JP3796214B2 - Method for regenerating degraded catalyst - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、活性が低下して劣化した触媒の細孔中に活性金属イオンを含む水溶液を吸収させて新たに触媒活性成分を担持させて再生する劣化した触媒の再生処理方法に関する。
【０００２】
【従来の技術】
火力発電所、各種工場などの燃焼排ガス中に含まれる窒素酸化物は、環境汚染物質であることから、排ガス煙道中に触媒を設置してアンモニアを還元剤として用いる選択接触還元方法により除去する方法が広く用いられている。触媒としては酸化チタンを主成分として、これにバナジウム、タングステンやモリブデンなどを活性成分として添加した触媒材料をハニカム形状、板状または粒状に成型して使用されている。
【０００３】
これらの触媒は、１０年前後使用されることが多く、使用中にＳＯＸが酸性硫安となったり、ハロゲン化合物がアンモニア塩となり細孔を閉塞したり、ダストによる閉塞やアルカリ分による被毒、さらには活性成分の変質により劣化してしまうため、使用済み廃触媒として廃棄されている。
【０００４】
廃触媒量が膨大であることから、再生利用することが古くより試みられており、水や無機ないし有機酸で洗浄した後、溶出したバナジウムやタングステン化合物を補うために再度含浸担持させることによる再生方法が行われている(例えば、特許文献１〜４参照)。
【０００５】
【特許文献１】
特開昭５４−１０２９４号公報
【０００６】
【特許文献２】
特開昭５９−４９８４９号公報
【０００７】
【特許文献３】
特開昭６０−２０９２５１号公報
【０００８】
【特許文献４】
特開昭６０−２０９２５２号公報
【０００９】
【発明が解決しようとする課題】
前記特許文献に記載の方法は、水ないし酸で強制的に数時間もの洗浄を行うためバナジウムさらにはタングステンといった活性成分が溶出してしまい、そのため再度、溶出分の各活性成分を担持させることから工程が長くなり、再生コストが高くなることや処理液量が多くなり、溶出した活性成分を含有する処理液の再利用などの問題がある。
【００１０】
そこで、本発明は、前記従来技術の問題点を解決し、性能が低下し劣化した触媒を簡便で低コストな再生処理による劣化した触媒の再生処理方法を提供することにある。
【００１１】
【課題を解決するための手段】
本発明の劣化した触媒の再生処理方法は、性能が低下し劣化した触媒の再生処理方法において、バナジウム化合物及びタングステン化合物を溶解させた水溶液を、吸収させる時間を０．５〜５分にて前記触媒の細孔内に吸収させ、吸収された前記水溶液中の水分を蒸発除去することにより酸化バナジウム及び酸化タングステンをそれぞれ０．１〜１質量％及び０．１〜５質量％の担持率で前記触媒の細孔内に担持させることを特徴とする。
【００１２】
【発明の実施の形態】
本発明者らは、劣化した触媒成形体の細孔内に活性成分であるバナジウムとタングステンを同時に短時間で吸収させることにより、前記課題を達成できることを見出し、さらに、再生処理後の触媒活性を高めるとともに副反応として問題のあるＳＯ２の酸化率を抑制することができたことにより、本発明に至ったものである。
【００１３】
本発明による再生方法は、例えば、排ガス中の窒素酸化物を浄化する脱硝触媒の再生に対して用いることができるが、この再生処理の対象とする触媒の使用される分野はこれだけに限定されるものではなく、排ガス中のダイオキシン浄化触媒や、さらには各種反応プロセスに用いられている触媒の再生処理方法として用いることができる。
【００１４】
本発明で再生処理の対象とする触媒として、例えば、脱硝触媒は０．１〜２質量％の酸化バナジウムないし０．２〜２０質量％の酸化タングステンを含有する酸化チタン系触媒であるが、酸化チタンは耐硫黄酸化物用の担体として使用されていることから、耐硫黄酸化物性を要求されない排ガス処理で用いられるアルミナ担体系触媒でも構わない。脱硝触媒は、通常はハニカム構造を有するモノリス体が用いられるが、これ以外の球状や円柱状のペレットなどでも構わない。
これらの脱硝触媒成形体はミクロないしマクロ細孔を有し、約２ｌ／Ｋgの細孔容積を有する。
【００１５】
本発明の方法では、劣化した触媒の細孔内にバナジウム及びタングステン化合物を溶解させた水溶液を吸収させ、水分を蒸発させることによりバナジウム及びタングステン化合物を使用済み触媒上に担持させることにより再生するものである。
【００１６】
吸収させる水溶液中のバナジウム化合物は水溶性のものであれば、塩化バナジウム、硫酸バナジル、シュウ酸バナジルなどいずれでもよいが、好ましくはシュウ酸バナジルが用いられる。タングステン化合物についても水溶性であれば何でもよく、塩化タングステン、タングステン酸、タングステン酸アンモニウム、タングストリン酸などいずれでもよいが、好ましくはメタタングステン酸アンモニウムが用いられる。
【００１７】
細孔に前記水溶液を吸収させるには担持成分の溶出を防ぐ意味から必要最少量の液を吸収させることが好ましく、前記水溶液を吸収させるために必要な液量は、含浸法、スプレー法や、液循環吸収などの操作方法により異なってくるが、処理時間は０．５〜５分で終了させることができる。これ以上、短いと細孔内への液の吸収が不十分となり、これ以上長いと活性成分の溶出の問題が生ずる。
【００１８】
水溶液吸収後は触媒を乾燥させるだけでもよく、さらに２００〜４００℃で焼成しても構わない。再生処理後に担持される酸化バナジウムと酸化タングステンの担持率は吸収させる水溶液中に含まれるバナジウム化合物とタングステン化合物の濃度で決まるが、各酸化物としての担持率は酸化バナジウムとして０．１〜１質量％、酸化タングステンとして０．１〜５質量％が好ましく、これよりも低い担持率とすると再生後の脱硝活性の改善が充分でなく、これよりも高い担持率とすると副反応のＳＯ２酸化率が高くなる問題が生ずる。また、酸化バナジウムのみを担持させると脱硝活性は改善されるもののＳＯ２酸化活性も著しく上昇する問題があり、酸化タングステンのみを担持させるとＳＯ２の酸化活性は低いものの脱硝活性の改善が充分でない問題がある。
【００１９】
【実施例】
以下、実施例と比較例を用いて具体的に説明する。
【００２０】
図１は本発明の方法を実施するための装置の一例を示す概略図である。
【００２１】
薬液タンク１でバナジウムとタングステンの含有水溶液を調整する。性能が低下した脱硝触媒２の上部からポンプ３により薬液タンク１から水溶液をスプレー部４に送って噴霧する。噴霧された水溶液は脱硝触媒２の細孔に吸収され、残りは集液部５に集められ薬液タンク１へ戻して循環させる。
【００２２】
[実施例１]
シュウ酸バナジル(７０．９％ＶＯＣ２Ｏ４ キシダ化学)４ｇを水に加熱溶解させ２０ｍｌ水溶液を調整した（以下「Ｖ液」という。）。これとは別に、市販のメタタングステン酸アンモニウム水溶液（５０％ＷＯ３ 日本無機化学工業）を水と混合し４５ｍｌとした(以下「Ｗ液」という。)。
【００２３】
Ｖ液２０ｍｌに水を加え８０ｍｌとした液から、２５ｍｌ分取したものと、Ｗ液に水を加え３０ｍｌとした液から２５ｍｌ分取したものを混合した液５０ｍｌを調製した。
【００２４】
上記の液５０ｍｌに０．７５Ｖ２Ｏ５、１５％ＷＯ３、６９％ＴｉＯ２を０．７５Ｖ２Ｏ５、１５％ＷＯ３、６９％ＴｉＯ２を含有する使用済みの単セルハニカム(８ｍｍ□×２１０ｍｍ、１２ｇ)１本を２分間浸漬し、細孔内へバナジウムとタングステンを含む水溶液を吸収させた後、液切り、乾燥することにより、０．２５％Ｖ２Ｏ３と１％ＷＯ３を新たに担持させた再生処理触媒を得た。
処理した触媒ハニカムを下記の条件で脱硝性能試験を行い脱硝率とＳＯ２酸化率を測定した。
【００２５】
空間速度 ：１２０００ｈ−１
反応ガス組成：２００ｐｐｍＮＯ−ＮＨ３−４％−Ｏ２−５００ｐｐｍＳＯ２−１０％Ｈ２Ｏ−Ｎ２バランス、ＮＨ３／ＮＯモル比１．０、０．７４
温度 ：３７０℃
[実施例２]
実施例１のＷ液中のタングステン濃度を１／２倍にした以外は同様な方法により、０．２５％Ｖ２Ｏ３−０．５％ＷＯ３を新たに再生処理担持し、性能測定を行った。
【００２６】
[実施例３]
実施例1のＷ液中のタングステン濃度を２．５倍にした以外は同様な方法により、０．２５％Ｖ２Ｏ３−２．５％ＷＯ３を新たに再生処理担持し、性能測定を行った。
【００２７】
[実施例4]
実施例１のＶ液中のバナジウム濃度を２倍にした以外は同様な方法により、０．５％Ｖ２Ｏ３−１％ＷＯ３を新たに再生処理担持し、性能測定を行った。
【００２８】
[比較例１]
実施例１で用いた再生処理前の使用済み触媒をそのまま用いて性能測定を行った。
【００２９】
[比較例２]
実施例１で用いた再生処理前の使用済み触媒について、Ｖ液中のバナジウム濃度を１／８にした溶液５０ｍｌを浸漬液とした以外は同様な方法により０．２５％Ｖ２Ｏ３を新たに再生担持し、性能測定を行った。
【００３０】
[比較例３]
実施例１で用いた再生処理前の使用済み触媒について、Ｖ液中のバナジウム濃度を１／４にした溶液５０ｍｌを浸漬液とした以外は同様な方法により、０．５％Ｖ２Ｏ３を新たに再生担持氏、性能測定を行った。
【００３１】
[比較例4]
実施例１で用いた再生処理前の使用済み触媒について、Ｖ液中のバナジウム濃度を３／４にした溶液５０ｍｌを浸漬液とした以外は同様な方法により、１．５％Ｖ２Ｏ３を新たに再生担持氏、性能測定を行った。
【００３２】
実施例１〜４及び比較例１〜４の性能試験結果についてＮＨ３／ＮＯモル比１．０と０．７４での脱硝率の平均値とＳＯ２酸化率をまとめて表1に示す。
【００３３】
【表１】
【００３４】
比較例１の使用済み触媒の脱硝率、ＳＯ２酸化率と比べて、これにＶ２Ｏ３とＷＯ３をポアフィリング法で新たに担持させた触媒は実施例１〜４に示すように平均脱硝率は１０％以上、上昇していると同時に、実施例１〜３ではＳＯ２酸化率も低く抑えられている。実施例４では脱硝率は上昇しているものの、ＳＯ２酸化率は比較例１と比べて若干、高くなっている。しかしながら、Ｖ２Ｏ３のみをポアフィリング法で担持させた比較例３に示す触媒は、比較例１よりも高い脱硝率とともに、ＳＯ２酸化率も高くなっているのに対して、比較例３と比べて、実施例４は脱硝率は高くなって、ＳＯ２酸化率は低くなっている。
【００３５】
上記の結果から、活性低下した使用済み脱硝触媒にポアフィリング法で新たにＶ２Ｏ３とＷＯ３を担持させることで、脱硝率が高くなると同時にＳＯ２酸化率が抑制されることが分かり、本発明による再生処理方法は劣化触媒の性能改善に対して非常に有効な方法である。
【００３６】
【発明の効果】
本発明により劣化した触媒にＶ２Ｏ３とＷＯ３を同時担持させることにより、脱硝率が向上することから還元用に供給するアンモニア量を低減できることや、ＳＯ２酸化率を低く抑えることができることから反応器出口で生成する酸性硫安の量を低減し、閉塞等の問題を回避できるなどの脱硝反応効率の点で大きな利点が生ずる上、本発明による再生処理方法は最少の処理液量で短時間で行うことができる結果、再生処理コストを非常に低くすることができる長所がある。
【図面の簡単な説明】
【図１】 本発明の方法を実施するための装置の一例を示す概略図である。
【符号の説明】
１：薬液タンク
２：脱硝触媒
３：ポンプ
４：スプレー部
５：集液部[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for regenerating a deteriorated catalyst in which an aqueous solution containing active metal ions is absorbed in the pores of a catalyst that has deteriorated due to a decrease in activity, and a catalyst active component is newly supported and regenerated.
[0002]
[Prior art]
Nitrogen oxides contained in combustion exhaust gas from thermal power plants, various factories, etc. are environmental pollutants. Therefore, a catalyst is installed in the exhaust gas flue and removed by a selective catalytic reduction method using ammonia as a reducing agent. Is widely used. As a catalyst, a catalyst material in which titanium oxide is a main component and vanadium, tungsten, molybdenum, or the like is added as an active ingredient is molded into a honeycomb shape, a plate shape, or a granular shape.
[0003]
These catalysts are often used for about 10 years. During use, SO X becomes acidic ammonium sulfate, halogen compounds become ammonia salts and block pores, blockage by dust and poisoning by alkali, Furthermore, since it deteriorates due to the alteration of the active component, it is discarded as a used waste catalyst.
[0004]
Since the amount of the waste catalyst is enormous, it has been tried to recycle for a long time, and after washing with water, inorganic or organic acid, it is regenerated by impregnating and supporting it again to supplement the eluted vanadium and tungsten compounds. The method is performed (for example, refer patent documents 1-4).
[0005]
[Patent Document 1]
Japanese Patent Laid-Open No. 54-10294 [0006]
[Patent Document 2]
Japanese Patent Laid-Open No. 59-49849
[Patent Document 3]
JP-A-60-209251 [0008]
[Patent Document 4]
JP-A-60-209252
[Problems to be solved by the invention]
Since the method described in the above-mentioned patent document forcibly cleans with water or acid for several hours, active components such as vanadium and tungsten are eluted, so that each active component of the eluted component is supported again. There are problems such as a long process, a high regeneration cost, a large amount of treatment liquid, and a reuse of the treatment liquid containing the eluted active ingredient.
[0010]
Accordingly, the present invention is to solve the above-mentioned problems of the prior art, and to provide a method for regenerating a deteriorated catalyst by a simple and low-cost regeneration process for a deteriorated catalyst whose performance has deteriorated.
[0011]
[Means for Solving the Problems]
The method for regenerating a deteriorated catalyst according to the present invention is the method for regenerating a deteriorated catalyst due to a decrease in performance, wherein the time for absorbing the aqueous solution in which the vanadium compound and the tungsten compound are dissolved is 0.5 to 5 minutes. The vanadium oxide and the tungsten oxide are absorbed in the pores of the catalyst by evaporating and removing the water in the aqueous solution, thereby supporting the vanadium oxide and the tungsten oxide at a loading ratio of 0.1 to 1% by mass and 0.1 to 5% by mass, respectively. The catalyst is supported in the pores of the catalyst.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have found that the above problems can be achieved by simultaneously absorbing the active components vanadium and tungsten in the pores of the deteriorated catalyst molded body in a short time, and further, the catalytic activity after the regeneration treatment is improved. The present invention has been achieved because the oxidation rate of SO 2 , which is a problem as a side reaction, can be suppressed while being increased.
[0013]
The regeneration method according to the present invention can be used for, for example, regeneration of a denitration catalyst that purifies nitrogen oxides in exhaust gas, but the field in which the catalyst to be subjected to regeneration treatment is used is limited to this. Instead, it can be used as a method for regenerating a dioxin purification catalyst in exhaust gas or a catalyst used in various reaction processes.
[0014]
As a catalyst to be regenerated in the present invention, for example, a denitration catalyst is a titanium oxide catalyst containing 0.1 to 2% by mass of vanadium oxide or 0.2 to 20% by mass of tungsten oxide. Since titanium is used as a support for sulfur oxides, it may be an alumina support catalyst used in exhaust gas treatment that does not require sulfur oxide resistance. As the denitration catalyst, a monolith body having a honeycomb structure is usually used, but other spherical or cylindrical pellets may be used.
These denitration catalyst compacts have micro to macro pores and a pore volume of about 2 l / Kg.
[0015]
In the method of the present invention, an aqueous solution in which vanadium and a tungsten compound are dissolved is absorbed in the pores of a deteriorated catalyst, and the vanadium and the tungsten compound are supported on the used catalyst by evaporating water, thereby regenerating. It is.
[0016]
As long as the vanadium compound in the aqueous solution to be absorbed is water-soluble, vanadium chloride, vanadyl sulfate, vanadyl oxalate and the like may be used, but vanadyl oxalate is preferably used. The tungsten compound may be anything as long as it is water-soluble and may be any of tungsten chloride, tungstic acid, ammonium tungstate, tungstophosphoric acid, etc., but preferably ammonium metatungstate is used.
[0017]
In order to absorb the aqueous solution in the pores, it is preferable to absorb a minimum amount of liquid from the viewpoint of preventing elution of the supported component, and the amount of liquid necessary to absorb the aqueous solution is impregnation method, spray method, The treatment time can be completed in 0.5 to 5 minutes, depending on the operation method such as liquid circulation absorption. If it is shorter than this, the absorption of the liquid into the pores is insufficient, and if it is longer than this, the problem of elution of the active ingredient occurs.
[0018]
After absorption of the aqueous solution, the catalyst may be simply dried, and may be calcined at 200 to 400 ° C. The supporting rate of vanadium oxide and tungsten oxide supported after the regeneration treatment is determined by the concentration of vanadium compound and tungsten compound contained in the aqueous solution to be absorbed, but the supporting rate as each oxide is 0.1 to 1 mass as vanadium oxide. %, Preferably 0.1 to 5% by mass as tungsten oxide. If the loading rate is lower than this, the denitration activity after regeneration is not sufficiently improved, and if the loading rate is higher than this, the side reaction SO 2 oxidation rate This raises the problem of increasing Further, there is a problem of markedly elevated even SO 2 oxidation activity but when supporting the only vanadium oxide denitration activity is improved, oxidation activity when supporting the only tungsten oxide SO 2 is not sufficient improvement in low denitration activity There's a problem.
[0019]
【Example】
Hereinafter, specific description will be given using Examples and Comparative Examples.
[0020]
FIG. 1 is a schematic view showing an example of an apparatus for carrying out the method of the present invention.
[0021]
An aqueous solution containing vanadium and tungsten is prepared in the chemical tank 1. An aqueous solution is sent from the chemical solution tank 1 to the
[0022]
[Example 1]
4 g of vanadyl oxalate (70.9% VOC 2 O 4 Kishida Chemical) was dissolved in water by heating to prepare a 20 ml aqueous solution (hereinafter referred to as “V solution”). Separately, a commercially available aqueous solution of ammonium metatungstate (50% WO 3 Nippon Inorganic Chemical Industry) was mixed with water to make 45 ml (hereinafter referred to as “W solution”).
[0023]
50 ml of a solution prepared by mixing 25 ml of a solution obtained by adding water to 20 ml of solution V and preparing a solution of 25 ml from a solution prepared by adding water to solution W and 30 ml was prepared.
[0024]
A used single cell honeycomb (8 mm □) containing 0.75V 2 O 5 , 15% WO 3 , 69% TiO 2 in 0.75V 2 O 5 , 15% WO 3 , 69% TiO 2 in 50 ml of the above solution. × 210mm, 12g) One piece was immersed for 2 minutes to absorb an aqueous solution containing vanadium and tungsten into the pores, then drained and dried to obtain 0.25% V 2 O 3 and 1% WO 3 A regenerated catalyst in which was newly supported was obtained.
The treated catalyst honeycomb was subjected to a denitration performance test under the following conditions to measure the denitration rate and the SO 2 oxidation rate.
[0025]
Space velocity: 12000h -1
Reaction gas composition: 200 ppm NO—NH 3 -4% -O 2 -500 ppm SO 2 -10% H 2 O—N 2 balance, NH 3 / NO molar ratio 1.0, 0.74
Temperature: 370 ° C
[Example 2]
0.25% V 2 O 3 -0.5% WO 3 was newly reclaimed and supported by the same method except that the tungsten concentration in the W liquid of Example 1 was halved. went.
[0026]
[Example 3]
0.25% V 2 O 3 -2.5% WO 3 was newly reclaimed and supported by the same method except that the tungsten concentration in the W liquid of Example 1 was increased by 2.5 times. went.
[0027]
[Example 4]
By the same method except that the vanadium concentration in the V liquid of Example 1 was doubled, 0.5% V 2 O 3 -1% WO 3 was newly reclaimed and supported, and the performance was measured.
[0028]
[Comparative Example 1]
The performance measurement was performed using the used catalyst before the regeneration treatment used in Example 1 as it was.
[0029]
[Comparative Example 2]
0.25% V 2 O 3 was renewed in the same manner as in Example 1 except that 50 ml of the solution having a vanadium concentration of 1/8 was used as the immersion liquid before the regeneration treatment. The performance was measured.
[0030]
[Comparative Example 3]
About the used catalyst before the regeneration treatment used in Example 1, 0.5% V 2 O 3 was obtained in the same manner except that 50 ml of the solution in which the vanadium concentration in the V liquid was ¼ was used as the immersion liquid. Mr. Rejuvenation carried out a new performance measurement.
[0031]
[Comparative Example 4]
With respect to the used catalyst before the regeneration treatment used in Example 1, 1.5% V 2 O 3 was obtained in the same manner except that 50 ml of the solution in which the vanadium concentration in the V liquid was 3/4 was used as the immersion liquid. Mr. Rejuvenation carried out a new performance measurement.
[0032]
Table 1 summarizes the average value of the denitration rate and the SO 2 oxidation rate at the NH 3 / NO molar ratio of 1.0 and 0.74 for the performance test results of Examples 1 to 4 and Comparative Examples 1 to 4.
[0033]
[Table 1]
[0034]
Compared with the denitration rate and SO 2 oxidation rate of the used catalyst of Comparative Example 1, the catalyst in which V 2 O 3 and WO 3 were newly supported by the pore filling method was averaged as shown in Examples 1 to 4 While the denitration rate has increased by 10% or more, in Examples 1 to 3, the SO 2 oxidation rate is also kept low. In Example 4, although the denitration rate is increasing, the SO 2 oxidation rate is slightly higher than that of Comparative Example 1. However, the catalyst shown in Comparative Example 3 in which only V 2 O 3 is supported by the pore filling method has a higher NO 2 removal rate and a higher SO 2 oxidation rate than Comparative Example 1, whereas Comparative Example 3 In comparison with Example 4, the denitration rate is high and the SO 2 oxidation rate is low.
[0035]
From the above results, by newly carrying V 2 O 3 and WO 3 in pore filling method used denitration catalyst activity decreased, found that the denitration rate increases simultaneously SO 2 oxidation rate is prevented, The regeneration treatment method according to the present invention is a very effective method for improving the performance of a deteriorated catalyst.
[0036]
【The invention's effect】
By simultaneously supporting V 2 O 3 and WO 3 on the catalyst deteriorated according to the present invention, the denitration rate is improved, so that the amount of ammonia supplied for reduction can be reduced, and the SO 2 oxidation rate can be kept low. In addition to reducing the amount of acidic ammonium sulfate produced at the reactor outlet and avoiding problems such as clogging, there are great advantages in terms of denitration reaction efficiency, and the regeneration treatment method according to the present invention is short with a minimum amount of treatment liquid. As a result of being able to perform in time, there is an advantage that the cost of the regeneration processing can be made very low.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing an example of an apparatus for carrying out the method of the present invention.
[Explanation of symbols]
1: Chemical tank 2: Denitration catalyst 3: Pump 4: Spray unit 5: Liquid collection unit
Claims (1)
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