JP7068907B2 - Method for measuring the amount of caulking in the catalyst layer - Google Patents

Method for measuring the amount of caulking in the catalyst layer Download PDF

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JP7068907B2
JP7068907B2 JP2018082520A JP2018082520A JP7068907B2 JP 7068907 B2 JP7068907 B2 JP 7068907B2 JP 2018082520 A JP2018082520 A JP 2018082520A JP 2018082520 A JP2018082520 A JP 2018082520A JP 7068907 B2 JP7068907 B2 JP 7068907B2
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信明 伊藤
等 堂野前
公仁 鈴木
憲治 中尾
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Kobe Steel Ltd
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Nippon Steel Engineering Co Ltd
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本発明は、化学反応装置内の触媒反応器の操業に用いる情報の測定方法に関し、特に触媒層のコーキング量の測定方法に関するものである。 The present invention relates to a method for measuring information used for operating a catalytic reactor in a chemical reaction apparatus, and particularly to a method for measuring a coking amount of a catalyst layer.

化学反応装置において、炭化水素ガスの水蒸気改質を、固定床触媒反応器を用いて行う場合には、しばしば触媒の表面に固体カーボン（コーク）微粒子を副生するコーキングが生じる。触媒粒子間に堆積したコーク粉は、触媒表面での目的の反応を妨げるとともに、触媒反応器の通気抵抗を増大させて触媒反応器を閉塞させる問題を生じる。 In a chemical reactor, when steam reforming of a hydrocarbon gas is carried out using a fixed bed catalyst reactor, coking is often produced on the surface of the catalyst as a by-product of solid carbon (cork) fine particles. The cork powder deposited between the catalyst particles hinders the desired reaction on the surface of the catalyst and causes a problem of increasing the aeration resistance of the catalyst reactor and closing the catalyst reactor.

触媒反応器からコークをオンラインで除去する方法としては、例えば、特許文献１に開示されている方法が知られている。特許文献１に開示されたコーク除去操作を行うことで、触媒層中のコークを除去できるものの、コーク除去操作を行う都度、一部の触媒が破損するという問題が生じる。このため、操作頻度を必要最低限にしなければならない。コークの触媒層中への堆積状況は操業ごとに大きく変動するため、操作頻度を必要最低限とするためには、定期的にコーク除去操作を行うような手段では不十分であり、操業中の触媒層中でのコーク堆積量（即ち、コーキング量）をオンラインで測定し、これが予め定めた許容値を超えたときのみコーク除去操作を行う必要がある。 As a method for removing cork from a catalytic reactor online, for example, the method disclosed in Patent Document 1 is known. Although the cork in the catalyst layer can be removed by performing the cork removing operation disclosed in Patent Document 1, there arises a problem that a part of the catalyst is damaged each time the cork removing operation is performed. Therefore, the operation frequency must be minimized. Since the state of deposit of caulk in the catalyst layer fluctuates greatly from operation to operation, it is not sufficient to perform the caulk removal operation on a regular basis in order to minimize the operation frequency. It is necessary to measure the amount of coke deposits (ie, the amount of caulking) in the catalyst layer online and perform the coke removal operation only when this exceeds a predetermined allowable value.

触媒層中のコーキング量を測定する方法としては、例えば、特許文献１に一例が示されるように、触媒層入側および出側で圧力を測定し、その差圧を用いる方法がある。しかし、この方法の場合、触媒層中のコーキング量が極めて大きくなるまで（すなわち、触媒層が閉塞する直前まで）差圧を検出することができない。すなわち、差圧を用いる方法では、閉塞直前の状態を検出できたとしても、これ以前の状態のコーキング量の測定を行えないという問題がある。 As a method of measuring the amount of caulking in the catalyst layer, for example, as shown in Patent Document 1, there is a method of measuring the pressure on the inlet side and the outlet side of the catalyst layer and using the differential pressure. However, in the case of this method, the differential pressure cannot be detected until the amount of caulking in the catalyst layer becomes extremely large (that is, until just before the catalyst layer is closed). That is, the method using the differential pressure has a problem that even if the state immediately before the blockage can be detected, the caulking amount in the state before this cannot be measured.

つまり、コーキングは、一般に触媒層の局所に集中して生じる傾向を持ち、局所的に閉塞を生じた触媒部分およびその下流部分では触媒反応が妨げられて反応速度の低下を招く。一方、局所的な閉塞を触媒層内に生じたとしても、触媒層内の自由空間が十分に広い段階では、触媒層内に容易にガスのう回路が形成されるため、局所的な閉塞は触媒層前後での差圧には容易には影響しない。触媒層内のいたるところで局所的な閉塞を生じて触媒層内の自由空間が著しく減少して初めて、触媒層前後の圧力差は検出可能なレベルまで上昇する。したがって、差圧を用いてコーキング量を測定し、その結果に基づいてコーク除去操作の要否を判断した場合、触媒層が閉塞する直前の段階（すなわち、触媒層全体での反応速度が極めて低下した段階）で初めてコーク除去操作が行われることになる。これでは、触媒反応の効率が非常に悪い。 That is, caulking generally tends to occur locally in the catalyst layer, and the catalytic reaction is hindered in the locally clogged catalyst portion and the downstream portion thereof, resulting in a decrease in the reaction rate. On the other hand, even if local blockage occurs in the catalyst layer, local blockage occurs because a gas sac circuit is easily formed in the catalyst layer when the free space in the catalyst layer is sufficiently wide. It does not easily affect the differential pressure before and after the catalyst layer. The pressure difference before and after the catalyst layer rises to a detectable level only when local blockage occurs everywhere in the catalyst layer and the free space in the catalyst layer is significantly reduced. Therefore, when the amount of caulking is measured using the differential pressure and the necessity of the caulking operation is determined based on the result, the reaction rate in the stage immediately before the catalyst layer is closed (that is, the reaction rate in the entire catalyst layer is extremely reduced). The cork removal operation will be performed for the first time. This makes the catalytic reaction very inefficient.

上述したように、触媒層前後の差圧が検出下限以下の状態であっても、触媒層中に局所的な閉塞が触媒層内の広い領域に多く存在して触媒層全体での反応速度が有意に低下する場合がある。このような状態でもコーキング量を測定し、より早い段階でコーク除去操作を行う必要がある。 As described above, even when the differential pressure before and after the catalyst layer is below the lower limit of detection, many local blockages exist in the catalyst layer in a wide region in the catalyst layer, and the reaction rate in the entire catalyst layer is high. May be significantly reduced. Even in such a state, it is necessary to measure the amount of caulking and perform the caulking operation at an earlier stage.

特に、複数の触媒反応器を共通の流入集合管、流出集合管に接続させた化学反応装置では、いずれかの触媒反応器が閉塞状態となっても、他の触媒反応器が閉塞状態でなければ、他の触媒反応器がガスのう回路となってしまう。したがって、特許文献１の方法では、全ての触媒反応器が閉塞状態（あるいはその直前の状態）とならなければ、差圧を検出することができない。したがって、全ての触媒反応器が閉塞状態（あるいはその直前の状態）とならなければ、触媒層の閉塞を検知することができず、コーク除去操作を行うことができない。 In particular, in a chemical reaction device in which a plurality of catalytic reactors are connected to a common inflow collecting pipe and outflow collecting pipe, even if one of the catalytic reactors is in a closed state, the other catalytic reactor must be in a closed state. If so, other catalytic reactors will become gas-filled circuits. Therefore, in the method of Patent Document 1, the differential pressure cannot be detected unless all the catalytic reactors are in the closed state (or the state immediately before). Therefore, unless all the catalytic reactors are in the blocked state (or the state immediately before the blocked state), the blocked state of the catalyst layer cannot be detected and the cork removal operation cannot be performed.

内視鏡等の接触的なセンサを触媒層内に挿入してコーキング量を測定する方法も考えられる。しかし、このような方法を高温、かつ、高い密閉性を求められる触媒反応器に適用することは、装置の設計が困難であり、また、高価になるため、合理的でない。 A method of measuring the amount of caulking by inserting a contact sensor such as an endoscope into the catalyst layer is also conceivable. However, it is not rational to apply such a method to a catalytic reactor that requires high temperature and high airtightness because the design of the apparatus is difficult and expensive.

音波を利用して充填層内での粒子の充填率を非接触的に測定する方法を触媒層内のコーキング量の測定に応用することも考えうる。例えば、音波で固体材料中の気孔率を測定する方法が特許文献２に開示されている。しかし、この方法は、多孔質体を通過する音波の伝達速度遅れを検出して充填率に換算する原理を用いている。このため、音波に関して多数の反射パス（例えば、反応器に接続する多数の配管）が存在する実機の化学反応装置に本方法を適用することは困難である。 It is also conceivable to apply a method of non-contactly measuring the packing rate of particles in the packed bed using sound waves to measure the amount of caulking in the catalyst layer. For example, Patent Document 2 discloses a method of measuring porosity in a solid material by sound waves. However, this method uses the principle of detecting the delay in the transmission speed of the sound wave passing through the porous body and converting it into the filling rate. For this reason, it is difficult to apply this method to an actual chemical reaction device having a large number of reflection paths (for example, a large number of pipes connected to a reactor) for sound waves.

また、特許文献３には、蓄水タンク内の氷充填率を測定するために、単一波長の音波を蓄水タンクに照射し、貯水タンクを透過した音波の透過損失から氷充填率を求める方法も開示されている。しかし、音波の透過率は、本来、周波数の依存性が高く、系の寸法や音速等との関係でわずかに周波数が変化しても、音波の透過率は、例えば数十ｄＢのレベルで変化しうる。このため、寸法と物性がほぼ一様と想定される蓄水タンクには適用できても、触媒充填率、コーク充填率、または、温度分布が絶えず変動する（即ち、音速が絶えず変動する）触媒反応器に本技術を適用したとしても、測定精度を十分確保できない。 Further, in Patent Document 3, in order to measure the ice filling rate in the water storage tank, a sound wave having a single wavelength is irradiated to the water storage tank, and the ice filling rate is obtained from the transmission loss of the sound wave transmitted through the water storage tank. The method is also disclosed. However, the transmittance of sound waves is inherently highly frequency-dependent, and even if the frequency changes slightly due to the size of the system, the speed of sound, etc., the transmittance of sound waves changes at the level of, for example, several tens of dB. Can be done. Therefore, even if it can be applied to a water storage tank whose dimensions and physical properties are assumed to be almost uniform, the catalyst filling rate, cork filling rate, or temperature distribution constantly fluctuates (that is, the speed of sound constantly fluctuates). Even if this technology is applied to the reactor, sufficient measurement accuracy cannot be ensured.

特許文献４には、複数の周波数の超音波を用いて懸濁液中の微粒子を励起し、前記超音波の減衰スペクトルをパターン判定して懸濁液中の粒径分布および濃度を測定する方法が開示されている。しかし、本発明が対象とするガス流れによるコーク粒子（触媒粒子間の空間に固定されている）を音波によって励起することは、ガスと固体の密度差が大きいためにそもそも困難であり、特許文献４の方法を触媒反応器には適用できない。なぜならば、本発明が対象とする触媒層内での音波の減衰は、微粒子の高速励起（超音波による励起）による流体粘性に基づくエネルギ損失のみによるものではなく、固定された粒子間の空間で音波が多重反射して互いに打ち消しあうことによって音響エネルギを損失することによる影響が大きく、特許文献４での原理とは異なるからである。 Patent Document 4 describes a method of exciting fine particles in a suspension using ultrasonic waves having a plurality of frequencies, determining a pattern of the attenuation spectrum of the ultrasonic waves, and measuring the particle size distribution and concentration in the suspension. Is disclosed. However, it is difficult to excite cork particles (fixed in the space between catalyst particles) due to the gas flow, which is the subject of the present invention, by sound waves because the density difference between the gas and the solid is large. Method 4 cannot be applied to a catalytic reactor. This is because the attenuation of sound waves in the catalyst layer targeted by the present invention is not only due to energy loss due to fluid viscosity due to high-speed excitation of fine particles (excitation by ultrasonic waves), but also in the space between fixed particles. This is because the effect of losing acoustic energy due to multiple reflections of sound waves and canceling each other is large, which is different from the principle in Patent Document 4.

また、これらの音波を用いる測定方法は、いずれも空間に粒子が一様に分布する状況を想定している。しかし、本発明が対象とする触媒層ではコークの分布は不均一であり、音波が減衰するとしてもその減衰量を直接に測定するわけでは必ずしもなく、特に、コーキング量の少ない状態では、触媒層内でコーキングのない自由空間の配置によって減衰量が決定する。また、触媒層内には、触媒粒子とコークという、２種類の極端に大きさのことなる粒子が任意の配合で存在しうる多様性が存在する。さらに、触媒層の充填率は、上記のコーク除去操業によってしばしば変化し、かつ、触媒層の音波透過減衰は、コークの音波透過減衰に比べて十分に小さいとも必ずしもいえない。このため、コーキング量と音波の透過減衰量の関係は、自明ではない。 In addition, all of these measurement methods using sound waves assume a situation in which particles are uniformly distributed in space. However, in the catalyst layer targeted by the present invention, the distribution of cork is non-uniform, and even if the sound wave is attenuated, the amount of attenuation is not always measured directly. The amount of attenuation is determined by the arrangement of the free space without coking inside. Further, in the catalyst layer, there is a variety in which two kinds of particles having extremely different sizes, that is, catalyst particles and cork, can exist in an arbitrary composition. Further, the filling rate of the catalyst layer is often changed by the above-mentioned cork removal operation, and the sound wave transmission attenuation of the catalyst layer is not always sufficiently smaller than the sound wave transmission attenuation of cork. Therefore, the relationship between the amount of caulking and the amount of transmission attenuation of sound waves is not obvious.

特開２０１７－５６３７５号公報Japanese Unexamined Patent Publication No. 2017-56375 特開平６－１８４０３号公報Japanese Unexamined Patent Publication No. 6-18403 特開２０００－３２９６０２号公報Japanese Unexamined Patent Publication No. 2000-329602 特公平６－２７６９５号公報Special Fair 6-27695 Gazette

城戸健一:ディジタルフーリエ解析（ＩＩ）,コロナ社,２００７,第９章Kenichi Kido: Digital Fourier Analysis (II), Corona Publishing Co., Ltd., 2007, Chapter 9.

このように、コーキング量が少ない状態であってもコーキング量を高精度で測定する技術は存在しなかった。 As described above, there has been no technique for measuring the amount of caulking with high accuracy even when the amount of caulking is small.

そこで、本発明は、上記問題に鑑みてなされたものであり、本発明の目的とするところは、コーキング量が少ない状態であってもコーキング量を高精度で測定することが可能な、新規かつ改良された触媒層のコーキング量の測定方法を提供することにある。 Therefore, the present invention has been made in view of the above problems, and an object of the present invention is a novel and novel method capable of measuring the caulking amount with high accuracy even when the caulking amount is small. It is an object of the present invention to provide an improved method for measuring the amount of caulking in a catalyst layer.

上記課題を解決するために、本発明のある観点によれば、共通の流入集合管および流出集合管に並列に接続された複数の固定床触媒反応器のうち、いずれか一の固定床触媒反応器内に設けられた触媒層のコーキング量を測定する触媒層のコーキング量の測定方法であって、一の固定床触媒反応器が接続される配管系内に、スピーカおよび一の固定床触媒反応器に付属するマイクロフォンを、一の固定床触媒反応器内に設けられた触媒層がスピーカおよびマイクロフォンの間に配置され、かつ、スピーカおよびマイクロフォンが配管系の配管内側に向くようにそれぞれ設け、スピーカからパルス状の音波を出力させ、マイクロフォンで音波を時系列的に計測し、マイクロフォンでの音波測定値を処理して自己相関係数を測定し、位相差０秒近傍での自己相関係数のピーク幅に基づいて、一の固定床触媒反応器内に設けられた触媒層のコーキング量を、他の固定床触媒反応器内に設けられた触媒層のコーキング量に対する相対値として測定することを特徴とする、触媒層のコーキング量の測定方法が提供される。 In order to solve the above problems, according to a certain aspect of the present invention, any one of a plurality of fixed-bed catalytic reactors connected in parallel to a common inflow collecting pipe and an outflow collecting pipe is one of the fixed-bed catalytic reactions. It is a method of measuring the amount of coking of the catalyst layer for measuring the amount of coking of the catalyst layer provided in the vessel. In the piping system to which one fixed-bed catalytic reactor is connected, a speaker and one fixed-bed catalytic reaction are carried out. The microphone attached to the vessel is provided so that the catalyst layer provided in one fixed-bed catalytic reactor is arranged between the speaker and the microphone, and the speaker and the microphone face the inside of the piping of the piping system. A pulsed sound is output from the catalyst, the sound is measured in time series with a microphone, the self-correlation coefficient is measured by processing the sound measurement value with the microphone, and the autocorrelation coefficient in the vicinity of the phase difference of 0 seconds is measured. Based on the peak width, the amount of coking of the catalyst layer provided in one fixed-bed catalyst reactor is measured as a relative value to the amount of coking of the catalyst layer provided in another fixed-bed catalyst reactor. A characteristic method for measuring the amount of coking in the catalyst layer is provided.

ここで、一の固定床触媒反応器に対して測定された位相差０秒近傍での自己相関係数のピーク幅と、全ての固定床触媒反応器に対して測定された位相差０秒近傍での自己相関係数のピーク幅の平均値とを比較することによって、一の固定床触媒反応器内に設けられた触媒層のコーキング量を、他の固定床触媒反応器内に設けられた触媒層のコーキング量に対する相対値として測定してもよい。 Here, the peak width of the autocorrelation coefficient in the vicinity of the phase difference of 0 seconds measured for one fixed-bed catalytic reactor and the phase difference of the vicinity of 0 seconds measured for all the fixed-bed catalytic reactors. By comparing with the average value of the peak width of the autocorrelation coefficient in, the amount of coking of the catalyst layer provided in one fixed-bed catalyst reactor was provided in another fixed-bed catalyst reactor. It may be measured as a relative value to the amount of coking of the catalyst layer.

また、一の固定床触媒反応器に対して測定された位相差０秒近傍での自己相関係数のピーク幅と、全ての固定床触媒反応器の触媒層がコークを含まない状態で一の固定床触媒反応器に対して測定された位相差０秒近傍での自己相関係数のピーク幅とを比較することによって、一の固定床触媒反応器内に設けられた触媒層のコーキング量を、他の固定床触媒反応器内に設けられた触媒層のコーキング量に対する相対値として測定してもよい。 In addition, the peak width of the autocorrelation coefficient in the vicinity of the phase difference of 0 seconds measured for one fixed-bed catalyst reactor and one in the state where the catalyst layers of all the fixed-bed catalyst reactors do not contain cork. By comparing the peak width of the autocorrelation coefficient in the vicinity of the phase difference of 0 seconds measured for the fixed-bed catalyst reactor, the amount of coking of the catalyst layer provided in one fixed-bed catalyst reactor can be determined. , May be measured as a relative value to the amount of coking of the catalyst layer provided in another fixed-bed catalyst reactor.

また、パルス状の音波の波長は、スピーカから出力される音波が一の固定床触媒反応器を経由して一の固定床触媒反応器に付属するマイクロフォンまで伝播する経路長と、スピーカから出力される音波が一の固定床触媒反応器に隣接する他の固定床触媒反応器を経由して一の固定床触媒反応器に付属するマイクロフォンまで伝播する経路長との経路長差の４倍を超えるように設定されてもよい。
The wavelength of the pulsed sound wave is the path length that the sound wave output from the speaker propagates through one fixed bed catalyst reactor to the microphone attached to one fixed bed catalyst reactor, and the path length is output from the speaker. More than four times the path length difference from the path length at which the sound waves propagate to the microphone attached to one fixed bed catalytic reactor via another fixed bed catalytic reactor adjacent to one fixed bed catalytic reactor. It may be set as follows.

本発明の第１の特徴は、例えば、８００℃といった高温で反応する触媒層のコーキング量を、当該触媒層における音波の透過性を測定することによって、操業中に（オンラインに）、非接触、かつ、高精度で測定できることである。従来技術にはこのような目的を満足する技術は、存在しなかった。 The first feature of the present invention is that the amount of coking of a catalyst layer that reacts at a high temperature such as 800 ° C. is measured during operation (online) by measuring the permeability of sound waves in the catalyst layer. Moreover, it is possible to measure with high accuracy. There is no technique in the prior art that satisfies such an object.

本発明の第２の特徴は、並列に複数配置された固定床触媒反応器のうち、着目する固定床触媒反応器（一の固定床触媒反応器）でのパルス状の音波に対する音圧測定値の自己相関係数を用いることによって、一の固定床触媒反応器内に設けられた触媒層のコーキング量を、他の固定床触媒反応器内に設けられた触媒層のコーキング量に対する相対値として測定することができる。つまり、一の固定床触媒反応器のコーキング量が他の固定床触媒反応器のコーキング量に比べて大きいかどうかの判定を行うことができる。すなわち、コーキング量が少ない状態であってもコーキング量を高精度で測定することができる。このことによって、複数の固定床触媒反応器のうち、集中的にコーキングを生じた固定床触媒反応器を早期に（具体的には、閉塞状態に至る前に）発見し、この固定床触媒反応器のみに対してコーク除去を行うことができる。これにより、効果的にコークの除去を行うことができるとともに、コーク除去装置の操作頻度を必要最低限とすることができる。また、このような効果はパルス状の音波を用いる場合にのみ得られ、パルス状の音波の代わりに単に連続音波を与える場合には実現できないことを本発明者らは、見出した。 The second feature of the present invention is the sound pressure measurement value for pulsed sound waves in the fixed-bed catalytic reactor (one fixed-bed catalytic reactor) of interest among the plurality of fixed-bed catalytic reactors arranged in parallel. By using the autocorrelation coefficient of, the amount of coking of the catalyst layer provided in one fixed-bed catalyst reactor is used as a relative value to the amount of coking of the catalyst layer provided in the other fixed-bed catalyst reactor. Can be measured. That is, it is possible to determine whether or not the caulking amount of one fixed-bed catalyst reactor is larger than the caulking amount of another fixed-bed catalyst reactor. That is, the amount of caulking can be measured with high accuracy even when the amount of caulking is small. As a result, among the plurality of fixed-bed catalytic reactors, the fixed-bed catalytic reactor that caused intensive caulking was discovered at an early stage (specifically, before the blockage state was reached), and this fixed-bed catalytic reaction was performed. Caulk removal can be performed only on the vessel. As a result, the cork can be effectively removed, and the operation frequency of the cork removing device can be minimized. Further, the present inventors have found that such an effect can be obtained only when a pulsed sound wave is used, and cannot be realized when a continuous sound wave is simply applied instead of the pulsed sound wave.

このように、本発明では、自己相関係数を用いてコーキング量の相対値を測定する。自己相関係数がコーキング量の相対値とよく対応づくことは、本発明者が実施した試験によってはじめて見出されたものである。 As described above, in the present invention, the relative value of the caulking amount is measured using the autocorrelation coefficient. It was only found by the test conducted by the present inventor that the autocorrelation coefficient corresponds well with the relative value of the amount of caulking.

以上説明したように本発明によれば、自己相関係数を用いてコーキング量を測定するので、コーキング量を、非接触にオンラインで安価、かつ、高精度で測定することができる。これにより、コーキング量が少ない状態であってもコーキング量を高精度で測定することができる。したがって、触媒層からのコーク除去操作を必要最小限の頻度で実施できる。 As described above, according to the present invention, since the caulking amount is measured using the autocorrelation coefficient, the caulking amount can be measured online in a non-contact manner at low cost and with high accuracy. As a result, the amount of caulking can be measured with high accuracy even when the amount of caulking is small. Therefore, the cork removal operation from the catalyst layer can be performed with the minimum necessary frequency.

本実施形態を実施するための装置構成の一例を示す説明図である。It is explanatory drawing which shows an example of the apparatus configuration for carrying out this Embodiment. 図１の装置構成のうち触媒反応器周辺の詳細構成の一例を示す説明図である。It is explanatory drawing which shows an example of the detailed structure around a catalyst reactor in the apparatus structure of FIG. 本実施形態における音波の自己相関係数の一例を示すグラフである。It is a graph which shows an example of the autocorrelation coefficient of the sound wave in this embodiment. 本実施形態における音波の自己相関係数の他の一例を示すグラフである。It is a graph which shows another example of the autocorrelation coefficient of the sound wave in this embodiment. 本実施形態における音波の自己相関係数差の一例を示すグラフである。It is a graph which shows an example of the autocorrelation coefficient difference of the sound wave in this embodiment. 本実施形態における測定原理を説明するためのグラフである。It is a graph for demonstrating the measurement principle in this embodiment. 本実施形態における測定原理を説明するためのグラフである。It is a graph for demonstrating the measurement principle in this embodiment. 本実施形態における測定原理を説明するためのグラフである。It is a graph for demonstrating the measurement principle in this embodiment. 本実施形態における測定原理を説明するためのグラフである。It is a graph for demonstrating the measurement principle in this embodiment. 本実施形態における測定原理を説明するためのグラフである。It is a graph for demonstrating the measurement principle in this embodiment.

以下に添付図面を参照しながら、本発明の好適な実施の形態について詳細に説明する。なお、本明細書及び図面において、実質的に同一の機能構成を有する構成要素については、同一の符号を付することにより重複説明を省略する。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the present specification and the drawings, components having substantially the same functional configuration are designated by the same reference numerals, so that duplicate description will be omitted.

＜１．前提となる装置構成＞
本実施形態を実施するための化学反応装置の一例を図１に示す。化学反応装置内では、複数の触媒反応器１が流入管２および流出管３を介して共通の流入集合管１２および流出集合管１３に並列に接続されており、これらの触媒反応器１、流入集合管１２、流出集合管１３、流入管２、及び流出管３が加熱炉５内に収納される。ガスの流れ１１は、流入集合管１２、各流入管２、各触媒反応器１、各流出管３、流出集合管１３の順に与えられる。 <1. Prerequisite device configuration>
FIG. 1 shows an example of a chemical reaction apparatus for carrying out this embodiment. In the chemical reactor, a plurality of catalytic reactors 1 are connected in parallel to the common inflow collecting pipe 12 and outflow collecting pipe 13 via the inflow pipe 2 and the outflow pipe 3, and these catalytic reactors 1 and the inflow The collecting pipe 12, the outflow collecting pipe 13, the inflow pipe 2, and the outflow pipe 3 are housed in the heating furnace 5. The gas flow 11 is given in the order of the inflow collecting pipe 12, each inflow pipe 2, each catalytic reactor 1, each outflow pipe 3, and the outflow collecting pipe 13.

流出集合管１３から管が分岐し、当該分岐管が加熱炉５外に引き出され、弁１０を介してスピーカ７と第２のマイクロフォン９が接続される。スピーカ７及び第２のマイクロフォン９は、配管系の配管内側に向くように分岐管に接続される。図１に示す反応系（すなわち、１対の流入集合管１２、流出集合管１３、およびこれらに接続される複数の触媒反応器１）において、スピーカ７および第２のマイクロフォン９は１台のみであってもよい。一方で、触媒反応器１は２台以上設けられる。図１では模式的に触媒反応器１を４台示したが、触媒反応器１は、例えば、１００台以上であってもよい。第２のマイクロフォン９は、スピーカの出力を確認するためのものであるので、スピーカ７の特性と入力信号が既知の場合には省略してもよい。スピーカ７及び第２のマイクロフォン９は市販のものを用いることができる。 A pipe branches from the outflow collecting pipe 13, the branch pipe is pulled out of the heating furnace 5, and the speaker 7 and the second microphone 9 are connected via the valve 10. The speaker 7 and the second microphone 9 are connected to the branch pipe so as to face the inside of the pipe of the piping system. In the reaction system shown in FIG. 1 (that is, a pair of inflow collecting pipes 12, outflow collecting pipes 13, and a plurality of catalytic reactors 1 connected thereto), only one speaker 7 and a second microphone 9 are used. There may be. On the other hand, two or more catalyst reactors 1 are provided. In FIG. 1, four catalytic reactors 1 are schematically shown, but the number of catalytic reactors 1 may be 100 or more, for example. Since the second microphone 9 is for confirming the output of the speaker, it may be omitted if the characteristics of the speaker 7 and the input signal are known. Commercially available speakers 7 and the second microphone 9 can be used.

図１の装置構成のうち触媒反応器周辺の詳細構成を図２に示す。触媒粒子の充填された触媒層４を収納する固定床である触媒反応器１は、流入管２と流出管３に接続される。流入管２、触媒反応器１、流出管３の順にガスの流れ１１が与えられ、触媒層４内で原料ガス（流入管２側のガス）が改質され、改質ガス（流出管３側のガス）に化学変化する。流入管２、流出管３、並びに、触媒反応器１は、加熱炉５内に設置されて所定反応温度に保持される。なお、加熱炉５は各触媒反応器１の温度が略均一になるように各触媒反応器１を加熱するが、実際には各触媒反応器１の温度にばらつきが生じる。このばらつきのため、各触媒反応器１におけるコーキング量に差が生じる。そして、操業を継続していくと、いずれかの触媒反応器１において集中的にコーキングが生じ、他の触媒反応器１よりも速やかに閉塞状態に至る。このため、本実施形態では、コーキングが集中的に生じた触媒反応器１を早期に（すなわち、閉塞状態に至る前に）発見する。触媒反応器１には例えば、特許文献１に示すようなコーク除去装置６が付帯し、これを操作することによってオンラインで触媒反応器１からコークを除去できる。 Of the equipment configurations shown in FIG. 1, the detailed configuration around the catalytic reactor is shown in FIG. The catalyst reactor 1, which is a fixed bed for accommodating the catalyst layer 4 filled with the catalyst particles, is connected to the inflow pipe 2 and the outflow pipe 3. The gas flow 11 is given in the order of the inflow pipe 2, the catalyst reactor 1, and the outflow pipe 3, the raw material gas (gas on the inflow pipe 2 side) is reformed in the catalyst layer 4, and the reformed gas (outflow pipe 3 side) is reformed. Chemically changes to gas). The inflow pipe 2, the outflow pipe 3, and the catalytic reactor 1 are installed in the heating furnace 5 and maintained at a predetermined reaction temperature. The heating furnace 5 heats each catalytic reactor 1 so that the temperature of each catalytic reactor 1 becomes substantially uniform, but the temperature of each catalytic reactor 1 actually varies. Due to this variation, there is a difference in the amount of caulking in each catalytic reactor 1. Then, as the operation is continued, caulking occurs intensively in one of the catalytic reactors 1, and the closed state is reached more quickly than in the other catalytic reactors 1. Therefore, in the present embodiment, the catalytic reactor 1 in which caulking is intensively generated is detected at an early stage (that is, before the blocked state is reached). For example, the catalyst reactor 1 is provided with a cork removing device 6 as shown in Patent Document 1, and by operating the cork removing device 6, the cork can be removed from the catalyst reactor 1 online.

流入管２から管が分岐し、当該分岐管が加熱炉５外に引き出され、弁１０を介して第１のマイクロフォン８が接続される。第１のマイクロフォン８は、配管系の配管内側に向くように分岐管に接続される。第１のマイクロフォン８は市販のものを用いることができる。いずれの触媒反応器１も図２に示す構成を有することができる。 A pipe branches from the inflow pipe 2, the branch pipe is pulled out of the heating furnace 5, and the first microphone 8 is connected via the valve 10. The first microphone 8 is connected to the branch pipe so as to face the inside of the pipe of the piping system. As the first microphone 8, a commercially available one can be used. Any catalytic reactor 1 can have the configuration shown in FIG.

スピーカ７の制御や各マイクロフォンでのデータの記録には、図示しない市販の音響制御装置およびデータレコーダを用いることができる。弁１０にはボール弁等を用いればよく、測定を行わない際には弁１０を閉めることによってスピーカ７や各マイクロフォンを雰囲気による汚染や腐食から保護することができる。触媒反応器１の寸法は、例えば直径５０～３００ｍｍ程度であってもよく、触媒層４の高さは、１０ｃｍ～１０ｍ程度であってもよく、触媒の量は、１ｋｇ～１０００ｋｇであってもよいが、これらの数値範囲に限定されない。 Commercially available acoustic control devices and data recorders (not shown) can be used for controlling the speaker 7 and recording data with each microphone. A ball valve or the like may be used for the valve 10, and the speaker 7 and each microphone can be protected from contamination and corrosion due to the atmosphere by closing the valve 10 when the measurement is not performed. The dimensions of the catalyst reactor 1 may be, for example, about 50 to 300 mm in diameter, the height of the catalyst layer 4 may be about 10 cm to 10 m, and the amount of catalyst may be about 1 kg to 1000 kg. Good, but not limited to these numerical ranges.

なお、第１のマイクロフォン８、スピーカ７、並びに、触媒層４の位置関係は、化学反応装置の管路系内において、第１のマイクロフォン８とスピーカ７の間の空間に触媒層４を配置すればよいのであって、例えば、スピーカ７が流入集合管１２に接続され、かつ、第１のマイクロフォンが流出管３に接続されてもよい。第２のマイクロフォン９は、スピーカ７と流入集合管１２の間の空間に配置すればよい。 The positional relationship between the first microphone 8, the speaker 7, and the catalyst layer 4 is such that the catalyst layer 4 is arranged in the space between the first microphone 8 and the speaker 7 in the pipeline system of the chemical reaction apparatus. For example, the speaker 7 may be connected to the inflow collecting tube 12 and the first microphone may be connected to the outflow tube 3. The second microphone 9 may be arranged in the space between the speaker 7 and the inflow collecting pipe 12.

また、上記の例では全ての触媒反応器１に第１のマイクロフォン８を付属させているが、閉塞しやすい触媒反応器が予め判明している等の場合には、そのような触媒反応器のみに第１のマイクロフォン８を付属させ、これ以外の触媒反応器では第１のマイクロフォン８を省略してもよい。 Further, in the above example, the first microphone 8 is attached to all the catalytic reactors 1, but when the catalytic reactors that are easily clogged are known in advance, only such catalytic reactors are used. The first microphone 8 may be attached to the reactor, and the first microphone 8 may be omitted in other catalytic reactors.

＜２．前提となる操業＞
化学反応装置を用いた操業は、例えば以下のとおりである。すなわち、メタンやタール等の炭化水素ガスを含む原料ガスと水蒸気を流入管２に供給し、直径５ｍｍ～１００ｍｍ程度のＮｉ系触媒粒子を充填した触媒層４を通過させる。これにより、炭化水素ガスを水蒸気改質してＨ２ガスとＣＯガス等の改質ガスに化学変化させる。ついで、改質ガスを流出管３から流出させる。反応温度は、例えば、８００℃とされる。この反応の際、直径数μｍ～数百μｍのコーク粒子が多数、副生する。コーキング量は、最大で触媒質量の１０質量％程度である。本実施形態が対象とする操業は、上記のものに限られるわけではなく、触媒反応中に触媒粒子間の空間にコーキングを生じるものであれば、どのような操業であってもよい。 <2. Prerequisite operation>
The operation using the chemical reaction device is as follows, for example. That is, a raw material gas containing a hydrocarbon gas such as methane or tar and water vapor are supplied to the inflow pipe 2 and passed through the catalyst layer 4 filled with Ni-based catalyst particles having a diameter of about 5 mm to 100 mm. As a result, the hydrocarbon gas is steam reformed and chemically changed into reformed gases such as H2 gas and CO gas. Then, the reforming gas is discharged from the outflow pipe 3. The reaction temperature is, for example, 800 ° C. During this reaction, a large number of cork particles having a diameter of several μm to several hundred μm are by-produced. The maximum amount of caulking is about 10% by mass of the catalyst mass. The operation targeted by the present embodiment is not limited to the above, and may be any operation as long as it causes caulking in the space between the catalyst particles during the catalytic reaction.

＜３．測定手順＞
つぎに、本実施形態に係る触媒層のコーキング量の測定方法について説明する。第１の手順として、全ての触媒反応器１内の触媒層４がコークを含まない状態で、弁１０を全て開放し、スピーカ７に所定の音波を出力させる。ここで、所定の音波は、触媒層４を透過しても計測可能なレベルのパワー（すなわち、音圧）を保つことのできる低周波のパルス状の音波であることが好ましい。例えば、出力音圧レベルが９０ｄＢ／Ｗの仕様のスピーカ７に１０Ｗ（音波出力時）の電力を供給してスピーカ７から、２００Ｈｚの単一サイン波の音波を５Ｈｚの頻度で出力してもよい。ここで、スピーカ７から頻度の低いパルス状の音波（つまり、連続波ではない音波）を出力することとしたのは、本実施形態では、第１のマイクロフォン８が測定した音波の自己相関係数を用いてコーキング量を測定するからである。音波を連続波とした場合、コーキング量の大小によって自己相関係数にほとんど差が生じなくなる。 <3. Measurement procedure>
Next, a method for measuring the amount of caulking in the catalyst layer according to the present embodiment will be described. As a first procedure, in a state where the catalyst layer 4 in all the catalyst reactors 1 does not contain cork, all the valves 10 are opened and the speaker 7 is made to output a predetermined sound wave. Here, the predetermined sound wave is preferably a low-frequency pulsed sound wave that can maintain a measurable level of power (that is, sound pressure) even if it passes through the catalyst layer 4. For example, a speaker 7 having an output sound pressure level of 90 dB / W may be supplied with a power of 10 W (at the time of sound wave output), and a 200 Hz single sine wave sound wave may be output from the speaker 7 at a frequency of 5 Hz. .. Here, it was decided to output an infrequent pulsed sound wave (that is, a sound wave that is not a continuous wave) from the speaker 7, which is the autocorrelation coefficient of the sound wave measured by the first microphone 8 in the present embodiment. This is because the amount of coking is measured using. When the sound wave is a continuous wave, there is almost no difference in the autocorrelation coefficient depending on the magnitude of the caulking amount.

このように生成させた音波を各触媒反応器１の第１のマイクロフォン８にて測定・記録する。記録内容は、少なくとも音圧の時系列データを含む。各第１のマイクロフォンが音波を測定した後、全ての弁１０が閉塞される。ここで記録された各第１のマイクロフォン８の音圧データを処理して触媒反応器１ごとに音波の自己相関係数（初期自己相関係数と呼称する）を算出する。自己相関係数の算出方法には、例えば、非特許文献１に記載の方法を用いればよい。ここで、自己相関係数は、少なくとも位相差０秒近傍の値を算出すれば良い。位相差０秒近傍の範囲としては、例えば、位相差０秒を含み、かつ音波のパルス間隔時間より短い時間範囲であればよい。一例として、－０．０１～０．０１秒の範囲が挙げられるが、これに限定されない。 The sound waves generated in this way are measured and recorded by the first microphone 8 of each catalytic reactor 1. The recorded content includes at least time series data of sound pressure. After each first microphone measures the sound wave, all valves 10 are closed. The sound pressure data of each first microphone 8 recorded here is processed to calculate the autocorrelation coefficient (referred to as the initial autocorrelation coefficient) of the sound wave for each catalytic reactor 1. As a method for calculating the autocorrelation coefficient, for example, the method described in Non-Patent Document 1 may be used. Here, the autocorrelation coefficient may be calculated at least in the vicinity of the phase difference of 0 seconds. The range near the phase difference of 0 seconds may be, for example, a time range including the phase difference of 0 seconds and shorter than the pulse interval time of the sound wave. One example is, but is not limited to, the range of -0.01 to 0.01 seconds.

初期自己相関係数の一例を図３、図４に示す。図３、図４では、横軸が位相差（秒、ｓ）を示し、縦軸が自己相関係数を示す。「コークなし」のグラフが初期自己相関係数を示す。着目している触媒反応器１（以下、着目している触媒反応器を「第１の触媒反応器１ａ」とも称する）に付属する第１のマイクロフォン８には、第１の触媒反応器１ａを経由した音波が最初に到達し、他の触媒反応器（すなわち、「第１の触媒反応器１ａ」以外の任意の触媒反応器１。以下、このような触媒反応器１を「第２の触媒反応器１ｂ」とも総称する。）を経由した音波が遅れて到達する。したがって、第１の触媒反応器１ａに付属する第１のマイクロフォン８が測定する音波（具体的には、音圧の時系列データ）は、第１の触媒反応器１ａを経由した音波と、第２の触媒反応器１ｂを経由した音波との合成波となる。他の第１のマイクロフォン８が測定する音波も同様である。すなわち、ある第２の触媒反応器１ｂに付属する第１のマイクロフォン８が測定する音波は、その第２の触媒反応器１ｂを経由した音波と、他の第２の触媒反応器１ｂを経由した音波及び第１の触媒反応器１ａを経由した音波との合成波となる。 An example of the initial self-correlation coefficient is shown in FIGS. 3 and 4. In FIGS. 3 and 4, the horizontal axis indicates the phase difference (seconds, s), and the vertical axis indicates the autocorrelation coefficient. The "no cork" graph shows the initial autocorrelation coefficient. A first catalyst reactor 1a is attached to the first microphone 8 attached to the catalyst reactor 1 of interest (hereinafter, the catalyst reactor of interest is also referred to as "first catalyst reactor 1a"). The sound passing through reaches first, and any catalytic reactor 1 other than another catalytic reactor (that is, "first catalytic reactor 1a". Hereinafter, such catalytic reactor 1 is referred to as "second catalyst". The sound wave passing through the reactor 1b (also collectively referred to as) arrives with a delay. Therefore, the sound wave (specifically, the time-series data of the sound pressure) measured by the first microphone 8 attached to the first catalyst reactor 1a is the sound wave passing through the first catalyst reactor 1a and the first. It is a combined wave with a sound wave that has passed through the catalyst reactor 1b of 2. The same applies to the sound waves measured by the other first microphone 8. That is, the sound wave measured by the first microphone 8 attached to the second catalyst reactor 1b passed through the second catalyst reactor 1b and the other second catalyst reactor 1b. It is a combined wave with a sound wave and a sound wave passing through the first catalytic reactor 1a.

ここで、第１の触媒反応器１ａにコーキングが生じていない場合、第１のマイクロフォン８に最初に到達した音波は、当該音波に遅れて到達した音波（以下、「遅延音波」とも称する。遅延音波は、第２の触媒反応器１ｂを経由しているため音圧が低い）に卓越している。したがって、第１のマイクロフォン８が測定する音波（合成波）は、遅延音波の影響をほとんど受けない。さらに、スピーカ７から出力された音波はパルス状の音波である。このため、初期自己相関係数は、位相差０秒近傍において高いピークを有し、かつ、ピーク幅が狭くなる。 Here, when caulking does not occur in the first catalytic reactor 1a, the sound wave that first reaches the first microphone 8 is a sound wave that arrives later than the sound wave (hereinafter, also referred to as “delayed sound wave”). The sound wave is predominant because it passes through the second catalytic reactor 1b and therefore has a low sound pressure). Therefore, the sound wave (synthetic wave) measured by the first microphone 8 is hardly affected by the delayed sound wave. Further, the sound wave output from the speaker 7 is a pulsed sound wave. Therefore, the initial autocorrelation coefficient has a high peak in the vicinity of the phase difference of 0 seconds, and the peak width becomes narrow.

第２の手順として、いずれかの触媒反応器１内の触媒層４にコークが含まれることが想定される状態、例えば、上述した触媒改質操業（前提となる操業）を長時間実施した状態で、上記と同様の方法で触媒反応器１ごとに音波の自己相関係数（比較自己相関係数と呼称する）を算出する。ここでも、自己相関係数は、少なくとも位相差０秒近傍の値を算出すれば良い。位相差０秒近傍の範囲は上述したとおりである。比較自己相関係数の一例を図３、図４に示す。図３、図４では、「コークあり」のグラフが比較自己相関係数を示す。図３は、操業後にすべての触媒反応器１間でコーキングの差のない（一様にコーキングする）場合の第１の触媒反応器１ａの自己相関係数を示し、図４は、操業後に、着目している第１の触媒反応器１ａのコーキングのみが他の触媒反応器（つまり第２の触媒反応器１ｂ）よりも極端に多く生じる（コーキングが集中する）場合の第１の触媒反応器１ａの自己相関係数を示す。図３、４に示すように、すべての触媒反応器１間で一様にコーキングが生じた場合、第１の触媒反応器１ａでは、比較自己相関係数と初期自己相関係数との間にほとんど違いがないのに対し、第１の触媒反応器１ａにコーキングが集中した場合、当該第１の触媒反応器１ａでは、比較自己相関係数のピーク幅が初期自己相関係数のものよりも広くなっている。なお、ここでの「コークあり」は、いずれかの触媒反応器１でコーキングが発生したことを想定する操業後の状態を意味する。 As a second procedure, a state in which it is assumed that the catalyst layer 4 in any of the catalyst reactors 1 contains cork, for example, a state in which the above-mentioned catalyst reforming operation (premise operation) is carried out for a long time. Then, the autocorrelation coefficient (referred to as a comparative autocorrelation coefficient) of the sound wave is calculated for each catalytic reactor 1 by the same method as described above. Again, the autocorrelation coefficient may be calculated at least in the vicinity of the phase difference of 0 seconds. The range in the vicinity of the phase difference of 0 seconds is as described above. An example of the comparative autocorrelation coefficient is shown in FIGS. 3 and 4. In FIGS. 3 and 4, the “with cork” graph shows the comparative autocorrelation coefficient. FIG. 3 shows the autocorrelation coefficient of the first catalytic reactor 1a when there is no difference in coking (uniformly coking) among all the catalytic reactors 1 after the operation, and FIG. 4 shows the autocorrelation coefficient of the first catalytic reactor 1a after the operation. The first catalytic reactor when only the coking of the first catalytic reactor 1a of interest occurs significantly more (coking is concentrated) than the other catalytic reactors (ie, the second catalytic reactor 1b). The autocorrelation coefficient of 1a is shown. As shown in FIGS. 3 and 4, when coking occurs uniformly among all the catalytic reactors 1, in the first catalytic reactor 1a, between the comparative autocorrelation coefficient and the initial autocorrelation coefficient. Whereas there is little difference, when coking is concentrated in the first catalytic reactor 1a, the peak width of the comparative autocorrelation coefficient in the first catalytic reactor 1a is larger than that of the initial autocorrelation coefficient. It is getting wider. In addition, "with caulking" here means a state after the operation assuming that caulking has occurred in any of the catalytic reactors 1.

第１の触媒反応器１ａにコーキングが生じた場合、第１の触媒反応器１ａを通過する際に音波の音圧は、減衰する。第１の触媒反応器１ａに付属する第１のマイクロフォン８には、第１の触媒反応器１ａを経由した音波が最初に到達し、第２の触媒反応器１ｂを経由した音波、すなわち遅延音波が遅れて到達する。ここで、図４に対応する第１の触媒反応器１ａにコーキングが集中する場合、第１のマイクロフォン８に最初に到達した音波は、他の触媒反応器（すなわち第２の触媒反応器１ｂ）を経由して到達する遅延音波に比べてより大きな減衰を受け、遅延音波並みの音圧まで低下している。このため、第１のマイクロフォン８が測定する音波（合成波）は、遅延音波（第２の触媒反応器１ｂを経由しているため音圧が低い）による影響を有意に受ける。具体的には、第１のマイクロフォン８が測定する音波（合成波）は、初期自己相関係数の測定時の合成波よりも波長が有意に長くなる。このため、比較自己相関係数は、位相差の存在する（すなわち、位相差０以外の）領域でも０を超える値を有し、位相差０近傍におけるピーク幅が広くなる。ここで、第１の触媒反応器１ａのコーキング量と第２の触媒反応器１ｂのコーキング量との差、すなわち第１の触媒反応器１ａのコーキング量の相対値が大きいほど、遅延音波の影響が大きくなり、合成波の波長が長くなる。この結果、比較自己相関係数のピーク幅が広くなる。一方、すべての触媒反応器１間でコーキングの差のない（一様にコーキングする）場合、第１の触媒反応器１ａでは、操業の前後で音波の到達状況にほとんど変化はない（すなわち、第１のマイクロフォン８に最初に到達した音波と遅延音波とが一様に減衰する）ことから、第１のマイクロフォン８に最初に到達した音波は、依然として他の触媒反応器１を経由した音波に卓越する。したがって、比較自己相関係数にほとんど変化はない。なお、第１の触媒反応器１ａにコーキングが集中した場合、第２の触媒反応器１ｂ（コーキングが一様に生じている触媒反応器１）の比較自己相関係数も同様の挙動を示す（すなわち、比較自己相関係数は初期自己相関係数からほとんど変化しない）。詳細な測定原理は後述する。 When coking occurs in the first catalytic reactor 1a, the sound pressure of the sound wave is attenuated as it passes through the first catalytic reactor 1a. The sound wave that has passed through the first catalytic reactor 1a first reaches the first microphone 8 attached to the first catalytic reactor 1a, and the sound wave that has passed through the second catalytic reactor 1b, that is, a delayed sound wave. Arrives late. Here, when the coking is concentrated on the first catalytic reactor 1a corresponding to FIG. 4, the sound wave that first reaches the first microphone 8 is the other catalytic reactor (that is, the second catalytic reactor 1b). It receives a larger attenuation than the delayed sound wave that arrives via, and the sound pressure drops to the same level as the delayed sound wave. Therefore, the sound wave (synthetic wave) measured by the first microphone 8 is significantly affected by the delayed sound wave (the sound pressure is low because it passes through the second catalytic reactor 1b). Specifically, the sound wave (combined wave) measured by the first microphone 8 has a significantly longer wavelength than the synthesized wave at the time of measuring the initial autocorrelation coefficient. Therefore, the comparative autocorrelation coefficient has a value exceeding 0 even in a region where the phase difference exists (that is, other than the phase difference 0), and the peak width in the vicinity of the phase difference 0 becomes wide. Here, the larger the difference between the caulking amount of the first catalytic reactor 1a and the caulking amount of the second catalytic reactor 1b, that is, the larger the relative value of the caulking amount of the first catalytic reactor 1a, the more the influence of the delayed sound wave. Becomes larger and the wavelength of the combined wave becomes longer. As a result, the peak width of the comparative autocorrelation coefficient becomes wider. On the other hand, when there is no difference in coking between all the catalytic reactors 1 (coking uniformly), in the first catalytic reactor 1a, there is almost no change in the arrival state of the sound wave before and after the operation (that is, the first catalyst reactor 1a). Since the sound wave that first reaches the microphone 8 of 1 and the delayed sound wave are uniformly attenuated), the sound wave that first reaches the first microphone 8 still predominates to the sound wave that has passed through the other catalytic reactor 1. do. Therefore, there is almost no change in the comparative autocorrelation coefficient. When coking is concentrated in the first catalytic reactor 1a, the comparative autocorrelation coefficient of the second catalytic reactor 1b (catalytic reactor 1 in which coking is uniformly generated) also shows the same behavior (). That is, the comparative autocorrelation coefficient hardly changes from the initial autocorrelation coefficient). The detailed measurement principle will be described later.

第３の手順として、触媒反応器１ごとに比較自己相関係数と初期自己相関係数の差の絶対値（自己相関係数差と呼称する）を算出する。自己相関係数差は、位相差毎に算出される。自己相関係数差の一例を図５に示す。図５の横軸は位相差（秒、ｓ）を示し、縦軸は自己相関係数差を示す。図５の例では、第１の触媒反応器１ａでコーキングの集中が生じており（すなわち、比較自己相関係数が図４の特性を示し）、第２の触媒反応器１ｂではコーキングが一様である（すなわち、第２の触媒反応器１ｂ間でコーキング量に大きな差がなく、各第２の触媒反応器１ｂの比較自己相関係数が図３の特性を示す）。第１の触媒反応器１ａでは、コーキングの集中が生じているので、比較自己相関係数のピーク幅が広くなっている。このため、自己相関係数差が大きなピークを有する。これに対し、第２の触媒反応器１ｂでは、コーキングが一様なので、比較自己相関係数と初期自己相関係数との間に差は殆ど無い。このため、自己相関係数差は非常に小さくなる。 As a third procedure, the absolute value of the difference between the comparative autocorrelation coefficient and the initial autocorrelation coefficient (referred to as the autocorrelation coefficient difference) is calculated for each catalytic reactor 1. The self-correlation coefficient difference is calculated for each phase difference. An example of the difference in the autocorrelation coefficient is shown in FIG. The horizontal axis of FIG. 5 shows the phase difference (seconds, s), and the vertical axis shows the autocorrelation coefficient difference. In the example of FIG. 5, the concentration of coking occurs in the first catalytic reactor 1a (that is, the comparative autocorrelation coefficient shows the characteristics of FIG. 4), and the coking is uniform in the second catalytic reactor 1b. (That is, there is no significant difference in the amount of coking between the second catalytic reactors 1b, and the comparative autocorrelation coefficient of each second catalytic reactor 1b shows the characteristics of FIG. 3). In the first catalytic reactor 1a, since the concentration of caulking occurs, the peak width of the comparative autocorrelation coefficient is wide. Therefore, the difference in the autocorrelation coefficient has a large peak. On the other hand, in the second catalytic reactor 1b, since the caulking is uniform, there is almost no difference between the comparative autocorrelation coefficient and the initial autocorrelation coefficient. Therefore, the difference in the autocorrelation coefficient becomes very small.

そして、上述したように、第１の触媒反応器１ａのコーキング量と第２の触媒反応器１ｂのコーキング量との差、すなわち第１の触媒反応器１ａのコーキング量の相対値が大きいほど、比較自己相関係数のピーク幅が広くなる。すなわち、自己相関係数差の最大値が大きくなる。したがって、本実施形態では、比較自己相関係数のピーク幅、より具体的には自己相関係数差に基づいて、第１の触媒反応器１ａのコーキング量の相対値を測定することができる。これにより、例えば、第１の触媒反応器１ａの自己相関係数差の最大値（図５のグラフのピーク値）が所定値を超える場合、第１の触媒反応器１ａをコークによる閉塞が生じたものと判定することができる。また、第１の触媒反応器１ａの自己相関係数差が大きいほど、第１の触媒反応器１ａのコーキング量の相対値が大きいと判定することもできる。 Then, as described above, the larger the difference between the caulking amount of the first catalytic reactor 1a and the caulking amount of the second catalytic reactor 1b, that is, the larger the relative value of the caulking amount of the first catalytic reactor 1a, the more. The peak width of the comparative autocorrelation coefficient becomes wider. That is, the maximum value of the autocorrelation coefficient difference becomes large. Therefore, in the present embodiment, the relative value of the caulking amount of the first catalytic reactor 1a can be measured based on the peak width of the comparative autocorrelation coefficient, more specifically, the difference in the autocorrelation coefficient. As a result, for example, when the maximum value (peak value in the graph of FIG. 5) of the autocorrelation coefficient difference of the first catalytic reactor 1a exceeds a predetermined value, the first catalytic reactor 1a is blocked by cork. It can be determined that it is a catalyst. Further, it can be determined that the larger the difference in the autocorrelation coefficient of the first catalytic reactor 1a is, the larger the relative value of the caulking amount of the first catalytic reactor 1a is.

触媒層４の閉塞判定条件は、装置ごとに適宜、調査して定めればよいが、例えば、第１の触媒反応器１ａの自己相関係数差が０．４を超えるような場合、当該第１の触媒反応器１ａでのコーキング量は、第２の触媒反応器１ｂに対して顕著なコーキングを生じているといえる。 The conditions for determining the blockage of the catalyst layer 4 may be appropriately investigated and determined for each device. For example, when the difference in the autocorrelation coefficient of the first catalyst reactor 1a exceeds 0.4, the first It can be said that the amount of coking in the catalyst reactor 1a of 1 causes remarkable coking with respect to the second catalyst reactor 1b.

以上の手順によって、触媒反応器間での相対的なコーキング量を測定することができる。この測定の結果、閉塞の生じたと判定された触媒反応器、または、他の触媒反応器よりも著しくコーキング量が多いと判定された触媒反応器に対して、当該触媒反応器に付属するコーク除去装置６を操作して、当該触媒反応器からコークを除去することができる。このように、本実施形態によれば、自己相関係数を用いてコーキング量を測定するので、コーキング量を、非接触にオンラインで安価、かつ、高精度で測定することができる。これにより、コーキング量が少ない状態であってもコーキング量を高精度で測定することができる。したがって、触媒層からのコーク除去操作を必要最小限の頻度で実施できる。 By the above procedure, the relative amount of caulking between the catalytic reactors can be measured. As a result of this measurement, for a catalytic reactor determined to have clogged or a catalytic reactor determined to have a significantly larger amount of coking than other catalytic reactors, the cork attached to the catalytic reactor is removed. The device 6 can be operated to remove cork from the catalytic reactor. As described above, according to the present embodiment, since the caulking amount is measured using the autocorrelation coefficient, the caulking amount can be measured online in a non-contact manner at low cost and with high accuracy. As a result, the amount of caulking can be measured with high accuracy even when the amount of caulking is small. Therefore, the cork removal operation from the catalyst layer can be performed with the minimum necessary frequency.

＜４．測定原理＞
上記の測定方法によって、触媒反応器間での相対的なコーキング量を測定することができる理由を説明する。複数の触媒反応器１が並列に配置される図１、図２の装置構成において、スピーカ７から出力される音波が第１の触媒反応器１ａに付属する第１のマイクロフォン８に伝播する経路には、スピーカ７、流出集合管１３、第１の触媒反応器１ａに連結する流出管３、第１の触媒反応器１ａ、第１の触媒反応器１ａに連結する流入管２、及び第１のマイクロフォン８の順に音波が伝播する経路（第１の伝播経路とも称する）と、スピーカ７、流出集合管１３、第２の触媒反応器１ｂに連結する流出管３、第２の触媒反応器１ｂ、第２の触媒反応器１ｂに連結する流入管２、流入集合管１２、第１の触媒反応器１ａに付属する流入管２、及び第１のマイクロフォン８の順に伝播する経路（以下、「第２の伝播経路」とも称する）の２種類が存在する。図１の例では、右端の触媒反応器１を第１の触媒反応器１ａとし、他の３本の触媒反応器１を第２の触媒反応器１ｂとしている。したがって、第２の伝播経路は３本存在する。もちろん、第１の触媒反応器１ａは任意の触媒反応器１でよい。 <4. Measurement principle>
The reason why the relative amount of caulking between catalytic reactors can be measured by the above measuring method will be described. In the apparatus configuration of FIGS. 1 and 2 in which a plurality of catalyst reactors 1 are arranged in parallel, the sound wave output from the speaker 7 propagates to the first microphone 8 attached to the first catalyst reactor 1a. 7 is a speaker 7, an outflow collecting tube 13, an outflow tube 3 connected to a first catalytic reactor 1a, a first catalytic reactor 1a, an inflow tube 2 connected to a first catalytic reactor 1a, and a first. A path through which sound waves propagate in the order of the microphone 8 (also referred to as a first propagation path), a speaker 7, an outflow collecting tube 13, an outflow tube 3 connected to a second catalytic reactor 1b, a second catalytic reactor 1b, The inflow pipe 2 connected to the second catalytic reactor 1b, the inflow collecting pipe 12, the inflow pipe 2 attached to the first catalytic reactor 1a, and the first microphone 8 propagate in this order (hereinafter, "second". There are two types (also referred to as "propagation path"). In the example of FIG. 1, the catalyst reactor 1 at the right end is a first catalyst reactor 1a, and the other three catalyst reactors 1 are a second catalyst reactor 1b. Therefore, there are three second propagation paths. Of course, the first catalytic reactor 1a may be any catalytic reactor 1.

触媒反応器間でコーキング量に差のない場合には、第１の伝播経路の方が第２の伝播経路よりも行程が短く、伝播途中での音波減衰が少ないため、第１の伝播経路による音波の伝播が卓越する。この状態でパルス状の音波（１波長分の音波）をスピーカ７から出力し、第１の触媒反応器１ａに付属する第１のマイクロフォン８で音波（具体的には、音圧の時系列データ）を測定する。そして、音波の自己相関係数をパルス間隔時間より短い時間範囲において求めると、第１の伝播経路を経由して第１のマイクロフォン８に到達した音波が第２の伝播経路を経由して第１のマイクロフォン８に到達した音波、すなわち遅延音波に卓越する。したがって、第１のマイクロフォン８が測定する音波（合成波）は、遅延音波の影響をほとんど受けない。さらに、スピーカ７から出力された音波はパルス状の音波である。したがって、自己相関係数は、位相差０秒の近傍に鋭い（ピーク幅の小さい）ピークを有する波形となる（図４の「コークなし」のグラフを参照）。 When there is no difference in the amount of caulking between the catalytic reactors, the first propagation path has a shorter stroke than the second propagation path, and the sound wave attenuation during propagation is smaller, so that the first propagation path is used. Sound wave propagation is predominant. In this state, a pulsed sound wave (sound wave for one wavelength) is output from the speaker 7, and a sound wave (specifically, time-series data of sound pressure) is output by the first microphone 8 attached to the first catalytic reactor 1a. ) Is measured. Then, when the autocorrelation coefficient of the sound wave is obtained in a time range shorter than the pulse interval time, the sound wave that reaches the first microphone 8 via the first propagation path is the first via the second propagation path. The sound wave that reaches the microphone 8 of the above, that is, the delayed sound wave is predominant. Therefore, the sound wave (synthetic wave) measured by the first microphone 8 is hardly affected by the delayed sound wave. Further, the sound wave output from the speaker 7 is a pulsed sound wave. Therefore, the autocorrelation coefficient is a waveform having a sharp (small peak width) peak in the vicinity of the phase difference of 0 seconds (see the “no cork” graph in FIG. 4).

一方、触媒反応器間でコーキング量に大きな差が存在する場合、例えば、第１の触媒反応器１ａのみ閉塞状態にあって（つまり、コーキング量が大きく）、全ての第２の触媒反応器１ｂでのコーキング量が第１の触媒反応器１ａのコーキング量に比べて極めて少ない場合には、第１の伝播経路を経由する音波は、多量のコークを含む触媒層４内で大きな透過減衰を受ける。このため、第１の伝播経路を経由して第１のマイクロフォン８に到達した音波が、第２の伝播経路を経由して第１のマイクロフォン８に到達した遅延音波よりも卓越しない状態になる。このため、第１のマイクロフォン８で測定された音波（すなわち、音波の合成波）には、遅延音波による影響が有意に生じる。第１および第２の伝播経路で伝播する音波は、いずれも同じスピーカ７から出力されたものなので、ほぼ同じ波形を有する。但し、第２の伝播経路の方が第１の伝播経路よりも伝播距離が長いので、第１のマイクロフォン８には、第２の伝播経路を経由した音波、すなわち遅延音波が第１の伝播経路を経由した音波に遅れて到達する。その結果、この状態（つまり、第１の伝播経路を経由した音波が遅延音波に卓越しない状態）での音波の自己相関係数は、位相差の存在する領域でも０を超える値を有する。ここで、第１の触媒反応器１ａのコーキング量と第２の触媒反応器１ｂのコーキング量との差、すなわち第１の触媒反応器１ａのコーキング量の相対値が大きいほど、遅延音波の影響が大きくなり、位相差の存在する領域での自己相関係数の値が大きくなる。 On the other hand, when there is a large difference in the amount of coking between the catalytic reactors, for example, only the first catalytic reactor 1a is in a closed state (that is, the amount of coking is large), and all the second catalytic reactors 1b When the amount of coking in the first catalyst reactor 1a is extremely small compared to the amount of coking in the first catalyst reactor 1, the sound wave passing through the first propagation path undergoes a large transmission attenuation in the catalyst layer 4 containing a large amount of coke. .. Therefore, the sound wave that reaches the first microphone 8 via the first propagation path is not superior to the delayed sound wave that reaches the first microphone 8 via the second propagation path. Therefore, the sound wave measured by the first microphone 8 (that is, the synthetic wave of the sound wave) is significantly affected by the delayed sound wave. Since the sound waves propagating in the first and second propagation paths are both output from the same speaker 7, they have substantially the same waveform. However, since the second propagation path has a longer propagation distance than the first propagation path, the sound wave passing through the second propagation path, that is, the delayed sound wave is the first propagation path in the first microphone 8. It arrives late at the sound wave via. As a result, the autocorrelation coefficient of the sound wave in this state (that is, the state in which the sound wave passing through the first propagation path does not predominate over the delayed sound wave) has a value exceeding 0 even in the region where the phase difference exists. Here, the larger the difference between the coking amount of the first catalytic reactor 1a and the coking amount of the second catalytic reactor 1b, that is, the larger the relative value of the coking amount of the first catalytic reactor 1a, the more the influence of the delayed sound wave. Increases, and the value of the autocorrelation coefficient in the region where the phase difference exists increases.

ここで、スピーカ７から出力される音波の波長を、第１の伝播経路と第１の触媒反応器１ａに隣接する第２の触媒反応器１ｂを経由する第２の伝播経路（主要な第２の伝播経路）との経路長差よりも十分長く設定することによって、主要な第２の伝播経路を経由して第１のマイクロフォン８に到達する音波の位相を第１の伝播経路を経由して第１のマイクロフォン８に到達する音波の位相に十分近づける（例えば、第１の伝播経路の音波の位相に対して－９０°超、－３０°未満）ことができる。つまり、第１の伝播経路を経由した音波に主要な第２の伝播経路を経由した音波を重ね合わせることができる。このとき、第１の伝播経路を経由して第１のマイクロフォン８に到達した音波と主要な第２の伝播経路を経由して第１のマイクロフォン８に到達した音波の相関は正となり、比較自己相関係数のピーク幅がより広くなる。つまり、コーキング量の増加をより早期に検出することができる。具体的には、スピーカ７から出力する音波の波長を、上述した経路長差の４倍を超える値に設定すればよい。もちろん、音波の波長はこの範囲に制限されないが、少なくとも第１のマイクロフォン８に到達する音波同士が重複するように設定されることが好ましい。 Here, the wavelength of the sound wave output from the speaker 7 is passed through the first propagation path and the second propagation path 1b adjacent to the first catalytic reactor 1a (main second propagation path). By setting it sufficiently longer than the path length difference from (propagation path), the phase of the sound wave that reaches the first microphone 8 via the main second propagation path is set to be via the first propagation path. It can be sufficiently close to the phase of the sound wave reaching the first microphone 8 (for example, more than −90 ° and less than −30 ° with respect to the phase of the sound wave of the first propagation path). That is, the sound wave that has passed through the first propagation path can be superimposed on the sound wave that has passed through the main second propagation path. At this time, the correlation between the sound wave that reached the first microphone 8 via the first propagation path and the sound wave that reached the first microphone 8 via the main second propagation path is positive, and the comparison self. The peak width of the correlation coefficient becomes wider. That is, an increase in the amount of caulking can be detected earlier. Specifically, the wavelength of the sound wave output from the speaker 7 may be set to a value exceeding four times the path length difference described above. Of course, the wavelength of the sound wave is not limited to this range, but it is preferable that the sound waves reaching at least the first microphone 8 are set so as to overlap each other.

従って、第１の触媒反応器１ａでのコーキング量が大きくなる場合、第１の触媒反応器１ａに付属する第１のマイクロフォン８で測定される音波の自己相関係数は、０秒の近傍でより広いピーク幅を有する（図４の「コークあり」のグラフを参照）。例えば、ガス温度８００℃で伝播経路長差が０．５ｍの場合、周波数２００Ｈｚの音波を出力すれば、このような条件を満足する。また、上記以外の好適な出力音波の周波数条件として、５０～１０００Ｈｚの範囲が挙げられる。音波の周波数が１０００Ｈｚを大きく超える場合、高周波数の音波ほど触媒層４での透過損失が大きくなり、第１のマイクロフォン８に到達する音波の音圧レベルが第１のマイクロフォン８の検出下限を下回る可能性がある。この問題を解消するためには、スピーカを巨大化する必要があり、コスト等の観点から不利である。一方、音波の周波数が５０Ｈｚを大幅に下回る場合、安定した波形の音波を出力するためにスピーカの直径を極端に大きく設定する必要がある。この場合もコスト等の観点から不利である。 Therefore, when the amount of coking in the first catalytic reactor 1a is large, the autocorrelation coefficient of the sound wave measured by the first microphone 8 attached to the first catalytic reactor 1a is in the vicinity of 0 seconds. It has a wider peak width (see the "with cork" graph in FIG. 4). For example, when the gas temperature is 800 ° C. and the propagation path length difference is 0.5 m, such a condition can be satisfied by outputting a sound wave having a frequency of 200 Hz. Further, as a suitable frequency condition of the output sound wave other than the above, a range of 50 to 1000 Hz can be mentioned. When the frequency of the sound wave greatly exceeds 1000 Hz, the higher the frequency of the sound wave, the larger the transmission loss in the catalyst layer 4, and the sound pressure level of the sound wave reaching the first microphone 8 is lower than the detection lower limit of the first microphone 8. there is a possibility. In order to solve this problem, it is necessary to enlarge the speaker, which is disadvantageous from the viewpoint of cost and the like. On the other hand, when the frequency of the sound wave is significantly lower than 50 Hz, it is necessary to set the diameter of the speaker extremely large in order to output a sound wave having a stable waveform. This case is also disadvantageous from the viewpoint of cost and the like.

ここで、第１の触媒反応器１ａのコーキング量と第２の触媒反応器１ｂのコーキング量との差、すなわち第１の触媒反応器１ａのコーキング量の相対値が大きいほど、遅延音波の影響が大きくなり、位相差０近傍における自己相関係数のピーク幅が広くなる。 Here, the larger the difference between the caulking amount of the first catalytic reactor 1a and the caulking amount of the second catalytic reactor 1b, that is, the larger the relative value of the caulking amount of the first catalytic reactor 1a, the more the influence of the delayed sound wave. Becomes larger, and the peak width of the autocorrelation coefficient near zero phase difference becomes wider.

したがって、第１の触媒反応器１ａでのコーキング量が第２の触媒反応器１ｂでのコーキング量よりも大きくなった場合、第１の触媒反応器１ａにおける比較自己相関係数のピーク幅が初期自己相関係数のピーク幅よりも広くなる。したがって、比較自己相関係数のピーク幅に基づいて、第１の触媒反応器１ａのコーキング量が第２の触媒反応器１ｂのコーキング量に対して大きいか否かを判定することができる。さらに、コーキング量の相対値が多いほどピーク幅が広くなることから、ピーク幅に基づいてコーキング量の相対値も測定することができる。より具体的には、上述した自己相関係数差に基づいて、上述した判定を行うことができる。 Therefore, when the amount of coking in the first catalytic reactor 1a becomes larger than the amount of coking in the second catalytic reactor 1b, the peak width of the comparative autocorrelation coefficient in the first catalytic reactor 1a is initially set. It becomes wider than the peak width of the autocorrelation coefficient. Therefore, based on the peak width of the comparative autocorrelation coefficient, it can be determined whether or not the caulking amount of the first catalytic reactor 1a is larger than the caulking amount of the second catalytic reactor 1b. Further, since the peak width becomes wider as the relative value of the caulking amount increases, the relative value of the caulking amount can also be measured based on the peak width. More specifically, the above-mentioned determination can be made based on the above-mentioned autocorrelation coefficient difference.

なお、上述した処理では、比較自己相関係数と対比する自己相関係数を初期自己相関係数（すなわち、全ての触媒反応器１内の触媒層４がコークを含まない状態）としたが、他の自己相関係数を初期自己相関係数としてもよい。具体的には、全ての触媒反応器１における自己相関係数の平均値（以下、「自己相関係数平均値」とも称する）と比較自己相関係数と対比しても良い。この場合にも、上述した処理が可能となる。すなわち、例えば第１の触媒反応器１ａのコーキング量が多くなり、第２の触媒反応器１ｂでのコーキング量がほとんど変動しない場合、第１の触媒反応器１ａの比較自己相関係数のピーク幅は広くなるが、自己相関係数平均値のピーク幅はほとんど変動しない。したがって、第１の触媒反応器１ａの比較自己相関係数のピーク幅と自己相関係数平均値のピーク幅とを対比することで、上述した判定が可能になる。具体的には、比較自己相関係数と自己相関係数平均値との差、すなわち自己相関係数差に基づいて上述した判定が可能になる。なお、初期自己相関係数及び自己相関係数平均値のいずれを使用しても良いが、初期自己相関係数を使用することで、触媒反応器１の個体差（例えば、コーキングが生じていない時における自己相関係数の差）を排除することができる。 In the above-mentioned processing, the autocorrelation coefficient to be compared with the comparative autocorrelation coefficient is set to the initial autocorrelation coefficient (that is, the catalyst layer 4 in all the catalyst reactors 1 does not contain cork). Another autocorrelation coefficient may be used as the initial autocorrelation coefficient. Specifically, the average value of the autocorrelation coefficients in all the catalytic reactors 1 (hereinafter, also referred to as “autocorrelation coefficient average value”) may be compared with the arithmetic autocorrelation coefficient. In this case as well, the above-mentioned processing is possible. That is, for example, when the amount of coking in the first catalytic reactor 1a is large and the amount of coking in the second catalytic reactor 1b hardly fluctuates, the peak width of the comparative autocorrelation coefficient of the first catalytic reactor 1a Is wide, but the peak width of the mean value of the autocorrelation coefficient hardly fluctuates. Therefore, the above-mentioned determination can be made by comparing the peak width of the comparative autocorrelation coefficient of the first catalytic reactor 1a with the peak width of the average value of the autocorrelation coefficient. Specifically, the above-mentioned determination can be made based on the difference between the arithmetic autocorrelation coefficient and the mean value of the autocorrelation coefficient, that is, the difference in the autocorrelation coefficient. Either the initial autocorrelation coefficient or the average value of the autocorrelation coefficient may be used, but by using the initial autocorrelation coefficient, individual differences in the catalyst reactor 1 (for example, caulking does not occur). The difference in the autocorrelation coefficient over time) can be excluded.

＜５．測定原理の詳細＞
上述したように、本実施形態では、音波の自己相関係数のピーク幅を用いてコーキング量の相対値を測定する。ここで、第１の触媒反応器１ａに付属する第１のマイクロフォン８が測定した音波（合成波）に関して、第１の伝播経路を経由した音波の音圧が第２の伝播経路を経由した遅延音波の音圧に近いほど、合成波に与える遅延音波の影響が大きくなり、音波の自己相関係数の位相差０秒近傍におけるピーク幅が広くなる。以下、図６～図１０に基づいて、その理由（原理）について詳細に説明する。なお、図６～図１０で示される位相差の単位は（ｒａｄ）となっている。位相差（ｒａｄ）と位相差（ｓ）とは、位相差（ｒａｄ）＝角周波数（ｒａｄ／ｓ）×位相差（ｓ）の関係がある。 <5. Details of measurement principle>
As described above, in the present embodiment, the relative value of the caulking amount is measured using the peak width of the autocorrelation coefficient of the sound wave. Here, with respect to the sound wave (synthetic wave) measured by the first microphone 8 attached to the first catalytic reactor 1a, the sound pressure of the sound wave passing through the first propagation path is delayed via the second propagation path. The closer to the sound pressure of the sound wave, the greater the influence of the delayed sound wave on the synthetic wave, and the wider the peak width in the vicinity of the phase difference of 0 seconds of the autocorrelation coefficient of the sound wave. Hereinafter, the reason (principle) will be described in detail with reference to FIGS. 6 to 10. The unit of the phase difference shown in FIGS. 6 to 10 is (rad). The phase difference (rad) and the phase difference (s) have a relationship of phase difference (rad) = angular frequency (rad / s) × phase difference (s).

本説明では、第１の伝播経路を伝播経路＃１とし、他の第２の伝播経路を２つピックアップし、それぞれ伝播経路＃２、＃３とする。そして、ここでは、第１の触媒反応器１ａに付属する第１のマイクロフォン８が測定する音波について検証する。なお、以下の解析では、音波は、管路内を一次元的に伝播し、反射の影響はないものとして計算した。 In this description, the first propagation path is referred to as propagation path # 1, and two other second propagation paths are picked up and referred to as propagation paths # 2 and # 3, respectively. Then, here, the sound wave measured by the first microphone 8 attached to the first catalytic reactor 1a will be verified. In the following analysis, the sound wave was calculated assuming that it propagated one-dimensionally in the pipeline and was not affected by reflection.

伝播経路＃１～＃３のうち、伝播経路＃１の経路長が最も短いので、伝播経路＃１を経由した音波が最短で第１のマイクロフォン８に到達し、他の伝播経路＃２、＃３を経由した音波は、これに遅れて第１のマイクロフォン８に到達する。即ち、第１のマイクロフォン８の設置位置では、伝播経路＃２、＃３経由の音波は、伝播経路＃１経由の音波に対して位相差が生じる。ただし、いずれの経路の音波も同一のスピーカ７が音源であるので全ての音波波形は相似であり、また、経路の構造の差によって音波の振幅には差が生じる。 Of the propagation paths # 1 to # 3, the path length of the propagation path # 1 is the shortest, so that the sound wave passing through the propagation path # 1 reaches the first microphone 8 at the shortest, and the other propagation paths # 2 and # 3 The sound wave passing through 3 reaches the first microphone 8 later than this. That is, at the installation position of the first microphone 8, the sound wave via the propagation path # 2 and # 3 has a phase difference with respect to the sound wave via the propagation path # 1. However, since the sound source of the sound wave of each path is the same speaker 7, all the sound wave waveforms are similar, and the amplitude of the sound wave is different due to the difference in the structure of the path.

このような条件でスピーカ７から１波長分の正弦波を出力し、第１のマイクロフォン８で音波を測定した。規格化した音圧値（伝播経路＃１の音圧値のピークを１．０としたもの）を模式化して図６、図７に示す。図６、図７の横軸は位相（ｒａｄ）を示し、縦軸は規格化した音圧値を示す。図６では、伝播経路＃１経由の音波の音圧が卓越していることを示すために、他の経路経由の音圧を０としている。図７では、伝播経路＃１、＃２、＃３経由の音波の音圧がいずれも同じ音圧（強度）を有することを示している。それぞれの図では、各経路で伝播した音波の合成波形を算出して併記している。以下の説明では、ケース１は図６での合成波、ケース２は図７での合成波を示すものとする。 Under such conditions, a sine wave for one wavelength was output from the speaker 7, and a sound wave was measured with the first microphone 8. The standardized sound pressure value (the peak of the sound pressure value of the propagation path # 1 is 1.0) is schematically shown in FIGS. 6 and 7. The horizontal axis of FIGS. 6 and 7 indicates the phase (rad), and the vertical axis indicates the standardized sound pressure value. In FIG. 6, the sound pressure via the other path is set to 0 in order to show that the sound pressure of the sound wave via the propagation path # 1 is predominant. FIG. 7 shows that the sound pressures of the sound waves via the propagation paths # 1, # 2, and # 3 all have the same sound pressure (intensity). In each figure, the composite waveform of the sound wave propagated in each path is calculated and shown together. In the following description, it is assumed that Case 1 shows the synthetic wave in FIG. 6 and Case 2 shows the synthetic wave in FIG. 7.

図６の合成波形と図７の合成波形とを比較すると、図７の合成波形では、音圧検出の開始-終了間の時間がより長い一方で、波形は正弦波に近い形状となっている。即ち、図７では図６よりも見かけ上、波長が大きくなる。このような状態でケース１、２について自己相関係数を算出し図８で比較する。図８の横軸は位相差（ｒａｄ）を示し、縦軸は自己相関係数を示す。図８から明らかな通り、ケース２（即ち、伝播経路＃１以外の伝播経路での音圧値がより高い状態）の方がケース１よりも自己相関係数のピーク幅が広くなるのである。 Comparing the composite waveform of FIG. 6 with the composite waveform of FIG. 7, in the composite waveform of FIG. 7, the time between the start and the end of sound pressure detection is longer, but the waveform has a shape close to a sine wave. .. That is, in FIG. 7, the wavelength is apparently larger than that in FIG. In such a state, the autocorrelation coefficient is calculated for cases 1 and 2 and compared with reference to FIG. The horizontal axis of FIG. 8 shows the phase difference (rad), and the vertical axis shows the autocorrelation coefficient. As is clear from FIG. 8, the peak width of the autocorrelation coefficient is wider in the case 2 (that is, the state where the sound pressure value in the propagation path other than the propagation path # 1 is higher) than in the case 1.

ここで、合成波は、なるべく正弦波に近い連続的な波形であることが好ましい。この場合、ピーク幅がより広くなり、コーキング量の増加をより早期に検出することができるからである。合成派を正弦波に近い連続的な波形にするために、各経路経由で第１のマイクロフォン８に伝播する音波間の位相差（ｒａｄ）がπ／２未満であることが好ましい。設備構造から与えられる各経路の経路長差（特に、伝播経路＃１と第１の触媒反応器１ａに隣接する第２の触媒反応器１ｂを経由する伝播経路（主要な第２の伝播経路）との経路長差）がこの条件を満たすように、スピーカ７から出力される音波の波長（周波数）が設定されるべきである。好ましくは、上述したように、スピーカ７から出力する音波の波長を、伝播経路＃１と主要な第２の伝播経路との経路長差の４倍を超える値に設定すればよい。 Here, the synthesized wave is preferably a continuous waveform as close as possible to a sine wave. In this case, the peak width becomes wider, and an increase in the amount of caulking can be detected earlier. In order to make the synthetic wave a continuous waveform close to a sine wave, it is preferable that the phase difference (rad) between the sound waves propagating to the first microphone 8 via each path is less than π / 2. Path length difference of each path given from the equipment structure (in particular, the propagation path via the second catalytic reactor 1b adjacent to the propagation path # 1 and the first catalytic reactor 1a (main second propagation path)). The wavelength (frequency) of the sound wave output from the speaker 7 should be set so that the path length difference from the speaker 7 satisfies this condition. Preferably, as described above, the wavelength of the sound wave output from the speaker 7 may be set to a value more than four times the path length difference between the propagation path # 1 and the main second propagation path.

仮に伝播経路＃１を経由する音波と他の伝播経路＃２、＃３を経由する音波との位相差が極端に大きい場合、合成波の自己相関係数のグラフは、ピーク幅の拡大ではなく、位相差０の近傍から離れた位相差に孤立ピークが発生する波形を示す。実機の化学反応装置では、多数の触媒反応器を経由する音波とこれらの管内反射波が錯綜した音場が形成される。このため、位相差０の近傍から離れた位置に孤立ピークが存在したとしても、その由来を判別してなんらかのモデル化を施すことは困難であり、上記のような離れた位相差に発生する孤立ピークは、データ解析上、無視せざるをえない。このような観点から、スピーカ７から出力する音波の波長を、伝播経路＃１と主要な第２の伝播経路との経路長差の４倍を超える値に設定することが好ましい。 If the phase difference between the sound wave passing through the propagation path # 1 and the sound wave passing through the other propagation paths # 2 and # 3 is extremely large, the graph of the autocorrelation coefficient of the synthetic wave does not expand the peak width. , A waveform in which an isolated peak occurs in a phase difference away from the vicinity of the phase difference 0 is shown. In the actual chemical reactor, a sound field is formed in which sound waves passing through a large number of catalytic reactors and these reflected waves in the tube are intricate. Therefore, even if an isolated peak exists at a position far from the vicinity of the phase difference 0, it is difficult to determine its origin and perform some modeling, and the isolation generated in the above-mentioned distant phase difference occurs. The peak must be ignored for data analysis. From such a viewpoint, it is preferable to set the wavelength of the sound wave output from the speaker 7 to a value more than four times the path length difference between the propagation path # 1 and the main second propagation path.

以上の効果は、スピーカ７から出力する音波が単一のパルス波であることから生じる現象である。スピーカ７から特定周波数の連続波を出力した場合、各経路で伝播の位相遅れが生じたとしても、それぞれの経路で音波の波形は同一となる。このため、例えば、出力音波が正弦波の場合であれば、当該マイクロフォンで検出する合成派は、位相と振幅が出力波形とは異なるだけの上記特定周波数の音波となる。したがって、自己相関係数のピーク幅に差は生じない。実際、ケース３（ケース１の伝播経路条件でスピーカ出力を連続波としたもの）とケース４（ケース２の伝播経路条件でスピーカ出力を連続波としたもの）での自己相関係数を算出した結果を比較すると、図９に示すように両者間に差はみられない。 The above effect is a phenomenon caused by the fact that the sound wave output from the speaker 7 is a single pulse wave. When a continuous wave having a specific frequency is output from the speaker 7, the waveform of the sound wave is the same in each path even if a phase delay in propagation occurs in each path. Therefore, for example, when the output sound wave is a sine wave, the synthetic group detected by the microphone is a sound wave having the specific frequency whose phase and amplitude are different from those of the output waveform. Therefore, there is no difference in the peak width of the autocorrelation coefficient. In fact, the autocorrelation coefficient was calculated in Case 3 (the speaker output is a continuous wave under the propagation path condition of Case 1) and Case 4 (the speaker output is a continuous wave under the propagation path condition of Case 2). Comparing the results, there is no difference between the two as shown in FIG.

さらに、スピーカ出力波形を１波長ではなく半波長とした場合（位相０～１８０°の正弦波やパルス波形）を用いると、音波の経路長差による自己相関係数のピーク幅差は、より顕著になる。ケース５（ケース１の伝播経路条件でスピーカ出力を半波長の正弦波としたもの）とケース６（ケース２の伝播経路条件でスピーカ出力を半波長の正弦波としたもの）との自己相関係数を比較すると、図１０に示すように、より大きなピーク幅差が認められる。したがって、スピーカ７から出力するパルス波は半波長分の音波であることが好ましい。 Furthermore, when the speaker output waveform is not one wavelength but half wavelength (sine wave or pulse waveform with phase 0 to 180 °), the peak width difference of the autocorrelation coefficient due to the path length difference of the sound wave is more remarkable. become. Self-phase relationship between Case 5 (speaker output is a half-wavelength sine wave under the propagation path condition of Case 1) and Case 6 (speaker output is a half-wavelength sine wave under the propagation path condition of Case 2). Comparing the numbers, as shown in FIG. 10, a larger peak width difference is observed. Therefore, it is preferable that the pulse wave output from the speaker 7 is a sound wave having a half wavelength.

つぎに、本実施形態の実施例について説明する。本実施例では、図１及び図２に示す化学反応装置を用いて試験を行った。触媒反応器１の本数は７本とした。装置の詳細は、次のとおりである。スピーカの直径は１２０ｍｍとした。７本の触媒反応器１には、それぞれ第１のマイクロフォン８を付属させた。第１のマイクロフォン８には検出下限が－９０ｄＢのものを用いた。スピーカ７から各マイクロフォンまでの距離は、第１のマイクロフォン８で平均５ｍ（７つの第１のマイクロフォン８までの距離の算術平均値）、第２のマイクロフォン９で０．３ｍとした。スピーカ７および第１のマイクロフォン８が流入管２や流出管３と接続するための配管径（分岐管の内径）は、いずれも５０ｍｍとした。触媒反応器１は、直径２００ｍｍ、高さ６００ｍｍとし、隣接する触媒反応器間での音波の伝播経路長差は０．５ｍとした。触媒反応器１には４０ｋｇの直径２０ｍｍの触媒をそれぞれ充填した。ここで、最も下流の（すなわち、図１の右端に相当する）触媒反応器１を第１の触媒反応器１ａ、そのひとつ上流の触媒反応器１を第２の触媒反応器１ｂとよぶことにした。つまり、上述した説明では、第１の触媒反応器１ａ以外の触媒反応器１を全て第２の触媒反応器１ｂとしたが、第１の触媒反応器１ａを経由する音波にもっとも影響を与える音波は、第１の触媒反応器１ａに隣接する触媒反応器１を経由する音波である。そこで、このような触媒反応器１を代表として第２の触媒反応器１ｂとした。 Next, an embodiment of the present embodiment will be described. In this example, the test was performed using the chemical reaction apparatus shown in FIGS. 1 and 2. The number of catalyst reactors 1 was seven. The details of the device are as follows. The diameter of the speaker was 120 mm. A first microphone 8 was attached to each of the seven catalytic reactors 1. The first microphone 8 used had a lower limit of detection of −90 dB. The distance from the speaker 7 to each microphone was 5 m on average for the first microphone 8 (arithmetic mean value of the distance to the seven first microphones 8) and 0.3 m for the second microphone 9. The pipe diameter (inner diameter of the branch pipe) for connecting the speaker 7 and the first microphone 8 to the inflow pipe 2 and the outflow pipe 3 was set to 50 mm. The catalyst reactor 1 has a diameter of 200 mm and a height of 600 mm, and the difference in the length of the sound wave propagation path between the adjacent catalyst reactors is 0.5 m. The catalyst reactor 1 was filled with 40 kg of catalyst having a diameter of 20 mm. Here, the most downstream (that is, corresponding to the right end of FIG. 1) catalytic reactor 1 is referred to as a first catalytic reactor 1a, and the catalytic reactor 1 one upstream thereof is referred to as a second catalytic reactor 1b. bottom. That is, in the above description, all the catalyst reactors 1 other than the first catalyst reactor 1a are referred to as the second catalyst reactor 1b, but the sound waves that most affect the sound waves passing through the first catalyst reactor 1a. Is a sound wave passing through the catalyst reactor 1 adjacent to the first catalyst reactor 1a. Therefore, the second catalyst reactor 1b was designated as a representative of such a catalyst reactor 1.

上記化学反応装置において、各触媒反応器１を８００℃の雰囲気に保持し、スピーカ７から２００Ｈｚで１１０ｄＢ相当のサイン波を１波長分、２００ｍｓ周期で１分間出力した。そして、各触媒反応器１に付属する第１のマイクロフォン８で音圧の時系列データを測定、記録した（このデータを「コークなし条件」と呼称する）。また、この時系列データを処理することで得られる自己相関係数は、上述した初期自己相関係数に相当する。 In the above chemical reaction apparatus, each catalytic reactor 1 was maintained in an atmosphere of 800 ° C., and a sine wave equivalent to 110 dB was output from the speaker 7 at 200 Hz for one wavelength and at a cycle of 200 ms for one minute. Then, the time-series data of the sound pressure was measured and recorded by the first microphone 8 attached to each catalytic reactor 1 (this data is referred to as "cork-free condition"). Further, the autocorrelation coefficient obtained by processing this time series data corresponds to the above-mentioned initial autocorrelation coefficient.

その後、触媒を抜き出して第１の触媒反応器１ａの触媒層４に３ｋｇのコークを添加して閉塞状態とし、これ以外の第２の触媒反応器を含む６本の触媒反応器１の触媒層４にはそれぞれ５００ｇのコークを添加して非閉塞状態とした。その後、スピーカ７から上記と同じ音波条件の音波を出力し、各触媒反応器１に付属する第１のマイクロフォン８で音圧の時系列データを測定、記録した（このデータを「コークあり条件」と呼称する）。 After that, the catalyst was taken out and 3 kg of coke was added to the catalyst layer 4 of the first catalyst reactor 1a to make it in a closed state, and the catalyst layers of the six catalyst reactors 1 including the other second catalyst reactor 1 were used. 500 g of cork was added to each of 4 to make it a non-occluded state. After that, a sound wave with the same sound wave conditions as above was output from the speaker 7, and time-series data of sound pressure was measured and recorded by the first microphone 8 attached to each catalytic reactor 1 (this data is "condition with cork"). Called).

第２の触媒反応器１ｂにおける自己相関係数の算出値を図３に、第１の触媒反応器１における自己相関係数の算出値を図４に、それぞれ示す。第２の触媒反応器１ｂではコークあり、コークなしの条件間で自己相関係数の違いはほとんど存在しない。これは、コークありの条件でも第２の触媒反応器１ｂは、コークなしの条件のときと同様に装置全体での平均的なコーキング量に近いコーキング量であったからと解釈できる。一方、第１の触媒反応器１ａでは、コークありの条件での自己相関係数の波形は、コークなしの条件でのものに比べてピーク幅が著しく広い。これは、第１の触媒反応器１ａにおいて、閉塞した触媒層４での音波の透過損失が第２の触媒反応器１ｂを含む他の触媒反応器１に比べて極端に大きく、第２の触媒反応器１ｂを含む他の触媒反応器１を経由して第１の触媒反応器１ａの第１のマイクロフォン８に到達した音波の影響が無視できないほど大きかったことを示している。 The calculated value of the auto-correlation coefficient in the second catalyst reactor 1b is shown in FIG. 3, and the calculated value of the auto-correlation coefficient in the first catalyst reactor 1 is shown in FIG. 4, respectively. In the second catalytic reactor 1b, there is almost no difference in the autocorrelation coefficient between the conditions with and without cork. It can be interpreted that this is because the second catalytic reactor 1b had a caulking amount close to the average caulking amount in the entire apparatus as in the case of no caulking condition even under the condition with caulking. On the other hand, in the first catalytic reactor 1a, the waveform of the autocorrelation coefficient under the condition with cork has a significantly wider peak width than that under the condition without cork. This is because, in the first catalyst reactor 1a, the transmission loss of the sound wave in the closed catalyst layer 4 is extremely large as compared with the other catalyst reactor 1 including the second catalyst reactor 1b, and the second catalyst. It is shown that the influence of the sound wave reaching the first microphone 8 of the first catalytic reactor 1a via the other catalytic reactor 1 including the reactor 1b was not negligible.

第１の触媒反応器１ａおよび第２の触媒反応器１ｂについてコークありとコークなしの条件での自己相関係数差を図５に対比して示す。第２の触媒反応器１ｂでは自己相関係数差は、０．１未満と小さいものであるのに対し、閉塞状態の第１の触媒反応器１ａでは自己相関係数差は、最大で０．５を超える。このように自己相関係数差を用いることで、第１の触媒反応器１ａにおけるコーキング量が装置全体での平均に比べてどの程度大きいかを定量的に測定することができた。 The difference in the autocorrelation coefficient between the first catalytic reactor 1a and the second catalytic reactor 1b with and without cork is shown in comparison with FIG. In the second catalytic reactor 1b, the difference in autocorrelation coefficient is as small as less than 0.1, whereas in the first catalytic reactor 1a in the closed state, the difference in autocorrelation coefficient is 0. Over 5. By using the difference in the autocorrelation coefficient in this way, it was possible to quantitatively measure how large the amount of caulking in the first catalytic reactor 1a is compared to the average of the entire apparatus.

以上、添付図面を参照しながら本発明の好適な実施形態について詳細に説明したが、本発明はかかる例に限定されない。本発明の属する技術の分野における通常の知識を有する者であれば、特許請求の範囲に記載された技術的思想の範疇内において、各種の変更例または修正例に想到し得ることは明らかであり、これらについても、当然に本発明の技術的範囲に属するものと了解される。 Although the preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, the present invention is not limited to these examples. It is clear that a person having ordinary knowledge in the field of the art to which the present invention belongs can come up with various modifications or modifications within the scope of the technical ideas described in the claims. , These are also naturally understood to belong to the technical scope of the present invention.

１ 触媒反応器
１ａ 第１の触媒反応器
１ｂ 第２の触媒反応器
２ 流入管
３ 流出管
４ 触媒層
５ 加熱炉
６ コーク除去装置
７ スピーカ
８ 第１のマイクロフォン
９ 第２のマイクロフォン
１０ 弁
１１ ガス流れ
１２ 流入集合管
１３ 流出集合管 1 Catalyst reactor 1a 1st catalyst reactor 1b 2nd catalyst reactor 2 Inflow pipe 3 Outflow pipe 4 Catalyst layer 5 Heating furnace 6 Cork remover 7 Speaker 8 First microphone 9 Second microphone 10 Valve 11 Gas Flow 12 Inflow collecting pipe 13 Outflow collecting pipe

Claims (4)

共通の流入集合管および流出集合管に並列に接続された複数の固定床触媒反応器のうち、いずれか一の固定床触媒反応器内に設けられた触媒層のコーキング量を測定する触媒層のコーキング量の測定方法であって、
前記一の固定床触媒反応器が接続される配管系内に、スピーカおよび前記一の固定床触媒反応器に付属するマイクロフォンを、前記一の固定床触媒反応器内に設けられた触媒層が前記スピーカおよび前記マイクロフォンの間に配置され、かつ、前記スピーカおよび前記マイクロフォンが前記配管系の配管内側に向くようにそれぞれ設け、
前記スピーカからパルス状の音波を出力させ、前記マイクロフォンで前記音波を時系列的に計測し、
前記マイクロフォンでの音波測定値を処理して自己相関係数を測定し、位相差０秒近傍での前記自己相関係数のピーク幅に基づいて、前記一の固定床触媒反応器内に設けられた触媒層のコーキング量を、他の固定床触媒反応器内に設けられた触媒層のコーキング量に対する相対値として測定することを特徴とする、触媒層のコーキング量の測定方法。 Of a plurality of fixed-bed catalytic reactors connected in parallel to a common inflow collecting pipe and an outflow collecting pipe, a catalyst layer for measuring the amount of coking of the catalyst layer provided in any one of the fixed-bed catalytic reactors. It is a method of measuring the amount of coking,
In the piping system to which the one fixed bed catalyst reactor is connected, a speaker and a microphone attached to the one fixed bed catalyst reactor are provided, and a catalyst layer provided in the one fixed bed catalyst reactor is described. It is arranged between the speaker and the microphone, and is provided so that the speaker and the microphone face the inside of the pipe of the piping system, respectively.
A pulsed sound wave is output from the speaker, and the sound wave is measured in time series with the microphone.
The autocorrelation coefficient is measured by processing the sound wave measurement value of the microphone, and is provided in the one fixed bed catalytic reactor based on the peak width of the autocorrelation coefficient in the vicinity of the phase difference of 0 seconds. A method for measuring the amount of coking in a catalyst layer, which comprises measuring the amount of coking in the catalyst layer as a relative value to the amount of coking in the catalyst layer provided in another fixed-bed catalyst reactor. 前記一の固定床触媒反応器に対して測定された位相差０秒近傍での前記自己相関係数のピーク幅と、全ての前記固定床触媒反応器に対して測定された位相差０秒近傍での前記自己相関係数のピーク幅の平均値とを比較することによって、前記一の固定床触媒反応器内に設けられた触媒層のコーキング量を、前記他の固定床触媒反応器内に設けられた触媒層のコーキング量に対する相対値として測定することを特徴とする、請求項１に記載の触媒層のコーキング量の測定方法。 The peak width of the autocorrelation coefficient in the vicinity of the phase difference of 0 seconds measured for the one fixed-bed catalytic reactor and the phase difference of the vicinity of 0 seconds measured for all the fixed-bed catalytic reactors. By comparing with the average value of the peak width of the auto-correlation coefficient in the above, the amount of coking of the catalyst layer provided in the one fixed-bed catalyst reactor is transferred to the other fixed-bed catalyst reactor. The method for measuring the amount of coking in a catalyst layer according to claim 1, wherein the measurement is performed as a relative value with respect to the amount of coking in the provided catalyst layer. 前記一の固定床触媒反応器に対して測定された位相差０秒近傍での前記自己相関係数のピーク幅と、全ての前記固定床触媒反応器の触媒層がコークを含まない状態で前記一の固定床触媒反応器に対して測定された位相差０秒近傍での前記自己相関係数のピーク幅とを比較することによって、前記一の固定床触媒反応器内に設けられた触媒層のコーキング量を、前記他の固定床触媒反応器内に設けられた触媒層のコーキング量に対する相対値として測定することを特徴とする、請求項１または２に記載の触媒層のコーキング量の測定方法。 The peak width of the autocorrelation coefficient in the vicinity of the phase difference of 0 seconds measured for the one fixed-bed catalytic reactor and the catalyst layer of all the fixed-bed catalytic reactors without cork. By comparing with the peak width of the autocorrelation coefficient in the vicinity of the phase difference of 0 seconds measured for one fixed-bed catalyst reactor, the catalyst layer provided in the one fixed-bed catalyst reactor is provided. The measurement of the amount of coking of the catalyst layer according to claim 1 or 2, wherein the amount of coking of the above is measured as a relative value with respect to the amount of coking of the catalyst layer provided in the other fixed bed catalyst reactor. Method. 前記パルス状の音波の波長は、前記スピーカから出力される音波が前記一の固定床触媒反応器を経由して前記一の固定床触媒反応器に付属するマイクロフォンまで伝播する経路と、前記スピーカから出力される音波が前記一の固定床触媒反応器に隣接する他の固定床触媒反応器を経由して前記一の固定床触媒反応器に付属するマイクロフォンまで伝播する経路との経路長差の４倍を超えるように設定されることを特徴とする、請求項１～３の何れか１項に記載の触媒層のコーキング量の測定方法。 The wavelength of the pulsed sound wave is the path through which the sound wave output from the speaker propagates through the one fixed bed catalyst reactor to the microphone attached to the one fixed bed catalyst reactor, and the path from the speaker. 4 of the path length difference from the path in which the output sound wave propagates to the microphone attached to the one fixed bed catalyst reactor via another fixed bed catalyst reactor adjacent to the one fixed bed catalyst reactor. The method for measuring the amount of coking in the catalyst layer according to any one of claims 1 to 3, wherein the method is set so as to exceed a doubling.
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