JP2015116512A - Adsorbent for removing arsenic or phosphorus from flue gas and flue gas purification method using the same - Google Patents
Adsorbent for removing arsenic or phosphorus from flue gas and flue gas purification method using the same Download PDFInfo
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Abstract
Description
本発明は、燃焼排ガスから砒素またはリンを除去するための吸着剤およびそれを用いた燃焼排ガスの浄化方法に関する。より詳細に、本発明は、使用済み脱硝触媒の再利用などによって安価に得られる、燃焼排ガスから砒素またはリンを除去するための吸着剤およびそれを用いた燃焼排ガスの浄化方法に関する。 The present invention relates to an adsorbent for removing arsenic or phosphorus from combustion exhaust gas and a method for purifying combustion exhaust gas using the same. More specifically, the present invention relates to an adsorbent for removing arsenic or phosphorus from combustion exhaust gas, which can be obtained at low cost by reusing a used denitration catalyst, and a method for purifying combustion exhaust gas using the same.
脱硝触媒の存在下で燃焼排ガス中の窒素酸化物をアンモニア若しくは尿素で接触還元することを含む燃焼排ガス浄化方法が知られている。この浄化方法に用いられる脱硝触媒として、酸化チタンを主成分とするものが、活性が高く耐久性に優れるということで、国内外で広く用いられている。燃焼排ガスには砒素やリンなどの触媒毒が含まれていることがある。これら触媒毒が脱硝触媒に付着して堆積すると、脱硝性能が低下する。そのため、脱硝率が規格値未満になった使用済み脱硝触媒は新しい脱硝触媒に取り換えられる。 A combustion exhaust gas purification method including catalytic reduction of nitrogen oxides in combustion exhaust gas with ammonia or urea in the presence of a denitration catalyst is known. As a denitration catalyst used in this purification method, a catalyst mainly composed of titanium oxide is widely used both at home and abroad because of its high activity and excellent durability. Combustion exhaust gas may contain catalyst poisons such as arsenic and phosphorus. When these catalyst poisons adhere to and accumulate on the denitration catalyst, the denitration performance decreases. Therefore, the used denitration catalyst whose denitration rate is less than the standard value is replaced with a new denitration catalyst.
砒素やリンなどの触媒毒による脱硝触媒の劣化を防止するために、脱硝触媒の組成や成分等の改良によりリンや砒素などに対する耐久性を高める方法(例えば、特許文献４)、アルミナやゼオライト等の吸着剤を用いてリンや砒素を燃焼排ガスから除去し、脱硝触媒に付着する量を低減させる方法（例えば、特許文献５、６または７）などが提案されている。 In order to prevent deterioration of the denitration catalyst due to catalyst poisons such as arsenic and phosphorus, a method for improving durability against phosphorus and arsenic by improving the composition and components of the denitration catalyst (for example, Patent Document 4), alumina, zeolite, etc. A method for removing phosphorus and arsenic from combustion exhaust gas using an adsorbent of the above and reducing the amount adhering to the denitration catalyst (for example, Patent Document 5, 6 or 7) has been proposed.
一方で、廃棄物の低減、資源の有効活用などの観点から、使用済み脱硝触媒を再生して再利用する方法が提案されている（特許文献１、２、３など）。 On the other hand, from the viewpoint of reducing waste and effectively utilizing resources, methods for regenerating and reusing used denitration catalysts have been proposed (Patent Documents 1, 2, 3, etc.).
本発明の目的は、使用済み脱硝触媒の再利用などによって安価に得られる、燃焼排ガスから砒素またはリンを除去するための吸着剤およびそれを用いた燃焼排ガスの浄化方法を提供することにある。 An object of the present invention is to provide an adsorbent for removing arsenic or phosphorus from combustion exhaust gas, which can be obtained at low cost by reusing a used denitration catalyst, and a method for purifying combustion exhaust gas using the same.
本発明者らは上記目的を達成するために検討した結果、以下の形態を包含する本発明を完成するに至った。 As a result of studies to achieve the above object, the present inventors have completed the present invention including the following modes.
〔１〕 酸化チタンと脱硝触媒活性を有する金属元素とを含有し、且つ燃焼排ガスの浄化処理における使用で砒素化合物またはリン化合物との反応性を有する鉄成分をさらに含有するようになった使用済み脱硝触媒からなる、砒素またはリンを除去するための吸着剤。
〔２〕 砒素化合物またはリン化合物との反応性を有する鉄成分が硫酸鉄である、〔１〕に記載の砒素またはリンを除去するための吸着剤。
[1] Used that contains titanium oxide and a metal element having denitration catalytic activity, and further contains an iron component that is reactive with an arsenic compound or phosphorus compound when used in purification treatment of combustion exhaust gas An adsorbent composed of a denitration catalyst for removing arsenic or phosphorus.
[2] The adsorbent for removing arsenic or phosphorus according to [1], wherein the iron component having reactivity with an arsenic compound or phosphorus compound is iron sulfate.
〔３〕 砒素またはリンを含有する燃焼排ガスを、
〔１〕または〔２〕に記載の吸着剤が設置された層を通過させ、
次いで、脱硝触媒が設置された層を通過させる
ことを含む、燃焼排ガスの浄化方法。
[3] Combustion exhaust gas containing arsenic or phosphorus,
[1] or [2] is passed through the layer in which the adsorbent is installed,
Next, a method for purifying combustion exhaust gas, including passing through a layer provided with a denitration catalyst.
〔４〕 酸化チタンを主成分とし、灰中の鉄分もしくは金属基板の腐食にともない鉄成分濃度が上昇した使用済み触媒を、砒素もしくは燐化合物を含む排ガスに用いる脱硝触媒の上流部に設置して、砒素もしくは燐の吸着剤として用いることを特徴とする脱硝触媒の再利用方法。 [4] Install a used catalyst whose main component is titanium oxide and whose iron content in the ash increases due to corrosion of the metal substrate or upstream of the denitration catalyst used for exhaust gas containing arsenic or phosphorus compounds. A method for reusing a denitration catalyst characterized by being used as an adsorbent for arsenic or phosphorus.
本発明に係る吸着剤は、燃焼排ガスからリンおよび砒素を効果的に除去することができ、リンや砒素による脱硝触媒の劣化を防止でき、脱硝触媒の寿命を延ばすことができる。本発明の吸着剤は使用済み脱硝触媒の再利用などによって得られるので安価である。 The adsorbent according to the present invention can effectively remove phosphorus and arsenic from combustion exhaust gas, can prevent deterioration of the denitration catalyst due to phosphorus and arsenic, and can extend the life of the denitration catalyst. The adsorbent of the present invention is inexpensive because it can be obtained by reusing a used denitration catalyst.
本発明に係る吸着剤は、酸化チタンと、脱硝触媒活性を有する金属元素と、砒素化合物またはリン化合物との反応性を有する鉄成分とを含有するものである。該吸着剤は、好ましくは、燃焼排ガス中の砒素またはリンの吸着に用いられる。 The adsorbent according to the present invention contains titanium oxide, a metal element having catalytic activity for denitration, and an iron component having reactivity with an arsenic compound or a phosphorus compound. The adsorbent is preferably used for adsorption of arsenic or phosphorus in the combustion exhaust gas.
本発明に用いられる酸化チタンとしては、二酸化チタン(TiO2)の粉末、スラリまたはペースト；オルトチタン酸もしくはメタチタン酸(H2TiO3)の粉末、スラリまたはペーストなどが挙げられる。
脱硝触媒活性を有する元素として、V、Mo、Wなどが挙げられる。係る金属元素を含有する化合物としては、メタバナジン酸アンモニウム、三酸化モリブデン、モリブデン酸アンモニウム、タングステン酸アンモニウムなどが挙げられる。
本発明に係る吸着剤にはSiやAlなどの元素が含まれていてもよい。Siはバインダとして機能することがある。SiやAlなどの元素を含むものとして、例えば、シリカ、アルミナ、カオリナイト、活性白土、酸性白土、ゼオライトなどが挙げられる。
砒素化合物またはリン化合物との反応性を有する鉄成分としては、好ましくは硫酸鉄が挙げられる。
Examples of the titanium oxide used in the present invention include titanium dioxide (TiO 2 ) powder, slurry or paste; orthotitanic acid or metatitanic acid (H 2 TiO 3 ) powder, slurry or paste.
V, Mo, W etc. are mentioned as an element which has a denitration catalyst activity. Examples of the compound containing such a metal element include ammonium metavanadate, molybdenum trioxide, ammonium molybdate, and ammonium tungstate.
The adsorbent according to the present invention may contain elements such as Si and Al. Si may function as a binder. Examples of elements containing elements such as Si and Al include silica, alumina, kaolinite, activated clay, acidic clay, and zeolite.
The iron component having reactivity with an arsenic compound or phosphorus compound is preferably iron sulfate.
本発明に係る吸着剤は、例えば、酸化チタンと、脱硝触媒活性を有する金属元素を含有する化合物と、砒素化合物またはリン化合物との反応性を有する鉄成分とを混ぜ合わせることによって製造することができる。さらに、混ぜ合わせた物を、ハニカム状、板状に成形してもよいし、金属製のラス基板や網、ガラス繊維製の織布などからなる基材に担持させて板状にしてもよい。また、酸化チタンと、脱硝触媒活性を有する金属元素を含有する化合物とを混ぜ合わせ、それを、上記のような形状に成形または基材に担持して脱硝触媒を得、次いで該脱硝触媒に鉄成分を含浸させることによって製造してもよい。 The adsorbent according to the present invention can be produced, for example, by mixing titanium oxide, a compound containing a metal element having denitration catalytic activity, and an iron component having reactivity with an arsenic compound or a phosphorus compound. it can. Further, the mixed product may be formed into a honeycomb shape or a plate shape, or may be formed into a plate shape by being supported on a base material made of a metal lath substrate, a net, a glass fiber woven fabric, or the like. . In addition, titanium oxide and a compound containing a metal element having a denitration catalytic activity are mixed and molded into a shape as described above or supported on a base material to obtain a denitration catalyst, and then iron is added to the denitration catalyst. You may manufacture by impregnating an ingredient.
本発明においては燃焼排ガスの浄化処理に使用済みの脱硝触媒を吸着剤として用いることが好ましい。脱硝触媒には、酸化チタンと脱硝触媒活性を有する金属元素とが含まれているものがある。この脱硝触媒を燃焼排ガスの浄化処理に使用すると、燃焼排ガスに含まれる灰が脱硝触媒に付着し堆積する。灰には鉄元素を含む化合物が含まれており、燃焼排ガスに含まれるSO2などの硫黄酸化物が該鉄元素を含む化合物と反応して硫酸鉄などを生成し、該硫酸鉄などが触媒層に移行することがある。また、酸化チタンと脱硝触媒活性を有する金属元素とをステンレス鋼（例えば、SUS430)製ラス基板などのような鉄製基材に担持してなる脱硝触媒の場合には、燃焼排ガスの浄化処理に使用している間に、基材の腐食などによって硫酸鉄などが生成し、それが基材から触媒層に移行することがある。このような使用済み脱硝触媒を本発明に係る吸着剤として用いることは、資源の有効利用、製造コストの削減に大きく寄与する。板状の吸着剤は圧力損失が低く、ダストなどによる摩耗にも強いので好ましい。
また、硫酸鉄などの鉄成分が触媒層に移行していない使用済み脱硝触媒は、含浸などの公知の方法に従って、それに砒素化合物またはリン化合物との反応性を有する鉄成分（硫酸鉄など）を含有させることによって、本発明に係る吸着剤を得ることもできる。
In the present invention, it is preferable to use a denitration catalyst that has been used for purification treatment of combustion exhaust gas as an adsorbent. Some denitration catalysts include titanium oxide and a metal element having denitration catalytic activity. When this denitration catalyst is used for purification treatment of combustion exhaust gas, ash contained in the combustion exhaust gas adheres to and accumulates on the denitration catalyst. Ash contains a compound containing iron element, and sulfur oxides such as SO 2 contained in combustion exhaust gas react with the compound containing iron element to produce iron sulfate and the like. May move to layer. Also, in the case of a denitration catalyst in which titanium oxide and a metal element having a denitration catalyst activity are supported on an iron base such as a stainless steel (for example, SUS430) lath substrate, it is used for purification treatment of combustion exhaust gas. During this process, iron sulfate or the like may be generated due to corrosion of the base material, and may be transferred from the base material to the catalyst layer. Use of such a used denitration catalyst as the adsorbent according to the present invention greatly contributes to effective use of resources and reduction of production costs. A plate-like adsorbent is preferable because it has a low pressure loss and is resistant to abrasion caused by dust.
In addition, a used denitration catalyst in which an iron component such as iron sulfate has not transferred to the catalyst layer is subjected to an iron component (such as iron sulfate) having reactivity with an arsenic compound or phosphorus compound according to a known method such as impregnation. By making it contain, the adsorption agent which concerns on this invention can also be obtained.
硫酸鉄などは、式(1)や式(2)で表わされる反応をして、燃焼排ガス中の砒素成分をヒ酸鉄のような安定な化合物に転化して捕捉する。
Fe2(SO4)3 + As2O5 → 2FeAsO4 + 3SO3 (1)
3FeSO4 + As2O5 → Fe3(AsO4)2 + 3SO3 (2)
また、燃焼排ガス中のリン成分は、砒素成分と同様に、硫酸鉄などと反応して捕捉される。
Iron sulfate or the like reacts by the formulas (1) and (2) to convert and capture arsenic components in the combustion exhaust gas into stable compounds such as iron arsenate.
Fe 2 (SO 4 ) 3 + As 2 O 5 → 2FeAsO 4 + 3SO 3 (1)
3FeSO 4 + As 2 O 5 → Fe 3 (AsO 4 ) 2 + 3SO 3 (2)
Further, the phosphorus component in the combustion exhaust gas reacts with iron sulfate or the like and is captured similarly to the arsenic component.
本発明に係る吸着剤は、例えば、次のような方法で燃焼排ガスの浄化に用いることができる。砒素またはリンを含有する燃焼排ガスを、本発明に係る吸着剤が設置された層を通過させ、次いで、脱硝触媒が設置された層を通過させる。例えば、使用済み脱硝触媒を、本発明に係る吸着剤として、脱硝装置に設置した脱硝触媒の前段に設置することを含む。本発明に係る吸着剤は、燃焼排ガス中の砒素やリンを捕捉し、後段に設置された脱硝触媒に砒素やリンが付着するのを抑制し、脱硝触媒の劣化を防止することができる。 The adsorbent according to the present invention can be used, for example, for purification of combustion exhaust gas by the following method. Combustion exhaust gas containing arsenic or phosphorus is passed through a layer in which an adsorbent according to the present invention is installed, and then passed through a layer in which a denitration catalyst is installed. For example, it includes installing a used denitration catalyst as an adsorbent according to the present invention in front of a denitration catalyst installed in a denitration apparatus. The adsorbent according to the present invention captures arsenic and phosphorus in the combustion exhaust gas, suppresses arsenic and phosphorus from adhering to the denitration catalyst installed in the subsequent stage, and prevents the denitration catalyst from deteriorating.
一般に、鉄成分（硫酸鉄など）は燃焼排ガス中のSO2を酸化させる作用を持つ。脱硝触媒に鉄成分が含まれていると脱硝触媒のSO2酸化率を高める。ところが、本発明によると、式(1)及び式(2)で表わされる反応によって砒素やリンが鉄成分に反応して鉄成分のSO2酸化活性を奪う。脱硝触媒の前段に設置された吸着剤には、新たな灰が付着し且つSO2などの硫黄酸化物が供給されるので、前述した反応で失われた硫酸鉄などが補給される。これによって、本発明の吸着剤は、長期に亘って砒素やリンを吸着し続けることができる。 In general, iron components (such as iron sulfate) have an action of oxidizing SO 2 in combustion exhaust gas. If the denitration catalyst contains an iron component, the SO 2 oxidation rate of the denitration catalyst is increased. However, according to the present invention, arsenic or phosphorus reacts with the iron component by the reactions represented by the formulas (1) and (2) to deprive the SO 2 oxidation activity of the iron component. Since the adsorbent installed in the front stage of the denitration catalyst is attached with new ash and supplied with sulfur oxides such as SO 2, iron sulfate lost in the above-described reaction is replenished. Thereby, the adsorbent of the present invention can continue to adsorb arsenic and phosphorus over a long period of time.
以下に実施例を示して本発明をより具体的に説明する。なお、本発明はこれら実施例によって限定されるものではない。 The present invention will be described more specifically with reference to the following examples. In addition, this invention is not limited by these Examples.
実施例１
脱硝触媒(SUS430製メタルラス基板に、チタン、タングステン及びバナジウムの各酸化物を含有する触媒(Ti/W/V原子比=95/4/1)が担持されてなる板状触媒)を用意した。これを20mm×20mmサイズに切り出した。この脱硝触媒に、使用済みの状態を模擬するために、硫酸鉄水溶液を浸み込ませて、酸化鉄換算で1.3重量％の鉄成分を含有する板状触媒を得た。これを吸着剤とした。
Example 1
A denitration catalyst (a plate-like catalyst in which titanium, tungsten, and vanadium oxide catalysts (Ti / W / V atomic ratio = 95/4/1) are supported on a SUS430 metal lath substrate) was prepared. This was cut into a size of 20 mm × 20 mm. In order to simulate the used state, this denitration catalyst was immersed in an iron sulfate aqueous solution to obtain a plate catalyst containing 1.3% by weight of an iron component in terms of iron oxide. This was used as an adsorbent.
（砒素吸着試験）
該吸着剤を流通式反応管内に設置し、反応管を350℃に加温した。表１に示す組成の石炭燃焼模擬排ガスを該反応管に350℃にてAV 85m/hで50時間流した。流通式反応管から吸着剤を取り出し、ラス基板から触媒層を剥がし、蛍光X線分析装置(XRF、(株)リガク製 RIX3000)を用いて、触媒層に含まれる砒素と鉄の量を分析した。結果を表２に示す。
(Arsenic adsorption test)
The adsorbent was placed in a flow reaction tube, and the reaction tube was heated to 350 ° C. Coal combustion simulated exhaust gas having the composition shown in Table 1 was allowed to flow through the reaction tube at 350 ° C. at AV 85 m / h for 50 hours. The adsorbent was taken out from the flow type reaction tube, the catalyst layer was peeled off from the lath substrate, and the amount of arsenic and iron contained in the catalyst layer was analyzed using a fluorescent X-ray analyzer (XRF, RIX3000 manufactured by Rigaku Corporation). . The results are shown in Table 2.
比較例１
硫酸鉄を含浸させなかった以外は実施例1と同じ方法で吸着剤を得た。この吸着剤について実施例１と同じ試験を行って、砒素および鉄の量を分析した。結果を表２に示す。
Comparative Example 1
An adsorbent was obtained in the same manner as in Example 1 except that iron sulfate was not impregnated. This adsorbent was subjected to the same test as in Example 1 to analyze the amounts of arsenic and iron. The results are shown in Table 2.
表２に示すとおり、本発明の吸着剤（実施例１）は燃焼排ガス中の砒素の吸着能が高い。 As shown in Table 2, the adsorbent of the present invention (Example 1) has a high ability to adsorb arsenic in combustion exhaust gas.
実施例２
脱硝触媒(SUS430製メタルラス基板に、チタン、タングステン及びバナジウムの各酸化物を含有する触媒(Ti/W/V原子比=95/4/1)が担持されてなる板状触媒)を用意した。これを20mm×100mmサイズに切り出した。この脱硝触媒に、使用済みの状態を模擬するために、硫酸鉄水溶液を浸み込ませ、次いでAs2O5水溶液を浸み込ませて、酸化鉄換算で1.3重量％の鉄成分と、As2O3換算で1.2重量％の砒素成分を含有する板状触媒を得た。これを吸着剤とした。
Example 2
A denitration catalyst (a plate-like catalyst in which titanium, tungsten, and vanadium oxide catalysts (Ti / W / V atomic ratio = 95/4/1) are supported on a SUS430 metal lath substrate) was prepared. This was cut into a size of 20 mm × 100 mm. In order to simulate the used state, this denitration catalyst is immersed in an aqueous iron sulfate solution and then in an As 2 O 5 aqueous solution, and the iron component in terms of iron oxide of 1.3% by weight and As A plate catalyst containing 1.2% by weight of an arsenic component in terms of 2 O 3 was obtained. This was used as an adsorbent.
（SO2酸化率試験）
該吸着剤３枚を流通式反応管内に設置し、反応管を350℃に加温した。表３に示す組成の石炭燃焼模擬排ガスを該反応管に350℃にてAV 17m/hで流した。SO2酸化率を測定した。
また、流通式反応管から吸着剤を取り出し、ラス基板から触媒層を剥がし、蛍光X線分析装置(XRF、(株)リガク製 RIX3000)を用いて、触媒層に含まれる砒素と鉄の量を分析した。結果を表４に示す。
(SO 2 oxidation rate test)
Three adsorbents were placed in a flow reaction tube, and the reaction tube was heated to 350 ° C. Coal combustion simulated exhaust gas having the composition shown in Table 3 was allowed to flow through the reaction tube at 350 ° C. at AV 17 m / h. The SO 2 oxidation rate was measured.
In addition, the adsorbent is taken out from the flow reaction tube, the catalyst layer is peeled off from the glass substrate, and the amount of arsenic and iron contained in the catalyst layer is measured using an X-ray fluorescence analyzer (XRF, RIX3000 manufactured by Rigaku Corporation). analyzed. The results are shown in Table 4.
実施例３
脱硝触媒(SUS430製メタルラス基板に、チタン、タングステン及びバナジウムの各酸化物を含有する触媒(Ti/W/V原子比=95/4/1)が担持されてなる板状触媒)を用意した。これを20mm×100mmサイズに切り出した。この脱硝触媒に、使用済みの状態を模擬するために、硫酸鉄水溶液を浸み込ませ、次いでH3PO4水溶液を浸み込ませて、酸化鉄換算で1.3重量％の鉄成分と、P2O5換算で1.2重量％のリン成分とを含有する板状触媒を得た。これを吸着剤とした。
該吸着剤について実施例２と同じ試験を行って、SO2酸化率を測定した。また、流通式反応管から吸着剤を取り出し、ラス基板から触媒層を剥がし、蛍光X線分析装置(XRF、(株)リガク製 RIX3000)を用いて、触媒層に含まれるリンと鉄の量を分析した。結果を表４に示す。
Example 3
A denitration catalyst (a plate-like catalyst in which titanium, tungsten, and vanadium oxide catalysts (Ti / W / V atomic ratio = 95/4/1) are supported on a SUS430 metal lath substrate) was prepared. This was cut into a size of 20 mm × 100 mm. In order to simulate the used state, this denitration catalyst is impregnated with an iron sulfate aqueous solution and then with an H 3 PO 4 aqueous solution, and an iron component of 1.3% by weight in terms of iron oxide, P A plate-like catalyst containing 1.2% by weight of a phosphorus component in terms of 2 O 5 was obtained. This was used as an adsorbent.
The same test as in Example 2 was performed on the adsorbent, and the SO 2 oxidation rate was measured. In addition, the adsorbent is taken out from the flow reaction tube, the catalyst layer is peeled off from the lath substrate, and the amount of phosphorus and iron contained in the catalyst layer is measured using a fluorescent X-ray analyzer (XRF, RIX3000 manufactured by Rigaku Corporation). analyzed. The results are shown in Table 4.
実施例４
As2O5水溶液を浸み込ませなかった以外は実施例２と同じ方法で吸着剤を得た。この吸着剤について実施例２と同じ試験を行って、SO2酸化率を測定した。また、流通式反応管から吸着剤を取り出し、ラス基板から触媒層を剥がし、蛍光X線分析装置(XRF、(株)リガク製 RIX3000)を用いて、触媒層に含まれる砒素、リンおよび鉄の量を分析した。結果を表４に示す。
Example 4
An adsorbent was obtained in the same manner as in Example 2 except that the As 2 O 5 aqueous solution was not soaked. This adsorbent was subjected to the same test as in Example 2 to measure the SO 2 oxidation rate. Also, take out the adsorbent from the flow reaction tube, peel off the catalyst layer from the glass substrate, and use an X-ray fluorescence analyzer (XRF, RIX3000 manufactured by Rigaku Corporation) to arsenic, phosphorus and iron contained in the catalyst layer. The amount was analyzed. The results are shown in Table 4.
表４に示すとおり、砒素またはリンを吸着した後の吸着剤（実施例２および３）は、SO2酸化率が、砒素またはリンを吸着していない吸着剤（実施例４）に比べて、低い。 As shown in Table 4, the adsorbents after adsorbing arsenic or phosphorus (Examples 2 and 3) have an SO 2 oxidation rate higher than that of the adsorbent not adsorbing arsenic or phosphorus (Example 4). Low.
実施例５
未使用の脱硝触媒(SUS430製メタルラス基板に、チタン、タングステン及びバナジウムの各酸化物を含有する触媒層(Ti/W/V原子比=95/4/1)が担持されてなる板状触媒)を用意した。この脱硝触媒を石炭炊きボイラの排ガス浄化用の脱硝装置に設置し、燃焼排ガスの脱硝に20,000時間使用した。その後、脱硝装置から使用済み脱硝触媒を取り出した。該使用済み脱硝触媒は、触媒層に硫酸鉄などの鉄成分が含まれていた。取り出した使用済み脱硝触媒を100mm角の大きさに切り出して、吸着剤とした。
Example 5
Unused denitration catalyst (plate catalyst in which a catalyst layer containing Ti, W, and V vanadium oxides (Ti / W / V atomic ratio = 95/4/1) is supported on a SUS430 metal lath substrate) Prepared. This denitration catalyst was installed in a denitrification device for exhaust gas purification of a coal-fired boiler and used for 20,000 hours for denitration of combustion exhaust gas. Thereafter, the used denitration catalyst was taken out from the denitration apparatus. The used denitration catalyst contained an iron component such as iron sulfate in the catalyst layer. The used spent denitration catalyst was cut out to a size of 100 mm square and used as an adsorbent.
（脱硝試験）
未使用の脱硝触媒(SUS430製メタルラス基板に、チタン、タングステン及びバナジウムの各酸化物を含有する触媒層(Ti/W/V原子比=95/4/1)が担持されてなる板状触媒)を用意した。この未使用脱硝触媒の脱硝率を測定した。結果を表５に示す。
未使用脱硝触媒３枚を流通式反応管内に設置した。前記未使用脱硝触媒３枚の総質量に対して、1/5の質量の前記吸着剤３枚を流通式吸着管内に設置した。流通式吸着管を前記流通式反応管の前段に設置した。流通式反応管を350℃に加温した。流通式吸着管および流通式反応管にこの順で表１に示す組成の石炭燃焼模擬排ガスを350℃にてAV 85m/hで50時間流した。次に、流通式反応管から脱硝触媒を取り出し、脱硝率と砒素蓄積量を測定した。結果を表５に示す。
(Denitration test)
Unused denitration catalyst (plate catalyst in which a catalyst layer containing Ti, W, and V vanadium oxides (Ti / W / V atomic ratio = 95/4/1) is supported on a SUS430 metal lath substrate) Prepared. The denitration rate of this unused denitration catalyst was measured. The results are shown in Table 5.
Three unused denitration catalysts were installed in the flow reaction tube. The three adsorbents having a mass of 1/5 with respect to the total mass of the three unused denitration catalysts were placed in a flow-type adsorption tube. A flow-type adsorption tube was installed in front of the flow-type reaction tube. The flow reaction tube was heated to 350 ° C. A coal combustion simulated exhaust gas having the composition shown in Table 1 was passed through the flow-type adsorption tube and flow-type reaction tube in this order at 350 ° C for 50 hours at AV 85 m / h. Next, the denitration catalyst was taken out from the flow reaction tube, and the denitration rate and the arsenic accumulation amount were measured. The results are shown in Table 5.
比較例２
流通式吸着管を流通式反応管の前段に設置しなかった以外は実施例５と同じ操作を行った。次に、流通式反応管から脱硝触媒を取り出し、脱硝性能と砒素蓄積量を測定した。結果を表５に示す。
Comparative Example 2
The same operation as in Example 5 was performed except that the flow-type adsorption tube was not installed in the previous stage of the flow-type reaction tube. Next, the denitration catalyst was taken out from the flow reaction tube, and the denitration performance and the arsenic accumulation amount were measured. The results are shown in Table 5.
表５に示すとおり、本発明に係る吸着剤を脱硝触媒が設置された反応管の前段に設置すると、脱硝触媒に付着する砒素の量を抑制することができるので、脱硝率の低下がほとんどない。 As shown in Table 5, when the adsorbent according to the present invention is installed in the front stage of the reaction tube in which the denitration catalyst is installed, the amount of arsenic adhering to the denitration catalyst can be suppressed, so there is almost no decrease in the denitration rate. .
Claims (4)
請求項１または２に記載の吸着剤が設置された層を通過させ、
次いで、脱硝触媒が設置された層を通過させる
ことを含む、燃焼排ガスの浄化方法。 Combustion exhaust gas containing arsenic or phosphorus,
Pass the layer in which the adsorbent according to claim 1 or 2 is installed,
Next, a method for purifying combustion exhaust gas, including passing through a layer provided with a denitration catalyst.
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| JP2017207047A (en) * | 2016-05-23 | 2017-11-24 | 日野自動車株式会社 | Exhaust emission control device |
| CN116510497A (en) * | 2023-06-26 | 2023-08-01 | 昆明理工大学 | Method and system for removing sulfur, phosphorus and nitrogen oxides in yellow phosphorus tail gas boiler by using phosphorus ore powder |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2017207047A (en) * | 2016-05-23 | 2017-11-24 | 日野自動車株式会社 | Exhaust emission control device |
| CN116510497A (en) * | 2023-06-26 | 2023-08-01 | 昆明理工大学 | Method and system for removing sulfur, phosphorus and nitrogen oxides in yellow phosphorus tail gas boiler by using phosphorus ore powder |
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