JP5286836B2 - Catalyst activity evaluation method - Google Patents
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Description
本発明は、触媒活性を簡易に評価することが可能な触媒活性評価装置及びそれを使用した触媒活性評価方法に関する。 The present invention relates to a catalyst activity evaluation apparatus capable of easily evaluating catalyst activity and a catalyst activity evaluation method using the same.
各種の化学反応において触媒が使用されているが、最適触媒を見つけることは容易な事ではない。従来の触媒探索は試行錯誤に頼るところが大きく、実際に触媒反応を行っていたのでは評価できる触媒の数が限られるため、多大な時間と労力を要してきた。また、複数の触媒を完全に同一な条件にて簡易に評価することができなかった。 Although catalysts are used in various chemical reactions, finding the optimal catalyst is not easy. The conventional catalyst search largely depends on trial and error, and since the number of catalysts that can be evaluated is limited by actually performing the catalytic reaction, a great deal of time and labor has been required. Moreover, it was not possible to easily evaluate a plurality of catalysts under completely identical conditions.
例えば、ＰＣＢ分解に使用する触媒は、高価であるため、再生して使用するのが経済的であるが、最適な再生方法を見出すためには再生した触媒を都度ＰＣＢ分解反応に供して触媒活性を評価しなければならず、再生方法を見出すのも容易ではなかった。しかも、多孔質の触媒であるため、細孔内に入り込んだ副生物や異物の除去も容易ではなく、細孔内を元通りに復活させることが触媒再生における重要課題と考えられていた。この多孔質の触媒作用によるＰＣＢ分解反応は、反応溶媒が触媒に吸着することにより発熱する吸着熱からくる、発熱反応である。 For example, since the catalyst used for PCB decomposition is expensive, it is economical to regenerate and use it. However, in order to find the optimum regeneration method, the regenerated catalyst is used for the PCB decomposition reaction each time for catalytic activity. It was not easy to find a reproduction method. In addition, since the catalyst is a porous catalyst, it is not easy to remove by-products and foreign substances that have entered the pores, and it has been considered that restoring the pores to the original state is an important issue in catalyst regeneration. The PCB decomposition reaction by the porous catalytic action is an exothermic reaction that comes from the heat of adsorption generated by the reaction solvent adsorbing to the catalyst.
反応熱に着目した触媒活性の評価方法として、エチルベンゼンを脱水素してスチレンを合成するのに用いられる触媒を反応管に充填して触媒層を形成し、この反応管を電気炉に収容して、反応管とヒーターブロックの間に断熱材を入れ、反応管側の温度とヒーターブロック側の温度の差を０としつつ、ヒーターブロックを加熱しながら触媒の性能を評価する方法が提案されている（特許文献１参照）。しかしながら、この反応装置は断熱反応型の実プラントでの触媒性能を予測する方法として有効ではあるが、利用範囲は吸熱反応に限られる。
本発明は、発熱反応型の触媒の性能を、迅速かつ簡易に評価、比較することを可能とする触媒活性評価装置、およびそれを使用した触媒活性評価方法を提供することを課題とする。
The present invention, the performance of exothermic reaction type catalysts, quick and evaluated easily, catalytic activity evaluation apparatus capable comparison, and it is an object to provide a catalytic activity evaluation method using the same.
前記課題を解決するため、本発明者らは鋭意検討した結果、発熱反応型の反応に使用する触媒に、該触媒の触媒作用により反応する溶媒を触媒に添加するとその吸着熱により触媒温度が上昇することに着目し、そのときの発生熱を温度変化として捕え、測定することにより迅速に、かつ簡便に触媒活性を評価できることを見出し、本発明に到達した。 In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, when a solvent that reacts by the catalytic action of the catalyst is added to the catalyst used in the exothermic reaction, the catalyst temperature rises due to the heat of adsorption. In particular, the present inventors have found that the catalytic activity can be evaluated quickly and easily by capturing and measuring the heat generated at that time as a temperature change, and have reached the present invention.
すなわち、本発明は以下の通りである。
That is, the present invention is as follows .
（１）発熱反応型の触媒の活性を簡易評価する方法であって、外管と触媒を収容する反応管（内管）との二重管で構成され、触媒の温度変化を測定する熱電対とデータロガーが備えられている評価装置を用い、金属担持多孔質触媒を前記反応管の中に入れて静置し、次いで、該触媒の触媒作用により反応する溶媒を反応管内の触媒に注入し、溶媒を注入することによる温度上昇変化を、触媒のほぼ真中に挿入した熱電対により測定し、上昇した温度変化量の大きさを触媒活性の強さの指標として評価することを特徴とする触媒活性評価方法。
（２）触媒作用により反応する溶媒の沸点が６０〜２００℃である前記（１）に記載の触媒活性評価方法。
（３）溶媒がアルコール類である前記（２）に記載の触媒活性評価方法。
( 1 ) A method for simply evaluating the activity of an exothermic reaction type catalyst , comprising a double tube with an outer tube and a reaction tube (inner tube) containing the catalyst, and measuring the temperature change of the catalyst And an evaluation apparatus equipped with a data logger, the metal-supported porous catalyst is placed in the reaction tube and allowed to stand, and then a solvent that reacts by the catalytic action of the catalyst is injected into the catalyst in the reaction tube. The catalyst is characterized in that the temperature rise change caused by injecting the solvent is measured by a thermocouple inserted almost in the middle of the catalyst, and the magnitude of the rise in temperature change amount is evaluated as an indicator of the strength of the catalyst activity. Activity evaluation method.
( 2 ) The method for evaluating catalytic activity according to (1) above, wherein the solvent reacting by catalytic action has a boiling point of 60 to 200 ° C.
( 3 ) The method for evaluating catalytic activity according to ( 2 ), wherein the solvent is an alcohol.
本発明の触媒活性評価装置および方法を採用することにより、同一条件で迅速かつ簡便に、対象触媒の比較、活性の評価を行うことが可能となる。触媒はごく少量で評価可能であり、多くの触媒を試作し評価する場合でも、触媒の試作量は少なく済むため、省力化、コスト低減が期待できる。 By employing the catalyst activity evaluation apparatus and method of the present invention, it is possible to compare the target catalysts and evaluate the activity quickly and easily under the same conditions. The catalyst can be evaluated in a very small amount, and even when many catalysts are manufactured and evaluated, the amount of the catalyst manufactured is small, so that labor saving and cost reduction can be expected.
また、温度変化量の測定結果は、触媒比表面積と相関が見られたことより、比表面積の指標として活用できる。 Further, the measurement result of the temperature change amount can be used as an index of the specific surface area because the correlation with the specific surface area of the catalyst was observed.
以下、本発明で用いる触媒活性評価装置を、図面を参照しつつ詳細に説明する。
図１は、本発明で用いる触媒活性評価装置の好ましい一例を示す概略説明図である。触媒活性評価装置は、外管１と、触媒を収容する反応管（内管）２との二重管で構成されてなり、触媒の温度変化を測定する熱電対３とデータロガー４が備えられている。データロガー４をパーソナルコンピュータ５に接続すると、データの収集測定と測定データの比較が容易である。データロガーとしては、市販のデジタル・マルチメータ（例えば、岩通計測（株））などを使用すると簡易に測定でき、ＰＣレコーダーでもよい。
Hereinafter, the catalyst activity evaluation apparatus used in the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic explanatory view showing a preferred example of a catalyst activity evaluation apparatus used in the present invention. The catalyst activity evaluation apparatus is composed of a double tube of an outer tube 1 and a reaction tube (inner tube) 2 containing the catalyst, and is equipped with a thermocouple 3 and a data logger 4 for measuring the temperature change of the catalyst. ing. When the data logger 4 is connected to the personal computer 5, it is easy to collect data and compare the measured data. The data logger can be easily measured by using a commercially available digital multimeter (for example, Iwatori Measurement Co., Ltd.), and may be a PC recorder.
外管および反応管は、厚さが１ｍｍ程度のガラス、耐熱性プラスチックなど透明な材料で構成し、外側から反応管内の触媒を観察できるようにするのがよい。反応管だけで構成すると外熱の影響を受けるおそれがあるが、外管と反応管との二重管で構成することにより、反応管に対する外熱の影響を排除することができる。 The outer tube and the reaction tube are preferably made of a transparent material such as glass or heat-resistant plastic having a thickness of about 1 mm so that the catalyst in the reaction tube can be observed from the outside. Although it may be affected by external heat if it is constituted only by the reaction tube, the influence of external heat on the reaction tube can be eliminated by constituting it by a double tube of the outer tube and the reaction tube.
次に、触媒活性評価装置を使用した触媒評価方法を説明する。
先ず、所定量の発熱反応型の触媒（試料）を、反応管２の中に入れ静置する。次いで、静置した触媒のほぼ真中に熱電対を挿入し、温度が安定するのを待つ。温度が安定したら、該触媒の触媒作用により反応する溶媒を、マイクロピペットで所定量を量り取り、反応管内の触媒に注入する。溶媒を注入することによる温度上昇変化は、熱電対により測定しデータロガーにて収録する。触媒表面状態が試料によって多少ばらつくおそれがあるため、温度変化の測定は、１試料につき、複数回実施すると精度が向上する。測定は常温下で行えばよいが、必要に応じて恒温槽などで２５℃程度に調整して測定することにより、温度変化が分かり易くなる。温度上昇がなくなった時点で、測定を終了する。
Next, a catalyst evaluation method using the catalytic activity evaluation device.
First, a predetermined amount of exothermic reaction type catalyst (sample) is placed in the reaction tube 2 and allowed to stand. Next, a thermocouple is inserted almost in the middle of the stationary catalyst and waits for the temperature to stabilize. When the temperature is stabilized, a predetermined amount of the solvent that reacts by the catalytic action of the catalyst is measured with a micropipette and injected into the catalyst in the reaction tube. Changes in temperature rise due to solvent injection are measured with a thermocouple and recorded with a data logger. Since there is a possibility that the catalyst surface state varies somewhat depending on the sample, the measurement of temperature change improves the accuracy when it is performed a plurality of times per sample. The measurement may be performed at room temperature, but the temperature change can be easily understood by adjusting the temperature to about 25 ° C. in a thermostatic bath as necessary. The measurement is terminated when the temperature rise has ceased.
触媒（試料）は、発熱反応型の多孔質触媒に適用すると触媒活性の比較、評価の精度が高い。かかる触媒は特に限定されるものではないが、好ましい例として、ゼオライト等の複合金属酸化物；鉄、銀、白金、ルテニウム、パラジウム、ロジウム等の金属を担持した金属担持炭素化合物（例えば、Ｐｄ／Ｃ、Ｒｕ／Ｃ、Ｐｔ／Ｃ）；鉄、銀、白金、ルテニウム、パラジウム、ロジウム等の金属を担持したＳｉＯ２、ＴｉＯ２、ＺｒＯ２、Ａｉ２Ｏ３、ＺｎＯ、Ｃｒ２Ｏ３、ＭｇＯ等の金属担持酸化物あるいは金属担持複合金属酸化物等を挙げることができる。 When the catalyst (sample) is applied to an exothermic reaction type porous catalyst, the accuracy of comparison and evaluation of catalytic activity is high. Such a catalyst is not particularly limited, but preferred examples include a composite metal oxide such as zeolite; a metal-supported carbon compound carrying a metal such as iron, silver, platinum, ruthenium, palladium, rhodium (for example, Pd / C, Ru / C, Pt / C); SiO 2 , TiO 2 , ZrO 2 , Ai 2 O 3 , ZnO, Cr 2 O 3 , MgO supporting a metal such as iron, silver, platinum, ruthenium, palladium, rhodium And metal supported oxides such as metal supported composite metal oxides.
触媒（試料）の形態は、微粉末、粗粒子、球状や円柱状などの成形品、ペレットなど種々の形態であってよいが、比較対象となる触媒（試料）は同じ形態でできるだけ粒径が近いものを使用することが好ましい。 The form of the catalyst (sample) may be various forms such as fine powder, coarse particles, molded products such as spherical and cylindrical shapes, and pellets, but the catalyst (sample) to be compared is the same form and has a particle size as much as possible. It is preferable to use a close one.
上記触媒の触媒作用により反応する溶媒としては、アルコール類、例えば、例えば、メタノール、エタノール、１−プロパノール、２−プロパノール、ｎ−ブタノール、ｓ−ブタノール、ｔ−ブタノール、１−ペンタノール、２−ペンタノール、３−ペンタノール、１−ヘキサノール、２−ヘキサノール、３−ヘキサノール、１−ヘプタノール、２−ヘプタノール、３−ヘプタノール、１−オクタノール、２−オクタノール等の脂肪族アルコール、シクロプロピルアルコール、シクロブチルアルコール、シクロペンチルアルコール、シクロヘキシルアルコール、シクロヘプチルアルコール、シクロオクチルアルコール等の脂環式アルコール、エチレングリコール、プロピレングリコール、デカリンジオール等の多価アルコール等が挙げられる。用いられる溶媒の沸点は６０〜２００℃のものが好ましく、６０〜１００℃のものが特に好ましい。これらの反応は殆んどが発熱反応であるが、反応の前後において熱収支があるものであれば、本発明において用いることができる。 Examples of the solvent that reacts by the catalytic action of the catalyst include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, n-butanol, s-butanol, t-butanol, 1-pentanol, 2- Pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol and other aliphatic alcohols, cyclopropyl alcohol, cyclo Examples include alicyclic alcohols such as butyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, cycloheptyl alcohol, and cyclooctyl alcohol, and polyhydric alcohols such as ethylene glycol, propylene glycol, and decalin diol.The solvent used preferably has a boiling point of 60 to 200 ° C, particularly preferably 60 to 100 ° C. Most of these reactions are exothermic reactions, but any reaction having a heat balance before and after the reaction can be used in the present invention.
触媒（試料）に溶媒を含有させるには、例えば反応管の中に入れた溶媒に触媒を浸漬したり、同様に触媒に溶媒を含浸させた後混合することも可能であるが、反応管の中に静置して温度が安定した触媒に溶媒を添加して静置する方が、触媒が空気に接触した際の発熱量の影響を排除して触媒の細孔内に入り込んだ溶媒の吸着熱を正確に測定することができる。このようにして、溶媒添加前の触媒温度と、溶媒添加後の触媒温度との差を、温度変化量として求めることができる。 In order to contain the solvent in the catalyst (sample), for example, it is possible to immerse the catalyst in a solvent put in the reaction tube, or to impregnate the catalyst with the solvent, and then mix them. Adsorbing the solvent that has entered the pores of the catalyst eliminates the effect of the amount of heat generated when the catalyst is in contact with air, by adding a solvent to the catalyst that has been stabilized in the temperature and allowed to stand. Heat can be measured accurately. In this way, the difference between the catalyst temperature before the addition of the solvent and the catalyst temperature after the addition of the solvent can be obtained as the temperature change amount.
測定は通常、常温（室温）で行うため、溶媒の沸点が低すぎると反応熱によって溶媒が蒸発して触媒活性を正確に測定できないことがあり、一方溶媒の沸点が高すぎると溶媒の反応が抑制されて触媒活性を正確に測定できないことがある。 Since the measurement is usually performed at room temperature (room temperature), if the boiling point of the solvent is too low, the solvent may evaporate due to the heat of reaction, and the catalyst activity may not be measured accurately. It may be suppressed and the catalytic activity may not be measured accurately.
このようにして測定された温度上昇試験の結果は、触媒細孔内への吸着熱が大きく影響を与えていると考えられるため、比表面積や細孔容積が大きい程、温度変化量も大きくなる。すなわち、比表面積や細孔容積が大きい触媒は温度変化量が大きく、逆に比表面積や細孔容積が小さい触媒は温度変化量が小さい。したがって、温度変化量を触媒活性の強さの指標とすることができる。例えば、ＰＣＢ分解反応に使用した触媒を再生した再生触媒としては、本発明の装置および方法を用いて測定した温度変化量すなわち温度上昇が高く、できるだけ未使用触媒の測定結果に近い触媒を選択すればよい。 The temperature rise test results measured in this way are considered to have a large influence on the heat of adsorption into the catalyst pores, so the larger the specific surface area and pore volume, the greater the amount of temperature change. . That is, a catalyst with a large specific surface area or pore volume has a large amount of temperature change, and conversely, a catalyst with a small specific surface area or pore volume has a small amount of temperature change. Therefore, the amount of temperature change can be used as an indicator of the strength of the catalyst activity. For example, as a regenerated catalyst that regenerates the catalyst used in the PCB decomposition reaction, a catalyst that has a high temperature change amount measured using the apparatus and method of the present invention, that is, a temperature rise, and is as close as possible to the measurement result of the unused catalyst is selected. That's fine.
次に、本発明を実施例により詳細に説明するが、本発明は以下の実施例にのみ限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited only to a following example.
（実施例１）
図１に示した触媒活性評価装置を作製した。外管１は内径３８ｍｍφのガラス管、反応管（内管）２は内径１３ｍｍφの１０ｍｌ容ガラス管を使用した。データロガー４は、ＮＲ−６００システム、ＫＥＹＥＮＣＥ製を使用した。
Example 1
The catalyst activity evaluation apparatus shown in FIG. 1 was produced. The outer tube 1 was a glass tube having an inner diameter of 38 mmφ, and the reaction tube (inner tube) 2 was a 10 ml glass tube having an inner diameter of 13 mmφ. The data logger 4 used was an NR-600 system manufactured by KEYENCE.
触媒として、ＰＣＢ分解反応用のＰｄ担持炭素化合物を使用した。溶媒は、イソプロピルアルコール（ＩＰＡ）を使用した。 As a catalyst, a Pd-supported carbon compound for PCB decomposition reaction was used. Isopropyl alcohol (IPA) was used as the solvent.
反応管２の中に、触媒（試料）６を１ｇを入れ、静置した。触媒に熱電対３を挿入し温度が安定するのを待った。温度が安定したら、イソプロピルアルコール（溶媒）７をマイクロピペットで５ｍｌ量り、反応管内の触媒に注入した。イソプロピルアルコール注入による温度上昇変化は熱電対によりデータロガー４（サンプリング速度１００ｍｓｅｃ）にて収録し、接続したパーソナルコンピュータ５にてデータ処理した。
温度変化の測定は１試料につき５回実施し、５回の平均値をとった。
1 g of catalyst (sample) 6 was placed in the reaction tube 2 and allowed to stand. The thermocouple 3 was inserted into the catalyst and waited for the temperature to stabilize. When the temperature was stabilized, 5 ml of isopropyl alcohol (solvent) 7 was weighed with a micropipette and injected into the catalyst in the reaction tube. Changes in temperature rise due to isopropyl alcohol injection were recorded with a data logger 4 (sampling speed 100 msec) by a thermocouple and processed with a connected personal computer 5.
The temperature change was measured 5 times per sample, and the average value of 5 times was taken.
上記の方法により、未使用触媒、ＰＣＢ分解反応使用後の触媒、ＰＣＢ分解反応使用後の触媒を再生した再生触媒Ａ〜Ｆの評価を行った。その結果を、触媒性状と併せて表１に示した。各触媒における、測定時間と温度変化量（ΔＴ）との関係を図２に、温度変化量と比表面積との関係を図３に示した。 Evaluation of the regenerated catalysts A to F obtained by regenerating the unused catalyst, the catalyst after using the PCB decomposition reaction, and the catalyst after using the PCB decomposition reaction was performed by the above method. The results are shown in Table 1 together with the catalyst properties. The relationship between the measurement time and the temperature change (ΔT) in each catalyst is shown in FIG. 2, and the relationship between the temperature change and the specific surface area is shown in FIG.
表１および図２の結果から、未使用触媒は最も活性が高く、次いで再生触媒Ｆの活性が高く、使用後触媒は活性が極めて低いことが分かる。 From the results of Table 1 and FIG. 2, it can be seen that the unused catalyst has the highest activity, then the regeneration catalyst F has the highest activity, and the used catalyst has the extremely low activity.
また、比表面積および細孔容積分析の結果から、図３にも示したように比表面積が大きい程温度変化量も大きくなり、温度変化量と比表面積との間に相関関係があることが確認できた。 From the results of specific surface area and pore volume analysis, as shown in FIG. 3, the larger the specific surface area, the larger the temperature change amount, and it is confirmed that there is a correlation between the temperature change amount and the specific surface area. did it.
本発明に係る触媒活性評価装置およびそれを使用した触媒評価方法によれば、極めて迅速に、簡易な操作で触媒の活性を評価することができるため、各種の発熱反応における触媒の評価、探索に有効である。 According to the catalyst activity evaluation apparatus and the catalyst evaluation method using the same according to the present invention, the activity of the catalyst can be evaluated very quickly and with a simple operation. Therefore, it is possible to evaluate and search for a catalyst in various exothermic reactions. It is valid.
１ 外管
２ 反応管（内管）
３ 熱電対
４ データロガー
５ パ−ソナルコンピュータ
６ 触媒（試料）
７ 溶媒
1 Outer tube 2 Reaction tube (inner tube)
3 Thermocouple 4 Data Logger 5 Personal Computer 6 Catalyst (Sample)
7 Solvent
Claims (3)
The method for evaluating catalytic activity according to claim 2 , wherein the solvent is an alcohol.
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