 미만에서는 이온교환이 충분하지 않으며, 수용액의 온도가 90℃보다 높은 범위에서는 처리설비의 비용이 높아지기 때문이다.The acid aqueous solution mentioned above may use an acid aqueous solution of an organic acid or an inorganic acid, and specifically, an aqueous solution such as HCl, HNO 3 , HF, or H 2 SO 4 . To as the HCl, HNO 3, HF, or the case of using an aqueous solution of H 2 SO 4, the range of concentration in the range of 0.1 to 25% by weight, and the temperature of the aqueous solution of the aqueous solution is 10 ~ 90 ℃ is preferred. This is because ion exchange is not sufficient when the temperature of the aqueous solution is less than 10 ° C, and the cost of the treatment equipment becomes high when the temperature of the aqueous solution is higher than 90 ° C.
본 발명에 따른 판형 배연탈질 폐 촉매의 재생방법은 판형 SCR 폐 촉매를 케이싱 상태로 세정용액을 0.1- 0.5M 황산용액(H2SO4) 및 0.01- 0.05M 티오우레아(CSN2H4) 용액을 함유한 혼합액으로 세정장치에서 재생시키는 것을 특징으로 하는데, 상기 혼합액은 물: H2SO4: CSN2H4을 98.93: 1.0: 0.07 내지 90.4: 9: 0.6의 부피비로, 바람직하게는 96.8: 3: 0.2의 부피비로 혼합하여 사용할 수 있다.Regeneration method of the plate-type flue gas denitrification waste catalyst according to the present invention is a 0.1-0.5M sulfuric acid solution (H 2 SO 4 ) and 0.01-0.05M thiourea (CSN 2 H 4 ) It is characterized in that the mixed liquid containing the regeneration in the washing apparatus, the mixed liquid is water: H 2 SO 4 : CSN 2 H 4 in a volume ratio of 98.93: 1.0: 0.07 to 90.4: 9: 0.6, preferably 96.8: 3: It may be used by mixing in a volume ratio of 0.2.
즉, 본 발명에 따르면 질소산화물을 환원 제거하는 활성물질(이산화티타늄, 바나듐, 텅스텐)을 메탈(metal) 판에 코팅한 판 (plate)형 촉매로서, 장기간 비 산회 (fly ash)의 중금속, 알칼리 금속, 비소, 유황 등 피독물질에 노출되어 활성 저하된 판형 촉매의 모듈을 황산 또는 유기산 수용액으로 재생함에 있어서 아민, 사이오화합물(thioureas, sulfoxides) 또는 질산을 첨가하는 방법을 사용할 수 있다.That is, according to the present invention, a plate-type catalyst coated with a metal plate of an active material (titanium dioxide, vanadium, tungsten) which reduces and removes nitrogen oxides, and is a heavy metal, alkali of fly ash for a long time. In the regeneration of a module of a plate-type catalyst deactivated by exposure to poisoning substances such as metals, arsenic, and sulfur with an aqueous solution of sulfuric acid or organic acid, amines, thioureas, sulfoxides or nitric acid may be added.
또한, 본 발명은 질소산화물을 환원 제거하는 활성물질(이산화티타늄, 바나듐, 텅스텐)을 스테인레스 판에 코팅한 판 (plate)형 촉매로서, 장기간 비 산회 (fly ash)의 중금속, 알칼리 금속, 비소, 유황 등 피독물질에 노출되어 활성 저하된 판형 촉매를 염산 수용액으로 재생함에 있어서 아세틸레닉 알코올을 첨가하거나, 수산화나트륨 수용액으로 재생함에 있어서는 질산 또는 폴리썰파이드 용액을 첨가하는 방법을 사용할 수도 있다.
In addition, the present invention is a plate-type catalyst coated with a stainless plate of an active material (titanium dioxide, vanadium, tungsten) to reduce and remove nitrogen oxides, heavy metals, alkali metals, arsenic, In the regeneration of the plate-type catalyst deactivated by exposure to poisoning substances such as sulfur in an aqueous hydrochloric acid solution, an acetylenic alcohol may be added, or in the regeneration of an aqueous sodium hydroxide solution, a nitric acid or polysulfide solution may be used.
이하 본 발명을 아래와 같은 실시예에 의거하여 상세하게 설명하며 단 아래의 예는 본 발명을 예시하기 위한 것일 뿐, 이에 한정하지 않으며 본 발명의 실시예에서 제조한 산물의 분석은 다음과 같은 방법으로 실시했다.
Hereinafter, the present invention will be described in detail with reference to the following examples, but the following examples are only intended to illustrate the present invention, and the present invention is not limited thereto. Carried out.
<< 실시예Example 1-3> 1-3> HH 22 SOSO 44 및 And HH 22 SOSO 44 + + CSNCSN 22 HH 44 혼합용액에 의한 판형 Plate type by mixed solution SCRSCR 폐 촉매 재생 Waste catalyst regeneration
본 발명에서는 화력발전소 SCR 설비에서 탈질효율이 신 촉매 대비 약 60%로 낮아진 폐 촉매를 시험촉매로 선택하였다. 상기 촉매는 메탈 지지체에 이산화티타늄, 바나듐과 텅스텐을 활성물질로 코팅한 상업용 촉매로서 판 간격(pitch)은 7 mm 크기의 판형 촉매이다.In the present invention, the waste catalyst whose denitrification efficiency is lowered to about 60% compared to the new catalyst in the thermal power plant SCR facility was selected as the test catalyst. The catalyst is a commercial catalyst coated with an active material of titanium dioxide, vanadium and tungsten on a metal support, and is a plate catalyst having a sheet pitch of 7 mm.
시험촉매는 비교시험을 위하여 2개의 모듈을 준비하였는데, 케이싱 크기는 가로 0.8m x 세로 0.5m x 높이 0.7m 이고, 재질은 스테인레스 스틸이다. 상기 모듈을 재생장치에 장착하여 한 모듈은 0.25M H2SO4 에서 나머지 모듈은 0.25M H2SO4 + 0.025M CSN2H4 혼합 용액에서 각각 60 분간 세정하였다.
The test catalyst prepared two modules for the comparative test, the casing size is 0.8mx horizontal 0.5mx height 0.7m, the material is stainless steel. The module was mounted in a regeneration apparatus, and one module was washed for 60 minutes in 0.25MH 2 SO 4 and the other module in 0.25MH 2 SO 4 + 0.025M CSN 2 H 4 mixed solution.
(부피비 물: H2SO4 : CSN2H4 = 96.8 : 3 : 0.2)0.25MH 2 SO 4 + 0.025M CSN 2 H 4 Mixed Solution Regeneration Catalyst
(Volume ratio water: H 2 SO 4 : CSN 2 H 4 = 96.8: 3: 0.2)
<< 시험예Test Example 1～3> 질소산화물 제거율 측정 1 ～ 3> Nitrogen oxide removal rate measurement
실시예 1～3에 따라 준비된 촉매와 상용촉매 반응기를 각각 제작하여 중유 발전소의 배기가스(산소농도 3.0%, 수분 11%, 질소산화물 300ppm, 이산화황 1,400ppm 등)에서 약 1,000Nm3/h(반응기당) 추출하여 암모니아/질소산화물 몰비 1.0, 반응온도 350℃에서 약 10,000 시간 동안 운영 시험을 하였다. 질소산화물의 농도는 비분산적외선법을 사용하는 계측기를 사용하여 측정한 결과, 하기 표 2와 같이 2,500시간, 5,000시간 및 10,000 시간을 기준으로 황산용액 및 황산 + 티오우레아 혼합용액으로 재생된 촉매에서 모두 85% 이상의 질소산화물 제거율을 보였다.
About 1,000 Nm3 / h (per reactor) was produced in the exhaust gas (oxygen concentration 3.0%, moisture 11%, nitrogen oxide 300ppm, sulfur dioxide 1,400ppm, etc.) of the heavy oil power plant by producing catalysts and commercial catalyst reactors prepared according to Examples 1 to 3, respectively. Extraction was carried out for an operation test for about 10,000 hours at an ammonia / nitrogen oxide molar ratio of 1.0 and a reaction temperature of 350 ° C. The concentration of nitrogen oxide was measured using a non-dispersive infrared method. As a result, the catalyst was regenerated with sulfuric acid solution and sulfuric acid + thiourea mixed solution based on 2,500 hours, 5,000 hours, and 10,000 hours as shown in Table 2 below. All showed more than 85% NOx removal.
CSN2H4 혼합용액 재생촉매0.25MH 2 SO 4 + 0.025M
CSN 2 H 4 Mixed Solution Regeneration Catalyst
<시험예 4～6> SO3/SO2 산화율<Test Examples 4-6> Oxidation Rate of SO 3 / SO 2
실시예 1-3 촉매 및 시험예 1-3 조건에서 CCD(Controlled Condensation Method) 방법을 이용하여 촉매에 의해 산화된 SO3 농도를 촉매 반응온도 350℃를 유지한 상태로 약 1시간을 H2SO4로 응축 포집하여 이온크로마토그래피로 측정하였다. 표 3과 같이 황산 + 티오우레아혼합용액으로 재생된 촉매의 SO2 산화율은 0.4 %이하로 10,000 시간 경과 후에 황산용액으로만 재생한 촉매와 비교하여 약 70% 이상 줄었다. 이는 혼합용액으로 재생시, 촉매표면에 SO2 산화반응을 촉진시키는 철(Fe)이온이 감소하였다는 것을 의미한다. 즉, 혼합용액 재생시에 스테인레스로 만들어진 판형 (plate) 촉매 케이싱의 부식정도가 크게 감소하였기 때문이다.
Example 1-3 Catalyst and Test Example 1-3 Using the CCD (Controlled Condensation Method) under the conditions, the concentration of SO3 oxidized by the catalyst was maintained for about 1 hour while maintaining the catalytic reaction temperature of 350 ° C. in H 2 SO 4 It was collected by condensation and measured by ion chromatography. As shown in Table 3, the SO 2 oxidation rate of the catalyst regenerated with the sulfuric acid + thiourea mixture solution was 0.4% or less, and was reduced by about 70% or more compared to the catalyst regenerated with sulfuric acid solution after 10,000 hours. This means that when regenerating with the mixed solution, iron (Fe) ions that promote the SO 2 oxidation reaction on the catalyst surface were reduced. That is, the corrosion degree of the plate catalyst casing made of stainless steel was greatly reduced when the mixed solution was regenerated.
CSN2H4 혼합용액 재생촉매0.25MH 2 SO 4 + 0.025M
CSN 2 H 4 Mixed Solution Regeneration Catalyst
<시험예 7～9> 질소산화물 제거율 측정<Test Examples 7-9> Determination of nitrogen oxide removal rate
시험촉매의 표면에 침투한 철(Fe) 농도를 Inductively Coupled Plasma-AtomicEmission Spectrometry(ICP-AES)로 분석하였다.The iron (Fe) concentration penetrating the surface of the test catalyst was analyzed by Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES).
10,000 시간 경과 된 촉매의 경우, 혼합용액 재생 시에 촉매표면의 Fe 농도가 황산용액재생 촉매보다 약 50 % 감소했음을 알 수 있다.
In the case of the catalyst which has passed 10,000 hours, it can be seen that the Fe concentration on the surface of the catalyst was reduced by about 50% compared to the sulfuric acid solution regeneration catalyst when the mixed solution was regenerated.
CSN2H4 혼합용액 재생촉매0.25MH 2 SO 4 + 0.025M
CSN 2 H 4 Mixed Solution Regeneration Catalyst
본 발명은 첨부된 도면에 도시된 일 실시예를 참고로 설명되었으나 이는 예시적인 것에 불과하며, 당해 기술분야에서 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 타 실시예가 가능하다는 점을 이해할 수 있을 것이다. 따라서, 본 발명의 진정한 보호 범위는 첨부된 청구 범위에 의해서만 정해져야 할 것이다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation and that those skilled in the art will recognize that various modifications and equivalent arrangements may be made therein. It will be possible. Accordingly, the true scope of protection of the present invention should be determined only by the appended claims.
Claims (8)
상기 세정액에 아민 또는 사이오화합물을 추가로 첨가한 혼합액을 사용하여 재생공정을 거치는 판형 배연탈질 폐촉매의 재생방법.
In a regeneration process in which a waste denitrification catalyst module containing titanium dioxide, vanadium and tungsten having reduced activity is used in a washing apparatus with an aqueous acid solution as a washing liquid,
Regeneration method of the plate-type flue gas denitrification waste catalyst is subjected to a regeneration process using a mixed solution in which the amine or thio compound is further added to the cleaning liquid.
상기 혼합액은 물, 산 및 첨가물의 부피비가 각각 98.93:1.0:0.07 내지 90.4:9:0.6 의 범위내인 것을 만족하는 것을 특징으로 하는 판형 배연탈질 폐촉매의 재생방법.
The method according to claim 1,
The mixed solution is a volume ratio of water, acid and additives are satisfied that the range of 98.93: 1.0: 0.07 to 90.4: 9: 0.6, respectively.
상기 산은 황산, 상기 첨가물은 티오우레아를 사용하고, 물, 황산 및 티오우레아의 부피비는 96.8:3:0.2인 것을 특징으로 하는 판형 배연탈질 폐촉매의 재생방법.
The method according to claim 2,
The acid is sulfuric acid, the additive is thiourea, the volume ratio of water, sulfuric acid and thiourea is 96.8: 3: 0.2, characterized in that the regeneration of the plate-type flue gas denitrification waste catalyst.
상기 판형촉매의 판 간격은 7mm인 것을 특징으로 하는 판형 배연탈질폐촉매의 재생방법.
The method according to claim 1,
Regeneration method of the plate-type flue gas denitrification catalyst, characterized in that the plate spacing of the plate catalyst is 7mm.
상기 산 수용액은 황산 또는 유기산 수용액인 것을 특징으로 하는 판형 배연탈질 폐촉매의 재생방법.
The method according to claim 1,
The acid solution is a sulfuric acid or organic acid aqueous solution of the plate-type flue gas denitrification waste catalyst, characterized in that.
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