JP6899786B2 - How to measure the leak rate of the valve mechanism and the catalytic reaction device - Google Patents

Description

The present invention relates to an operating method for operating the catalytic reactor under suitable reaction conditions and an apparatus used for the operation method, and particularly to a method for measuring a leak rate of a valve mechanism provided in the catalytic reactor and a catalytic reactor.

In an externally heated catalytic reactor that supplies the reaction heat required for the catalytic reaction to the catalytic reactor by heating the catalytic reactor from the outside, in order to secure a sufficient heating area, a thin tube filled with a catalyst as a fixed bed is used. It is common practice to arrange a plurality of catalytic reactors in parallel in a heating furnace. The individual catalytic reactors installed in parallel are often connected to a common inflow collecting pipe and a common outflow collecting pipe. Further, for various operational purposes, each catalytic reactor may be provided with a valve mechanism for shutting off or opening the flow of the source gas to each catalytic reactor independently of each other. Patent Documents 1 and 2 describe an example of such a catalytic reactor.

By the way, when the valve mechanism is exposed to a high temperature (eg, 800 ° C.), the elastic material constituting the valve mechanism is required to have good sealing performance even at a high temperature. However, it has been difficult to obtain such an elastic material. Therefore, when the valve mechanism is exposed to a high temperature (eg, 800 ° C.), a leak may occur even if the valve mechanism is in the closed state (the state in which the flow of the raw material gas is blocked).

As parameters for evaluating the leak property of the valve mechanism, the flow rate of the fluid flowing through the valve mechanism when the valve mechanism is opened (the state where the raw material gas is circulated) and the valve mechanism when the valve mechanism is closed are used. The leak rate, which is the ratio to the flow rate of the flowing fluid (that is, the leak flow rate), is generally used. The leak rate is defined by the following formula, for example, in a standard such as Non-Patent Document 1.
[Maximum leak amount (allowable leak flow rate)] = k · [Rated valve capacity]
k: Leak rate

Here, the leak rate k is a constant corresponding to the leak class, and for example, in the case of the leak class II, k = 5 × 10 ^-3 . Further, the Cv value is often used for the rated valve capacity. In design practice, k for a Cv value is generally expressed by the following mathematical formula (1).

JP-A-2017-56375 Japanese Unexamined Patent Publication No. 2016-159264

Accurately determining the leak rate k during operation is important for the following reasons. For example, in order to maintain only a specific catalytic reactor, the downstream side of the valve mechanism of the catalytic reactor may be opened to the atmosphere (or in a heating furnace). In this case, if the leak rate of the valve mechanism is excessive, a large amount of raw material gas leaks from the valve mechanism. Then, if the raw material gas is combustible and the raw material gas is mixed with the atmosphere and exceeds the explosion limit, it may ignite. If it is not clear that the leak rate does not satisfy the explosion limit, it is necessary to stop the supply of raw material gas including other catalysts to ensure safety. In this case, the efficiency of the operation is impaired. Therefore, it is important to measure and control the leak rate for such operations.

Alternatively, a particular catalytic reactor may be used as a bypass tube to open if all other catalytic reactors are blocked for some reason (eg, blocked by a by-product of the catalytic reaction). .. In this case, the catalyst reactor for the bypass tube will not be filled with the catalyst or will be filled with a small amount. A valve mechanism is also provided in the catalytic reactor for the bypass pipe. During normal operation, this valve mechanism is closed and all other catalytic reactors are set to ventilate most of the source gas. If the leak rate of this valve mechanism is excessive, a large amount of raw material gas leaks from this valve mechanism even when the valve mechanism is closed. The raw material gas that leaked the valve mechanism is hardly reformed. As a result, the reformed gas flowing out from the outflow collecting pipe contains a large amount of raw material gas that is hardly reformed. Therefore, there arises a problem that the reforming performance is lowered. In this case, if the leak rate of the valve mechanism can be accurately grasped, it is possible to easily make a judgment that the leak rate of the valve mechanism is improved by performing maintenance.

Alternatively, the following operations may be performed in order to stabilize the change in the reforming performance of the entire catalyst reaction apparatus due to the deterioration of the catalyst over time. That is, after the used catalyst is replaced with a new catalyst, the valve mechanism of some catalyst reactors is closed at the initial stage of operation to protect the catalyst from deterioration due to the aeration of the raw material gas, while the valve mechanism of other catalyst reactors is protected. The valve mechanism is opened. As a result, the raw material gas is reformed using another catalytic reactor. After that, when the reforming performance of other catalyst reactors deteriorates due to deterioration over time as the operation continues, the valve mechanism of some of the catalyst reactors that have been closed is opened. This allows the catalytic reaction to continue using the relatively high reforming capacity of the newly opened catalytic reactor. As a result, it is possible to improve the deterioration of the reforming performance of the entire catalytic reaction apparatus. In the above device, if the leak rate of the valve mechanism is excessive, a large amount of raw material gas will flow to the catalyst reactor corresponding to the closed valve mechanism from an early stage after the catalyst is filled. As a result, even in these catalyst reactors, catalyst deterioration occurs from an early stage after catalyst filling, so that it may not be possible to obtain a desired modification performance stabilizing effect. If the leak rate of the valve mechanism can be accurately grasped, it is possible to easily make a judgment that the leak rate of the valve mechanism is improved by performing maintenance.

In catalytic reactor comprising a single catalytic reactor, the differential pressure △ P and the leak flow rate Q _c in equation (1) it can be easily measured. For example, the valve mechanism provided on the supply side is a non-high-temperature portion may be measured △ P and Q _c of the valve mechanism. Therefore, it is not difficult to obtain the leak rate k. However, it is not easy to determine the leak rate in a catalytic reactor in which a plurality of catalytic reactors as disclosed in Patent Documents 1 and 2 are arranged in parallel and each catalytic reactor independently has a valve mechanism. .. Of these catalytic reactors, when only the valve mechanism of some catalytic reactors is closed, the raw material gas that cannot ventilate this valve mechanism is in the open state of other catalytic reactors (that is, the valve mechanism is open). The flow path can be easily changed to the catalyst reactor). Therefore, the change in the differential pressure ΔP (the differential pressure in this case is the differential pressure between the gas pressure in the inflow collecting pipe and the gas pressure in the outflow collecting pipe) is small in the first place.

Further, when the leak flow rate in the closed valve mechanism is sufficiently smaller than the gas flow rate that ventilates the open valve mechanism, the differential pressure ΔP that changes depending on the leak flow rate in the closed valve mechanism. The amount of gas is often undetectable due to measurement accuracy. As a method of grasping the leak flow rate in each valve mechanism in the closed state, a flow rate sensor capable of detecting a minute flow velocity in the catalytic reactor, for example, a flow rate sensor such as a Karman vortex current meter or a Koriori current meter is directly used. , Can be placed. However, catalytic reactors are often maintained at high temperatures. Therefore, such measurement is difficult due to the heat resistance of the sensor. Therefore, it was not easy to grasp the leak rate k.

If a very accurate pressure sensor can be used and the pressure-flow rate characteristics in the valve mechanism of the catalytic reactor are also known accurately, it will be in the closed state from the change in the differential pressure ΔP. It may be possible to measure the leak flow rate at the valve mechanism. However, for example, when the raw material gas is a gas containing a hydrocarbon, the catalytic reaction is a steam reforming reaction, and the generated gas (reforming gas) is a synthetic gas, the hydrocarbon is a side reaction during the operation. Cork (solid carbon or hydrocarbon) is produced by the catalytic cracking reaction of. Then, the cork gradually accumulates in the catalyst layer (that is, the fixed bed) and hinders the aeration of gas in the catalyst layer, so that the pressure-flow rate characteristics in the catalyst reactor change from moment to moment. Therefore, under such conditions, the leak flow rate of the valve mechanism cannot be obtained by the above method. Moreover, it is not realistic to use an extremely accurate pressure gauge from the viewpoint of economic rationality.

Alternatively, an orifice type flowmeter (an orifice is provided in the pipe, and the pressure difference before and after the orifice is detected and converted into a flow velocity) is provided for each catalytic reactor, and the differential pressure detector of this flowmeter is used as a catalyst. A method of installing the reactor in the low temperature part (on the side where the raw material gas enters) is also conceivable. This method has the potential to measure leak flow while reducing the cost of the flow meter. However, the flow velocity in the catalyst reactor is usually set to an extremely small value, for example, about several tens of cm / s in order to secure the contact time between the passing gas and the catalyst. Therefore, the differential pressure generated before and after the orifice becomes extremely small, and the measurement error becomes large, or it is necessary to arrange a large number of expensive precision differential pressure gauges. Therefore, it is not realistic from the viewpoint of economic rationality.

In this way, when a plurality of catalytic reactors are arranged in parallel and each catalytic reactor is provided with a valve mechanism independently, the leak flow rate and the leak rate of some of the valve mechanisms in the closed state can be easily detected. I couldn't.

On the other hand, installing a temperature measuring device such as a thermoelectric pair in each catalytic reactor is generally performed for the purpose of operation management and equipment protection because there are relatively few technical difficulties. If the temperature of the catalyst reactor, specifically the temperature of the catalyst layer, can be used to measure the leak rate of the valve mechanism for the catalyst reactor, the leak rate can be measured at low cost. However, such a proposal has not been made in the past.

Therefore, in the present invention, in a catalytic reactor including a plurality of catalytic reactors arranged in parallel in a heating furnace, the valve mechanism can be inexpensively and easily provided without providing an expensive measuring device for each catalytic reactor. The purpose is to provide a technique for measuring the leak rate online.

In order to solve the above problems, according to a certain viewpoint of the present invention, there is a method for measuring the leak rate of a valve mechanism, which measures the leak rate of a plurality of valve mechanisms arranged in parallel in a catalytic reactor, wherein the catalyst is used. N reactors are arranged in parallel, a catalyst reactor that treats the raw material fluid with a catalyst layer that is a fixed bed, an inflow collecting pipe that is a collecting pipe for supplying fluid to all the catalyst reactors, and the catalyst. The valve mechanism, which is provided for each reactor and can be independently set to either an open state for flowing a fluid into the catalytic reactor or a closed state for blocking the flow of a fluid to the catalytic reactor. The outflow collecting tube, which is a collecting tube for collecting the fluid flowing out from all the catalytic reactors and flowing out downstream, is provided in each of the catalyst layers of all the catalytic reactors, and the catalyst layer temperature _Ti is measured. It is equipped with a catalyst layer thermometer and an inflow thermometer that measures the inflow temperature, which is the fluid temperature of the inflow collecting pipe, and is supplied to the heating furnace device arranged in the heating furnace whose furnace temperature can be adjusted and the inflow collecting pipe. A fluid preheater for preheating the fluid to be used, a fluid switching device for switching the fluid supplied to the inflow collecting pipe between the raw material fluid and the non-reactor fluid, and a flow rate for measuring the flow rate passing through the inflow collecting pipe. A meter and a differential pressure measuring device for measuring the differential pressure between the inflow collecting pipe and the outflow collecting pipe are provided, and the method for measuring the leak rate is such that the inflow collecting is performed with all the valve mechanisms open. A first operation of setting the fluid switching device so that the non-reactor fluid passes through the tube, a second operation of adjusting the fluid preheating device so that the inflow thermometer shows a predetermined inflow temperature, and a second operation. after the valve mechanism corresponding to a predetermined n _c stand catalytic reactor in the n-number and a closed state, to maintain the operating state until a steady state, the differential pressure △ P ₃ in the steady _state, and the n _c stand catalytic reactor of the catalyst layer temperature _{T c3, i} was recorded,
k _i = α ₁ , Q _{c3, i}・ (ΔP ₃ ) ^{-1 / 2}
Q _{c3, i:} leakage flow rate of the valve mechanism in a closed state alpha _1: leakage rate k _i of i-th of the valve mechanism to be defined in the model constants becomes equation, as a function using the catalyst layer temperature T _{c3, i} A method of measuring the leak rate of the valve mechanism is provided, which comprises a third operation of calculation.

Here, the apparatus in the heating furnace further includes a furnace thermometer for measuring the furnace temperature of the heating furnace, and in the third operation, the furnace temperature T _f of the heating furnace is further recorded and the closing is performed. _{Leakage flow rate Q c3, i} of the valve mechanism in the state,
Q _{c3, i} = a ₁ · (T _f −T _{c3, i} )
a ₁ : Model coefficient may be calculated by the formula.

Further, the device in the heating furnace further includes a furnace temperature thermometer for measuring the furnace temperature of the heating furnace, and in the second operation, the inflow temperature _Tin2 , which is the predetermined inflow temperature, is recorded and i. th said catalyst layer temperature T _i of the catalytic reactor to maintain the operating state until a steady state, recording the catalyst layer temperature T _i at steady state as a catalyst layer temperature T _{2, i,} the third In the operation of, the reactor temperature T _f of the heating furnace is further recorded.
k _i = a ₂ Ln [(T _f −T in ₂ ) / (T _f −T _{2, i} )]
/ Ln [(T _f −T _in2 ) / (T _f −T _{c3, i} )]
a _2: may calculate the leak rate k _i using model coefficients becomes equation.

Further, in the second operation, records the inlet temperature T _in2 said a predetermined inlet temperature, in the third operation, showing different inlet temperature T _in4 from said inlet thermometer the inlet temperature T _in2 wherein adjusting the fluid preheater maintains the operating state until the catalyst layer temperature T _i is the steady state, recording the catalyst layer temperature T _i at steady state as a catalyst layer temperature T _{c4, i} like, _{The leak flow rate Q c3, i} of the valve mechanism in the closed state is
Q _{c3, i} = −β _i / Ln [(T _{c4, i} −T _{c3, i} ) / (T _in4- T in ₂ )]
β _i : The model coefficient may be calculated using an equation.

The raw material fluid may contain hydrocarbons.

According to another aspect of the present invention, it is a catalytic reactor for measuring the leak rate of a plurality of valve mechanisms arranged in parallel, and n units are arranged in parallel, and the raw material fluid is treated with a catalyst layer which is a fixed bed. A catalytic reactor, an inflow collecting tube which is an collecting tube for supplying a fluid to all the catalytic reactors, an open state provided for each catalytic reactor to allow a fluid to flow in the catalytic reactor, and the catalyst. The valve mechanism, which can be independently set to any of the closed states that block the flow of fluid to the reactor, is a collecting tube for collecting the fluid flowing out of all the catalytic reactors and causing it to flow downstream. outlet collecting pipe, respectively provided in all of the catalytic reactor of the catalyst layer, the catalyst layer thermometer for measuring the temperature of the catalyst layer T _i, and inlet temperature gauge for measuring the inlet temperature is a fluid temperature of the inlet manifold pipe A heater in-reactor device that is arranged in a heating reactor whose reactor temperature can be adjusted, a fluid preheating device that preheats the fluid supplied to the inflow collecting pipe, and a fluid supplied to the inflow collecting pipe are not the raw material fluid. A fluid switching device for switching between a reactive fluid, a flow meter for measuring the flow rate passing through the inflow collecting pipe, and a differential pressure for measuring the differential pressure between the inflow collecting pipe and the outflow collecting pipe. A first means for setting the fluid switching device so that the non-reactor fluid passes through the inflow collecting pipe with all the valve mechanisms open, and the inflow thermometer. second means for adjusting the fluid preheating device to indicate the predetermined inlet temperature, after the closed state the valve mechanism corresponding to a predetermined n _c stand catalytic reactor in the n stage, the steady-state made up to maintain the operational state, records the catalyst layer temperature T _{c3, i} of the differential pressure △ P _3, and the n _c stand catalytic reactor in the steady state,
k _i = α ₁ , Q _{c3, i}・ (ΔP ₃ ) ^{-1 / 2}
Q _{c3, i:} leakage flow rate of the valve mechanism in a closed state alpha _1: leakage rate k _i of i-th of the valve mechanism to be defined in the model constants becomes equation, as a function using the catalyst layer temperature T _{c3, i} Provided is a catalytic reaction apparatus comprising a third means for calculating and a valve mechanism leak rate measuring apparatus for executing the calculation.

In the system targeted by the present invention, the pressure change before and after the valve mechanism is sufficiently smaller than the absolute pressure before and after the valve mechanism, and the temperature change is also relatively small. D in the above mathematical formula (1) is a fixed value by design, and ζ _op is a fixed value that can be easily obtained by numerical analysis or the like. Furthermore, the fluid flowing through the valve mechanism is an incompressible fluid (as will be described later, in most cases, the fluid can actually be regarded as an incompressible fluid), and those that can be fixed values are summarized in the model constants as described above. The formula (1) can be simplified to the following formula (2).
k = α ₁ · Q _c · (ΔP) ^1/2 (2)
α ₁ : Model constant

When this formula is applied to the valve mechanism of the i-th catalyst reactor among a plurality of catalyst reactors provided in parallel, the following formula (3) is obtained. Hereinafter, the subscript i means the catalyst reactor number. The subscript 3 of ΔP means that it is a value obtained by the third operation. The subscript c means that each catalytic reactor is in a closed state.
k _i = α ₁ , Q _{c3, i} , (ΔP ₃ ) ^1/2 (3)
Q _{c3, i} : Leakage flow rate of the valve mechanism in the closed state

The leak rate in the present invention is not limited to that corresponding to the Cv value. That is, an arbitrary reference differential pressure (differential pressure before and after the valve mechanism) is appropriately set according to the application of the catalytic reactor, and the leak flow rate in the closed state and the flow rate in the open state (reference flow rate) under these conditions. The ratio with and can be used as the leak rate. The leak rate thus obtained can be easily converted into a value corresponding to the Cv value by a calculation based on simple engineering knowledge that is obvious to those skilled in the art.

(Features of the present invention)
In the catalytic reactor according to the present invention, a plurality of catalytic reactors are arranged in parallel in the heating furnace, and each catalytic reactor is provided with a valve mechanism. Therefore, a plurality of valve mechanisms are arranged in parallel in the catalytic reaction device. The first feature of the present invention is the change in the temperature distribution of these catalyst reactors, specifically, the change in the temperature distribution of the catalyst layer installed in the catalyst reactor, which is a relatively easy measurement. The leak rate of the valve mechanism can be easily measured online.

The raw material fluid may also contain hydrocarbons. In this case, since a large amount of cork is deposited in the catalyst reactor when the raw material fluid is modified, the aeration resistance coefficient of the catalyst reactor itself changes every moment during operation. A second aspect of the present invention, even in such a system, based on a change in the temperature distribution of the catalyst layer and the differential pressure △ P _3, can be measured independently leak rate of the valve mechanism for each valve mechanism , Higher measurement accuracy.

The present inventor has found that the change in the pressure loss coefficient (drag coefficient) η caused by cork deposition in the catalytic reactor has a unique relationship with the heat transmission coefficient h in the catalytic reactor. A third feature of the present invention is to measure the leak rate based on the relationship between the drag coefficient η and the thermal transmission rate h.

(Relationship between η and h)
Here, the correlation between the drag coefficient η in the catalytic reactor and the thermal transmissivity h will be described. The present inventor has found that there is a unique relationship between the drag coefficient η and the model constant β (specific details will be described later) that is proportional to the thermal transmission rate h. The present inventor _{investigated the relationship between η / η 0} and β / β ₀ with a specific catalytic reaction device. Here, the state where there is no cork deposition in the catalyst layer is represented by the subscript 0. As a result, the present inventor has found that there is a relationship as shown in FIG. 3 between the two. The horizontal axis and the vertical axis of FIG. 3 are both logarithmic axes. As shown in FIG. 3, there is a positive correlation between _{η / η 0} and β / β _0.

The present inventor considers this reason as follows. That is, compared to the initial state in which no cork is deposited in the catalyst layer, heat is more likely to be transferred in the catalyst reactor when cork is deposited. The main component of cork is solid carbon, which is a substance with relatively high thermal conductivity, and the cork fills the gaps between the catalyst particles and between the catalyst particles and the inner wall tube of the reactor. Therefore, heat transfer in the catalyst layer is mainly carried out by heat conduction via cork. As the amount of cork deposited increases (that is, the resistance coefficient increases), the thermal transmissivity h, that is, the value of the model constant β also increases. Therefore, it is considered that the relationship shown in FIG. 3 can be obtained.

The relationship of FIG. 3 can be formally expressed by the following equation. The value of the model constant _ai is 0.42 in the example of FIG. Specific method for calculating the leak rate k _i using this correlation will be described later.
β _i = β _{0, i} · (η _i / η _{0, i} ) ^ai
a _i : Model constant

As described above, according to the present invention, the leak rate of a plurality of valve mechanisms arranged in parallel in the heating furnace can be easily calculated by measuring the temperature in the catalytic reactor. Therefore, the leak rate of the valve mechanism can be easily and inexpensively measured online without providing an expensive measuring device in each catalytic reactor.

It is explanatory drawing which shows the whole structure of the catalyst reaction apparatus 1 used in 1st to 4th Embodiment of this invention. It is explanatory drawing which shows the schematic structure of the apparatus in a heating furnace. It is a graph which shows the correlation of a resistance coefficient η and a model constant β. (A) is a side sectional view showing an internal structure of a catalytic reactor. (B) is a plan view which shows the structure of the catalyst cage. (C) is a cross-sectional view on the AA side of (a). (A) is a side view showing the appearance of the catalyst reactor. (B) to (d) are cross-sectional views on the AA side of (a). (A) It is a top view which shows the shape when the catalyst cage is seen from the bottom. (B) is a side sectional view showing the catalyst cage and its peripheral structure. (A) It is a top view which shows the shape of a valve seat, a valve body and the like when viewed from below. (B) is a side sectional view showing a valve seat, a valve body and the like.

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. First Embodiment>
(1. Overall configuration)
First, the overall configuration of the catalyst reaction device 1 according to the first embodiment will be described with reference to FIGS. 1 and 2. The catalyst reaction device 1 includes a fluid switching device 110, a gas preheating device 111, a heating furnace device A1, a cooling device 117, a flow rate adjusting device 118, and a blower 119.

The heating furnace device A1 is provided in the heating section A, and includes an inflow collecting pipe 101, a flow meter 112, an inflow pressure meter 113, an inflow thermometer 114, and a plurality of (n units in the example of FIG. 1). . N is an integer of 3 or more), a catalyst reactor 2, a deposit removal device 3 in the catalyst layer provided for each catalyst reactor 2, a valve mechanism 4 provided for each catalyst reactor 2, and a catalyst reactor 2. A catalyst layer thermometer 115, an outflow collecting pipe 102, and an outflow pressure meter 116 provided for each are provided.

The device A1 in the heating furnace is heated by a heating furnace (not shown). As such a heating furnace, for example, a direct-fired heating furnace in which a large number of gas burners are arranged in the furnace can be used. A thermometer (furnace temperature thermometer) for measuring the furnace temperature is installed in the heating furnace at a representative point where the catalyst reactor 2 or the piping does not exist. Then, by controlling the combustion amount of the gas burner, the furnace temperature is adjusted so that the measured value of this thermometer matches the target value.

Therefore, the catalyst reactor 2 constituting the in-heating furnace device A1 is heated from the heating furnace (that is, the outside). As a result, the heat of reaction required for the catalytic reaction is supplied to the catalytic reactor 2. Therefore, the catalyst reactor 2 is an external thermal catalyst reactor. A plurality of catalyst reactors 2 (N in the example of FIG. 1) are arranged in parallel in the heating section A. The catalyst reactor 2 has a structure in which a catalyst is filled in a straight pipe, and the catalyst is fixed as a catalyst layer in the straight pipe as a fixed bed. In addition, a net or the like for preventing the catalyst from falling is provided in the lower part of the straight pipe. One end of the straight pipe is the entry side and the other end is the exit side. Then, the raw material gas is introduced from the inlet side, and a catalytic reaction occurs when the raw material gas passes through the catalyst layer (fixed bed). The raw material gas after the catalytic reaction, that is, the reformed gas, flows out from the outlet side. The detailed configuration of the heating furnace device A1 will be described later.

The fluid switching device 110 is connected to the raw material fluid supply device 100, the non-reactive fluid supply device 200, and the inflow collecting pipe 101. The fluid switching device 110 is a device that switches the gas supplied to the inflow collecting pipe 101 between the raw material gas supplied from the raw material fluid supply device 100 and the non-reactive gas supplied from the non-reactive fluid supply device 200. .. As the fluid switching device 110, for example, two ports on the upstream side are a raw material fluid supply device 100 (more specifically, a pipe extending from the raw material fluid supply device 100) and a non-reactive fluid supply device 200 (more specifically). Can be used as a three-way valve having a structure in which each is connected to a pipe extending from the non-reactive fluid supply device 200) and a port on the downstream side is connected to the inflow collecting pipe 101.

The raw material fluid supply device 100 is a device that supplies the raw material gas to the catalyst reactor 2, and is, for example, a gas holder, a gas generator, or the like. The raw material gas is a gas that is reformed by a catalytic reaction in the catalyst layer described later. The catalytic reaction targeted by the first embodiment and other embodiments described later is not particularly limited. As an example, the catalytic reaction may be such that the flow resistance of the catalyst layer can be significantly changed during the operation. In this case, examples of the raw material gas include natural gas, naphtha, coke oven gas and the like, and gases containing hydrocarbons such as coal carbonization gas containing tar. When the raw material gas contains hydrocarbons, the raw material gas is steam reformed by the catalyst layer. The reformed raw material gas, that is, the reformed gas is recovered by the reaction fluid recovery device 300.

At this time, cork, which is a by-product, may be produced by a catalytic cracking reaction of hydrocarbon, which is a side reaction. Since the cork generated in the catalyst layer is gradually deposited in the space between the catalysts in the catalyst layer (fixed bed), the flow resistance (in this case, the aeration resistance) of the catalyst layer increases during the operation. Further, even if the catalytic reaction targeted by the first embodiment and other embodiments described later produces a by-product whose thermal conductivity is not at least significantly smaller than that of the catalyst. Good. Cork is an example of a by-product that satisfies such a thermal conductivity condition. Hereinafter, for convenience of explanation, the case where the by-product is cork will be described as an example, but it goes without saying that the by-product is not limited to cork.

In order to ensure the reactivity of steam reforming, the temperature of the catalyst layer, that is, the catalyst layer temperature is set to a high temperature such as 700 ° C. or higher, and all the catalyst reactors 2 satisfy this catalyst layer temperature condition. The reactor temperature T _f of the heating furnace is adjusted as described above. Hereinafter, the catalyst layer temperature of the i-th catalyst reactor 2 is also referred _{to as “catalyst layer temperature Ti”.}

The non-reactive fluid supply device 200 is a device that supplies the non-reactive gas to the catalytic reactor 2, and examples thereof include a gas holder. The non-reactive gas is a gas that does not cause a chemical reaction by the catalyst heated to the catalyst layer temperature. Examples of such a chemical reaction include the steam reforming reaction of the above-mentioned raw material gas. Further, in the first embodiment and each of the embodiments described later, for convenience of operation, the non-reactive gas is independently aerated in the catalyst reactor 2 when the temperature of the catalyst reactor 2 is raised, for example. Sometimes. If the raw material gas is supplied to the catalyst reactor 2 in the middle of temperature rise, the reforming reaction does not occur and the raw material gas is wasted, and depending on the temperature conditions, a condensable gas (for example, tar gas). ) May condense and close the catalytic reactor 2. In order to prevent such a phenomenon, a non-reactive gas may be aerated in the catalyst reactor 2 instead of the raw material gas. In this case, the non-reactive gas needs to be a substance that is stable at least in the range of room temperature to the catalytic reaction temperature and does not cause a remarkable reaction with the catalyst. The non-reactive gas satisfying each of the above conditions corresponds to an inert gas such as argon or nitrogen gas. In the first embodiment and other embodiments described later, all the fluids (for example, raw material gas, non-reactive gas, reformed gas) flowing in the catalyst reaction device 1 are gas, but they are liquid. There is no problem at all.

The gas preheating device 111 is a device for preheating the raw material gas or the non-reactive gas introduced into the inflow collecting pipe 101. The raw material gas or non-reactive gas is introduced into the catalyst reactor 2 after being preheated. The gas preheating device 111 is provided at one end of the inflow collecting pipe 101, that is, at the inflow pipe 101a of a single pipe. The gas preheating device 111 is, for example, a heat exchanger. The gas preheating device 111 may be a heating pipe in which the wall surface of the pipeline is directly heated. A fluid transfer device such as a blower may be appropriately provided between the inflow collecting pipe 101 and the raw material fluid supply device 100.

The inflow collecting pipe 101 is a single collecting pipe for supplying a fluid, for example, a raw material gas or a non-reactive gas, to all the catalytic reactors 2. One end of the inflow collecting pipe 101 is a single inflow pipe 101a, and the inflow pipe 101a is connected to the fluid switching device 110. The other end is a plurality of (N) inflow branch pipes 101b, and the end on the inlet side of the catalyst reactor 2 is connected to each inflow branch pipe 101b. The inflow pipe 101a and the inflow branch pipe 101b are connected by a connecting pipe 101c.

The catalyst reactor 2 is a straight tubular device having a built-in catalyst layer which is a fixed bed, and a plurality of catalyst reactors 2 are arranged in parallel in the heating section A. The inlet end of the catalyst reactor 2 is connected to the inflow branch pipe 101b of the inflow collecting pipe 101, and the outlet end is connected to the outflow branch pipe 102b of the outflow collecting pipe 102. The catalyst reactor 2 reforms the raw material gas by a catalytic reaction using the catalyst layer. Then, the catalyst reactor 2 discharges the reformed raw material gas, that is, the reformed gas, into the outflow collecting pipe 102. The detailed configuration of the catalyst reactor 2 will be described later.

The catalyst layer in-catalyst deposit removing device 3 is provided for each catalyst reactor 2 and removes by-products such as cork deposited in the catalyst layer, that is, deposits during operation. The deposit removing device 3 in the catalyst layer can be driven independently of each other. A specific example of the deposit removing device 3 in the catalyst layer will be described later, but for example, the device disclosed in Patent Documents 1 and 2 can be used without particular limitation. The deposit removing device 3 in the catalyst layer may be omitted. For example, even if deposits are not generated by reforming the raw material gas, or if deposits are generated and the aeration resistance of the catalyst layer is increased, the amount of deposits can lead to blockage of the catalyst reactor. If not, the deposit removing device 3 in the catalyst layer may be omitted.

The valve mechanism 4 is provided for each catalyst reactor 2. That is, a plurality of valve mechanisms 4 are arranged in parallel in the catalytic reaction device 1. Specifically, the valve mechanism 4 is provided in the inflow branch pipe 101b. The valve mechanism 4 may be provided in the outflow branch pipe 102b, which will be described later, or may be provided in the catalyst reactor 2. The valve mechanism 4 can be independently set to either an open state in which the raw material gas or the like is circulated in the catalyst reactor 2 or a closed state in which the raw material gas or the like is blocked from flowing to the catalyst reactor 2. There is.

Examples of the valve mechanism 4 include high temperature valves listed in Patent Documents 1 and 2. In such a high temperature valve (for example, the valve seat and the valve body listed in Patent Document 1), the seal between the closed members (for example, the seal between the valve body and the valve seat) is pressed with a relatively small force. This is due to the contact between the metals. Therefore, it is inevitable that a slight gap will be generated between the members. If a material having a large amount of elastic deformation can be used for each member (for example, valve body and valve seat), the seal of the high temperature valve can be dramatically improved, but it can withstand large deformation at a high temperature of 700 ° C. or higher. There is no industrial elastic material that can be used. Therefore, in the valve mechanism 4 targeted by the first embodiment and each of the embodiments described later, a leak always occurs. It is practical to consider managing the leak rate appropriately based on such a premise.

The outflow collecting pipe 102 is a single collecting pipe for collecting the fluids flowing out from all the catalytic reactors 2, such as a reforming gas or a non-reactive gas, and causing them to flow downstream. One end of the outflow collecting pipe 102 is a plurality of (N) outflow branch pipes 102b, and the outlet end of the catalyst reactor 2 is connected to each outflow branch pipe 102b. The other end of the outflow collecting pipe 102 is a single outflow pipe 102a. The outflow pipe 102a and the outflow branch pipe 102b are connected by a connecting pipe 102c. The outflow pipe 102a is connected to the reaction fluid recovery device 300 via a cooling device 117, a flow rate adjusting device 118, and a blower 119. Therefore, the reformed gas flowing out from the outflow collecting pipe 102 is recovered by the reaction fluid recovery device 300 through the cooling device 117, the flow rate adjusting device 118, and the blower 119. The reaction fluid recovery device 300 is composed of, for example, a gas holder or the like.

Flowmeter 112 is provided in the inlet pipe 101a of the heating section A, for measuring the flow rate _{Q T} of the inlet manifold pipe 101. Flow rate Q _T is a total amount of gas introduced into the catalytic reactor 2. Examples of the flow meter 112 include a device using an orifice. Specifically, an orifice is provided in the inflow pipe 101a. Then, the flow meter 112, the flow velocity measured based from around the orifice differential pressure with the principles of Bernoulli, converted the value to the flow rate Q _T. Although details will be described later, in the first embodiment and other embodiments described below, as the flow rate Q _T, using a flow rate of non-reactive gases. Therefore, the flow meter 112 may be provided at the outlet of the non-reactive fluid supply device 200. In apparatus system of the present embodiment, since the gas temperature is varied depending on the location and time, the flow rate Q _T, for example, can be used in terms of flow rate at standard conditions.

Inlet temperature gauge 114, for example provided in connection pipe 101c, the gas temperature of the incoming collecting pipe 101, that measures the inlet temperature _{T in.} The catalyst layer temperature gauge 115 is provided for each catalytic reactor 2, the temperature in the catalyst layer, i.e., to measure the temperature of the catalyst layer T _i. Thermocouples can be used for these thermometers. In this case, for example, the temperature detection unit is inserted into the connecting pipe 101c or the catalyst reactor 2, and the signal line is pulled out of the heating furnace through the pipe wall of the connecting pipe 101c or the pipe wall of the catalyst reactor 2. Then, the signal line is connected to the temperature converter provided outside the heating furnace. The temperature transducer measures and records the temperature. The temperature detection unit of the catalyst layer thermometer 115 is preferably arranged in the center of the catalyst layer, but for convenience of design, the catalytic reaction on the downstream side in the catalyst layer and below the catalyst layer. It may be provided in the space inside the vessel or in the space sandwiched between the catalyst layer and the outer wall surface of the catalyst reactor 2.

The inflow pressure gauge 113 is provided in, for example, the inflow pipe 101a in the heating section A, and measures the gas pressure in the inflow collecting pipe 101. The outflow pressure gauge 116 is provided in the outflow pipe 102a in the heating section A, and measures the gas pressure in the outflow collecting pipe 102. These constitute a differential pressure measuring device. As a method of realizing these pressure gauges, for example, pressure conduits are provided in the inflow pipe 101a and the outflow pipe 102a, and the end of the pressure conduit is pulled out of the heating furnace, and a commercially available diaphragm type pressure gauge is attached to this end. You can connect it.

These measuring instruments included in the catalyst reactor 1 are often installed as standard for operation management in the technical field related to the industrial external thermal catalyst reactor 2.

The cooling device 117 removes condensed components (for example, tar) in the reforming gas and can supply the reforming gas to the flow rate adjusting device 118 and the reaction fluid recovery device 300 in the subsequent stage (eg, less than 80 ° C.). ). Specific examples of the cooling device 117 include a heat exchanger and a scrubber. The cooled reformed gas is introduced into the blower 119 through the flow rate adjusting device 118.

The flow rate adjusting device 118 is a device that adjusts the flow rate of the raw material gas, which is the sum of the flow rates of the raw material gas in all the inflow branch pipes 101b, so as to be the target value. The flow rate adjusting device 118 is, for example, a valve that adjusts the flow rate of the reformed gas, and includes a driving device such as an electric motor or an air cylinder. A commercially available flow control valve can be used.

The blower 119 supplies (blows) the reformed gas cooled by the cooling device 117 to the reaction fluid recovery device 300. The blower 119 is also not particularly limited, and may be a commercially available turbo type / positive displacement type blower. By adjusting the set values of the blower 119 and the flow rate adjusting device 118, the raw material gas flow rate can be adjusted to be the target value.

The catalytic reaction device 1 has been industrially put into practical use, and is, for example, a general material and structure used in an external thermal catalytic reaction device for steam reforming of hydrocarbons (for example, natural gas). Realized by.

(2. Specific example of catalytic reactor)
As the catalyst reactor 2, for example, those disclosed in Patent Documents 1 and 2 can be used without particular limitation. Hereinafter, some specific examples of the catalyst reactor 2 will be described. In the example described below, the catalyst layer deposit removing device 3 is incorporated in the catalyst reactor 2.

(2-1. First example)
First, a first example of the catalyst reactor 2 will be described with reference to FIG. The first example corresponds to the catalytic reactor disclosed in the first embodiment of Patent Document 1. Therefore, the parameters disclosed in Patent Document 1 can be appropriately applied to the parameters not disclosed here.

As shown in FIG. 4, the catalyst reactor 2 according to the first example is driven by a reaction vessel 40, an inflow path 41, an outflow path 42, a catalyst layer 43, a catalyst cage 44, a mandrel 48, and the like. A device 49 is provided. The catalyst cage 44 includes a plurality of rods 44a arranged in parallel with each other and a rod fixture 44b for connecting the ends of the rods 44a. Of these, the catalyst cage 44, the mandrel 48, and the driving device 49 realize the deposit removing device 3 in the catalyst layer. In this example, the valve mechanism 4 may be provided in the inflow branch pipe 101b.

(Shape of reaction vessel)
The reaction vessel 40 may have any shape as long as it has openings at both upper and lower ends and can accommodate the catalyst between these openings. The upper opening leads to the inflow path 41 and corresponds to the inflow port of the raw material gas for the catalytic reaction to the reaction vessel 40. The lower opening leads to the outflow passage 42 and corresponds to the outflow port of the reformed gas from the reaction vessel 40. The reaction vessel 40 can have a shape such as a cylindrical shape or a square duct shape. In the following, a square duct-shaped reaction vessel will be described as an example.

In the description of the catalytic reactor 2 according to the first example, the "central axis of the container" is defined as the center of gravity of the horizontal cross section of the container connected in the vertical direction. The "reaction vessel thickness" corresponds to the minimum length of the reaction vessel in the horizontal section, and the "reaction vessel width" is the maximum length of the reaction vessel in the horizontal plane. Corresponds to. If the container is cylindrical, the "width" and "thickness" of the container may be replaced with "diameter".

(Catalyst cage)
The catalyst cage 44 holds the catalyst layer 43 on the entire lower surface of the catalyst layer 43 in the reaction vessel 40 and has air permeability. As the catalyst cage 44, a net, a punching metal, a rod in which both rods are fixed in parallel with each other in the horizontal direction so as to create a space between the rods, or the like can be used. .. The catalyst cage 44 shown in FIG. 4 is an example of one manufactured by fixing both ends of a plurality of rods 44a with rod fixtures 44b.

(Catalyst layer drive mechanism)
In the present invention, the catalyst layer 43 is raised and lowered in the reaction vessel 40 by raising and lowering the catalyst cage 44. Therefore, the reaction vessel 40 is equipped with a drive device 49 for raising and lowering the catalyst cage 44. As the drive device 49, a general drive mechanism such as an elevating device using gears such as an air cylinder and a rack and pinion can be used. The catalyst cage 44 is coupled to the drive device 49 using the mandrel 48. When the drive device 49 is operated, the entire cage 44 moves along the axis of the reaction vessel 40 (the central axis of the reaction vessel 40), and the entire catalyst layer 43 also moves up and down along the axis of the reaction vessel 40. Move to.

At least a part of the mandrel 48 on the catalyst cage 44 side needs to be inside the reaction vessel 40, the inflow passage 41, and the outflow passage 42. The drive device 49 can be provided outside the reaction vessel 40. When the reaction vessel 40 is arranged in a heating device (not shown) such as a heating furnace, the drive device 49 may be provided outside the heating device. In this case, while a commercially available lifting device can be used, it is necessary to seal the portion where the mandrel 48 penetrates the reaction vessel 40 with a high temperature packing or the like.

When the entire drive device 49 is provided in the reaction vessel 40 as shown in FIG. 4, the drive device 49 is heat-resistant and corrosion-resistant in order to protect the drive device 49 from, for example, high temperature and corrosive substances in the reaction vessel 40. Must be. This can be achieved, for example, by making the entire air cylinder of the drive device 49 made of a heat-resistant alloy such as Hastelloy (registered trademark). In this case, the supply air pipe (not shown) to the air cylinder penetrates the reaction vessel 40, but since this portion is a non-movable part, the pipe may be sealed by welding all around.

(Raising and lowering the catalyst layer)
The entire upper surface of the catalyst cage 44 is filled with a catalyst to form a catalyst layer. The side surface of the catalyst layer thus formed is always in contact with the inner wall surface of the reaction vessel 40. When the catalyst cage is raised, an upward force is applied to the catalyst layer, and a downward frictional force is generated from the inner wall surface of the reaction vessel on the side surface of the catalyst layer. As a result, in the catalyst layer, since the catalyst near the wall surface is largely constrained by the wall surface, the amount of upward movement is smaller on average than the amount of increase of the catalyst cage, and the filling rate of the catalyst particles in this portion is small. Rise. On the other hand, since the constraint on the wall surface is weaker in the central portion of the catalyst layer, which is far from the wall surface, the amount of movement of the catalyst layer upward is relatively large, and the increase in the filling rate of the catalyst particles in this portion is small. As a result, during the ascent of the catalyst cage, shear deformation of the catalyst layer occurs from the vicinity of the wall surface to the center, and relative displacement between the catalyst particles occurs everywhere in the catalyst layer. Since the space between the catalyst particles is deformed by this relative displacement, the by-product coke (that is, by-product) deposited in this space can be crushed and extruded and discharged to the outside of the catalyst layer. In this way, the average filling rate of the catalyst layer increases as the catalyst cage rises.

On the other hand, when the catalyst cage is lowered, the average filling rate of the catalyst layer is lowered to the level before the start of raising and lowering. This is because when the catalyst cage is lowered, it gradually falls from the lower catalyst layer due to the restraint of the wall surface, so that the average distance between the catalyst particles increases during the lowering of the catalyst layer, and the positional relationship between the catalysts increases. Since a part of the catalyst layer is maintained until after the lowering of the catalyst layer is completed, the filling rate of the catalyst layer is lowered. Further, as the spacing between the catalyst particles increases as the filling rate decreases when the catalyst layer descends, the by-product coke deposited between the particles may move and be discharged to the outside of the catalyst. As a result, even if the catalyst layer is repeatedly raised and lowered, the filling rate does not continue to increase and close-packing is not achieved, and cork removal can be continued for a long period of time. In this way, the cork deposited in the catalyst layer can be removed by raising and lowering the catalyst layer. Further, since the principle for removing cork from the catalyst layer in this method is to deform the space between the catalyst particles, the ascending / descending speed of the catalyst layer does not necessarily have to be high. A sufficient effect can be obtained at an ascending / descending speed of about 10 mm / s. Further, the relative displacement amount between the particles may be about the size of the particles (for example, 10 mm).

(Inflow route, outflow route)
The inflow path 41 is connected to the inflow branch pipe 101b. Therefore, the raw material gas is introduced into the inflow path 41. The arrow P1 in FIG. 4 indicates the flow of the raw material gas (in the case of a downward flow in the catalyst layer). The outflow branch pipe 102b is connected to the outflow passage 42. The reformed gas is introduced into the outflow passage 42. After that, the reformed gas is introduced into the cooling device 117 through the outflow branch pipe 102b.

(Catalyst layer)
The catalyst layer 43 is formed by filling and laminating the catalyst particles on the catalyst cage 44 in the reaction vessel 40. The catalyst particles serve as a catalyst for reforming the raw material gas, and the raw material gas is reformed when it comes into contact with the catalyst particles. For example, when a catalytic reaction occurs on the catalyst particles, the water vapor and tar gas in the raw material gas are reformed to generate carbon monoxide gas, hydrogen gas, and cork.

The catalyst particles constituting the catalyst layer 43 may be any catalyst as long as it can reform the raw material gas (for example, steam reforming or cracking). For example, when the raw material gas contains a hydrocarbon, a Ni-alumina-based catalyst, a Ni-magnesia-alumina-based catalyst, or the like can be used as the catalyst particles.

(2-2. Second example)
Next, a second example of the catalyst reactor 2 will be described with reference to FIGS. 5 to 7. The second example corresponds to the catalytic reactor disclosed in the second embodiment of Patent Document 1. Therefore, the parameters disclosed in Patent Document 1 can be appropriately applied to the parameters not disclosed here.

The catalyst reactor 2 includes a reaction vessel 10, an inflow passage 11, an outflow passage 12, a catalyst layer 13, a catalyst cage 14, a valve seat 15, a vent hole 16, a valve body 17, and a mandrel 18. , A heat insulating material 19, a connecting pipe 20, and a driving device 21. The valve seat 15, the vent hole 16, the valve body 17, and the mandrel 18 function as the valve mechanism 4. Further, the catalyst cage 14, the mandrel 18, the connecting pipe 20, and the driving device 21 realize the catalyst layer deposit removing device 3. Further, the valve mechanism 4 is realized by the valve seat 15 and the valve body 17.

(Reaction vessel)
The reaction vessel 10 is a cylindrical member that houses the catalyst layer 13, the catalyst cage 14, the valve seat 15, the vent holes 16, the valve body 17, and the mandrel 18. By forming the reaction vessel 10 into a cylindrical shape, distortion in the radial direction (direction perpendicular to the length direction) is unlikely to occur even at high temperatures. Of course, the shape of the reaction vessel 10 may be changed to another shape for convenience of design or the like. For example, the reaction vessel 10 may have a square tubular shape having a regular polygonal horizontal cross section and an elliptical tubular shape having an elliptical horizontal cross section.

(Inflow route)
The inflow path 11 is connected to the reaction vessel 10 at the upper end of the reaction vessel 10. That is, a ventilation hole 11a is formed at the upper end of the reaction vessel 10, and the inflow path 11 and the reaction vessel 10 are connected to each other through the ventilation hole 11a. The inflow path 11 is connected to the inflow branch pipe 101b, and the raw material gas generated from the raw material fluid supply device 100 is introduced into the reaction vessel 10. The arrow P1 indicates the flow direction of the raw material gas.

(Outflow route)
The outflow channel 12 is connected to the reaction vessel 10 at the lower end of the reaction vessel 10. That is, a ventilation hole 12a is formed at the lower end of the reaction vessel 10, and the outflow passage 12 and the reaction vessel 10 are connected to each other through the ventilation hole 12a. The outflow passage 12 is connected to the outflow branch pipe 102b, and the reformed gas generated in the reaction vessel 10 is introduced into the dust collector 6. The arrow P2 indicates the flow direction of the reformed gas.

Since the inflow path 11 and the outflow path 12 are arranged on the side of the catalyst reactor 2, interference with the mandrel 18 penetrating the catalyst reactor 2 up and down can be avoided. Here, the catalyst reactors 2 may be connected in parallel by sharing the inflow path 11 and the outflow path 12 of each catalyst reactor 2 between the catalyst reactors 2.

(Catalyst layer)
The catalyst layer 13 is provided in the reaction vessel 10. The catalyst layer 13 is formed by filling and laminating the catalyst particles on the catalyst cage 14 in the reaction vessel 10. The catalyst particles serve as a catalyst for reforming the raw material gas, and the raw material gas is reformed when it comes into contact with the catalyst particles. For example, when a catalytic reaction occurs on the catalyst particles, the water vapor and tar gas in the raw material gas are reformed to generate carbon monoxide gas, hydrogen gas, and cork.

Further, the catalyst layer 13 is in contact with the inner wall surface of the reaction vessel 10. Therefore, when the catalyst layer 13 is moved up and down, the upper part of the catalyst layer 13 is delayed to the lower part due to the effect of wall friction. Therefore, the filling rate of the catalyst layer 13 temporarily decreases. At this time, since the average gap between the catalyst particles expands, the removal gas reaches a part where the removal gas is difficult to pass when the catalyst layer is stationary (eg, the catalyst particles directly above the catalyst cage), and the removal gas is there. By-products can be removed.

Further, the catalyst layer 13 is formed in three layers in the reaction vessel 10. Then, the catalyst layer 13 of each layer is held by the catalyst cage 14. By forming the catalyst layer 13 in a multilayer structure in this way, the load applied to each catalyst cage 14 can be reduced. Of course, the number of layers of the catalyst layer 13 is not limited to three.

The catalyst particles constituting the catalyst layer 13 may be any catalyst as long as it can reform the raw material gas (for example, steam reforming or cracking). For example, when the raw material gas contains a hydrocarbon, a Ni-alumina-based catalyst, a Ni-magnesia-alumina-based catalyst, or the like can be used as the catalyst particles. The size of the catalyst particles may be such that they do not pass through the ventilation holes 14c of the catalyst cage 14, which will be described later.

(Catalyst cage)
The catalyst cage 14 is a member that holds the catalyst layer 13, and is provided for each catalyst layer 13. The catalyst cage 14 is fixed to the mandrel 18 described later, and moves up and down integrally with the mandrel 18.

The catalyst cage 14 holds the catalyst layer 13 on the entire lower surface of the catalyst layer 13 in the reaction vessel 10 and has air permeability. Specifically, the catalyst cage 14 needs to have a structure for circulating various gases (raw material gas and reformed gas) while preventing the catalyst particles from falling. Specifically, as shown in FIG. 6, the catalyst cage 14 includes a plurality of ring-shaped members 14a and a connecting member 14b that connects the ring-shaped members 14a to each other. The ring-shaped members 14a have different diameters from each other and are arranged concentrically on the connecting member 14b. Here, the center point of each ring-shaped member 14a is arranged on the central axis of the mandrel 18. The cross-sectional shape (cross-section perpendicular to the circumferential direction) of the ring-shaped member 14a is not particularly limited, but is preferably rectangular from the viewpoint of strength. Further, a ventilation hole 14c is formed between the ring-shaped members 14a. Various gases and by-products pass through the vents 14c.

The connecting member 14b connects the ring-shaped members 14a to each other and fixes them to the mandrel 18. That is, the connecting member 14b is a member that extends radially from the mandrel 18. The cross section (cross section perpendicular to the length direction) of the connecting member 14b is also preferably rectangular. By increasing the cross-sectional area of the ring-shaped member 14a and the connecting member 14b, the strength of the catalyst cage 14 can be increased. The catalyst cage 14 may be, for example, a net, a punching metal, or the like processed into the same shape as the horizontal cross-sectional shape of the reaction vessel 10.

The catalyst cage 14 is preferably made of a metal material having heat resistance, corrosion resistance, strength against bending and shearing, and toughness at both normal temperature and when heated to the temperature of the catalytic reaction. Examples of such metal materials include stainless steel, nickel alloys such as Hastelloy (registered trademark) and Inconel (registered trademark), titanium, and titanium alloys.

(Valve seat, vent)
Next, as shown in FIG. 7, the valve seat 15 is provided on the inner wall surface of the reaction vessel 10. The valve seat 15 is a member that horizontally partitions the space inside the reaction vessel 10. Further, a ventilation hole 16 is formed in the central portion of the valve seat 15 so as to vertically penetrate the valve seat 15. The mandrel 18 penetrates the ventilation hole 16, and the raw material gas can pass through the ventilation hole 16. That is, the diameter of the ventilation hole 16 is larger than the diameter of the mandrel 18. Further, a substantially conical notch is formed on the lower end surface of the valve seat 15. Therefore, a concave shape is formed on the lower end surface of the valve seat 15. The material of the valve seat 15 may be the same as that of the catalyst cage 14.

(Valve body)
The valve body 17 is a member that moves up and down integrally with the mandrel 18, and has a conical trapezoidal shape. The valve body 17 can open or close the ventilation hole 16 by moving up and down together with the mandrel 18. For example, the valve body 17 opens the ventilation hole 16 when it exists at the position shown by the solid line in FIG. 7B (this position corresponds to the opening position 18a described later). In this case, the raw material gas can reach the catalyst layer 13 through the ventilation holes 16. On the other hand, the valve body 17 closes the ventilation hole 16 when it exists at the position indicated by the alternate long and short dash line in FIG. 7 (b) (this position corresponds to the closing position 18b described later). In this case, since the inflow path 11 and the catalyst layer 13 in the reaction vessel 10 are blocked by the valve seat 15 and the valve body 17, the raw material gas cannot reach the catalyst layer 13. That is, the distribution of the raw material gas to the reaction vessel 10 is blocked. The material of the valve body 17 may be the same as that of the catalyst cage 14.

The broken line 17d in FIG. 7A indicates the upper end of the valve body 17 in which the ventilation hole 16 is closed, and the broken line 17e and the straight line 17b in FIG. 7B are the valve body 17 in which the ventilation hole 16 is closed. The contact line between the valve seat 15 and the valve seat 15 is shown. This contact line is circular.

As described above, both the valve seat 15 and the valve body 17 have an axisymmetric shape (contact line 17b is circular). Therefore, the blocking property of the raw material gas can be further improved. For convenience of design and the like, the contact line 17b may have a smooth shape such as an ellipse and no corners. In this case, the horizontal cross-sectional shape of the valve seat 15 and the horizontal cross-sectional shape of the notch of the valve body 17 may be elliptical or the like.

(Mandrel)
The mandrel 18 is a cylindrical or cylindrical member (that is, a round bar or a circular tube) extending vertically in the reaction vessel 10. A catalyst cage 14 and a valve body 17 are fixed to the mandrel 18, and the catalyst cage 14 and the valve body 17 move up and down together with the catalyst cage 14. Further, the upper end of the mandrel 18 is connected to the drive device 21 via a heat insulating material 19. The mandrel 18 is moved up and down by the drive device 21. Specifically, the mandrel 18 has an open position 18a in which the valve body 17 opens the ventilation hole 16 as shown in FIG. 5 (b), and the valve body 17 has the ventilation hole as shown in FIG. 5 (c). It goes up and down between the closing position 18b that closes 16.

Further, the mandrel 18 can move up and down between the intermediate position 18c shown in FIG. 5D and the open position 18a shown in FIG. 5B when the by-product is removed. The intermediate position 18c is set between the open position 18a and the closed position 18b. In the example shown in FIG. 5, the intermediate position 18c is set at the midpoint between the open position 18a and the closing position 18b, but it goes without saying that the intermediate position 18c may be set at another position. is there.

The method of setting the intermediate position is not particularly limited, and examples thereof include a method of providing a limit switch at a position corresponding to the intermediate position in the air cylinder described above. More specifically, a 3-position type air cylinder having such a limit switch may be used as the drive device 21. Further, a 3-position type air cylinder may be realized by connecting a plurality of 2-position type air cylinders in series. The number of intermediate positions may be plural. In this case, the number of positions of the drive device 21 increases according to the number of intermediate positions.

The drive device 21 stops the mandrel 18 at the closing position 18b when the raw material gas is shut off, and stops the mandrel 18 at the opening position 18a when the raw material gas is reformed, under the control of a speed increasing device (not shown). Further, the drive device 21 raises and lowers the mandrel 18 between the intermediate position 18c and the open position 18a when removing by-products. The drive device 21 is controlled by a reactor group control device (not shown). Thereby, in the present embodiment, the catalyst layer 13 can be raised and lowered without interrupting the flow of the raw material gas. That is, in the present embodiment, the mandrel 18 is moved up and down between the intermediate position 18c and the open position 18a.

As described above, when the mandrel 18 is in the open position 18a (or the intermediate position 18c), the valve body 17 is not in contact with the valve seat 15 and the ventilation hole 16 is opened. In this case, the raw material gas is introduced into the catalyst reactor 2. Further, when the mandrel 18 is in the closing position 18b, the valve body 17 comes into contact with the valve seat 15 and the ventilation hole 16 is closed. In this case, the raw material gas is shut off from the catalyst reactor 2. Then, when the mandrel 18 is in the open position 18a (or the intermediate position 18c), the valve mechanism 4 is in the open state, and when the mandrel 18 is in the closing position 18b, the valve mechanism 4 is in the closed state.

The heat insulating material 19 is a member provided to make it difficult for the heat of the mandrel 18 to be transferred to the driving device 21. The heat insulating material 19 penetrates the upper end surface 10a of the reaction vessel 10 and extends into the connecting pipe 20. The heat insulating material 19 is connected to the drive rod 21a of the drive device 21 in the connecting pipe 20. The lower end of the heat insulating material 19 is arranged in the reaction vessel 10 when the mandrel 18 is raised and lowered. As a result, the heat of the mandrel 18 is less likely to be transferred to the drive device 21 even while the mandrel 18 is moving up and down. The heat insulating material 19 is made of, for example, ceramics. The structure of the heat insulating material 19 may be a structure in which the heat insulating material is sandwiched between the flanges, or a structure in which a large number of a plurality of metal plates are simply stacked in the axial direction. In the latter case, the heat flux in the axial direction can be suppressed by utilizing the contact thermal resistance between the metal plates. The heat insulating material 19 may be a high temperature packing.

(Connecting pipe and drive device)
The connecting pipe 20 is a tubular member that connects the reaction vessel 10 and the driving device 21. The drive device 21 is a member that raises and lowers the mandrel 18 between the open position 18a, the closing position 18b, and the intermediate position 18c, and includes a drive rod 21a, a cylinder 22, and a piston 23. Therefore, the drive device 21 is an elevating device using a so-called 3-position type air cylinder. The drive rod 21a is connected to the mandrel 18 via a heat insulating material 19. The cylinder 22 is a member in which the piston 23 is housed, and the piston 23 moves up and down in the cylinder 22 by the gas supplied into the cylinder 22. A drive rod 21a is connected to the piston 23. The drive rod 21a moves up and down in conjunction with the piston 23. As a result, the drive device 21 raises and lowers the mandrel 18. When the piston 23 reaches the lower end of the cylinder 22, the mandrel 18 reaches the open position 18a, and when the piston 23 reaches the upper end of the cylinder 22, the mandrel 18 reaches the closing position 18b. At the intermediate position, at 18c, the pressure above and below the cylinder is balanced to maintain the cylinder at a predetermined stop position between the open and closed positions. Of course, the drive device 21 is not limited to the air cylinder as long as the mandrel 18 can be raised and lowered in the above-described manner. For example, the drive mechanism of the drive device 21 may be a rack and pinion or the like.

The drive device 21 is provided outside the reaction vessel 10 as shown in FIG. Further, the drive device 21 may be arranged in a heating device (a device for heating the reaction vessel 10 or the like). In this case, in order to protect the drive device 21 from high temperature and corrosive substances, it is preferable that the drive device 21 is made of a material having high heat resistance and corrosion resistance. For example, the entire air cylinder of the drive device 21 may be made of a heat-resistant alloy such as Hastelloy (registered trademark). In this case, the pipe (not shown) that supplies gas to the air cylinder penetrates the reaction vessel 10, but since this portion is a non-movable part, the pipe may be sealed by welding all around. Since a part of the catalyst cage 14 may bite into the catalyst layer 13 and cannot fall freely when the mandrel 18 is raised, the drive device 21 is driven not only when the mandrel 18 is raised but also when it is lowered. Is preferable. The drive device 21 is driven by control by a reactor group control device (not shown).

In the second example, among the plurality of catalytic reactors 2, the valve mechanism 4 of any of the catalytic reactors 2 can be selectively closed. For example, the valve mechanism 4 of any one catalyst reactor 2 can be opened, and the valve mechanism 4 of the remaining catalyst reactor 2 can be closed. As a result, a large flow rate of the raw material gas can be circulated through the specific catalyst reactor 2, and the by-products in the catalyst reactor 2 can be easily removed.

(3. How to measure the leak rate of the valve mechanism)
Next, a method of measuring the leak rate of the valve mechanism 4 will be described. The leak rate measuring method comprises the first to third operations. The method for measuring the leak rate may be performed at an arbitrary timing during normal (regular) operation of reforming the raw material gas into a reformed gas.

(3-1. First operation)
In the first operation, all the valve mechanisms 4 are opened, and the fluid switching device 110 is operated to supply the non-reactive gas to the inflow collecting pipe 101. As a result, the non-reactive gas is passed through all the catalytic reactors 2. The gas preheating device 111 is adjusted so that the inflow temperature at this time becomes the first inflow temperature _Tin1. At the same time, the flow rate Q _{T of the inflow collecting tube 101 and the catalyst layer temperature T 1, i} measured by the catalyst layer thermometer 115 of each catalyst reactor 2 are recorded (subscript i is the catalyst reactor number and subscript). The character 1 indicates the time of the first operation, and the subscript 2 described later indicates the time of the second operation. The subscript 3 indicates the time of the third operation. The meanings of the subscripts are the same below.). Here, in order to save the time required for this operation, the inflow temperature _Tin1 is preferably the inflow temperature realized under the furnace temperature conditions during the normal catalytic reaction operation, or a temperature close to this temperature. The inflow temperature _Tin1 is the initial temperature.

(3-2. Second operation)
In the second operation, the gas preheating device 111 is adjusted to set the inflow temperature to a second inflow temperature _Tin2 (predetermined inflow temperature) _{different from the above-mentioned first inflow temperature Tin1. At this time, the catalyst layer temperatures T2 and i} measured by the catalyst layer thermometer 115 of each catalyst reactor 2 are recorded. The inflow temperature _Tin2 may be higher or lower than the inflow temperature _{Tin1, but at least a sufficient difference from the furnace temperature Tf} (that is, a difference such that the leak rate described later can be calculated, for example, about 10 ° C.). Is preferably given. In this embodiment, _{Tin 2} may have the same temperature as _{Tin 1 if Tin 1} is sufficiently different from _{T f.}

(3-3. Third operation)
The third operation is divided into a measurement operation and a leak rate calculation operation. In the measurement operation, the following operations are performed.

(3-3-1. Measurement operation)
In the measurement operation, of the n valve mechanisms 4, _{after the valve mechanism 4 corresponding to the predetermined n c} catalyst reactors 2 is closed (here, i = 1 to n _c is temporarily closed, n). _c + 1 to n are open), and the operating conditions are maintained until the catalytic reactor 1 is in a steady state. Here, in the steady state, at least the catalyst layer temperature in all the catalyst reactors 2 is constant, and the difference pressure between the gas pressure in the inflow collecting pipe 101 and the gas pressure in the outflow collecting pipe 102 is constant. It means the state that becomes.

Next, the differential pressure ΔP ₃ in the steady state, the furnace temperature T _{f , and the catalyst layer temperatures T c 3 and i} of the catalyst reactor 2 corresponding to the valve mechanism 4 in the closed state are recorded. The flow rate Q _T through the period of the first to the measuring operation is controlled to be constant. After the measurement operation is completed, the operation may be returned to the normal catalytic reaction operation.

(3-3-2. Leak rate calculation operation)
Next, the operation of calculating the leak rate will be described. In the catalytic reaction device 1 according to the first embodiment, the pressure change before and after the valve mechanism 4 is sufficiently smaller than the absolute pressure before and after the valve mechanism 4, and the temperature change is also relatively small. D in the above mathematical formula (1) is a fixed value by design, and ζ _op is a fixed value that can be easily obtained by numerical analysis or the like. Further, the flow rate Q _T is constant, summarized what may value fixing the model constants, the equation (1) can be simplified into the following equation.
k = α ₁ · Q _c · (ΔP) ^1/2 (2)
α ₁ : Model constant

When this formula is applied to the valve mechanism 4 (hereinafter, also referred to as “valve mechanism i”) corresponding to the i-th catalytic reactor 2 (hereinafter, also referred to as “catalytic reactor i”), the following formula (3) Is obtained.
k _i = α ₁ , Q _{c3, i} , (ΔP ₃ ) ^1/2 (3)
Q _{c3, i} : Leakage flow rate of valve mechanism i in the closed state

Here, α ₁ corresponds to a constant proportional to the pressure loss coefficient (drag coefficient) of the valve mechanism i in the closed state. As the differential pressure ΔP ₃ , the value measured by the above measurement operation may be used. Therefore, if it is possible to determine the leakage flow rate Q _{c3, i,} can be calculated leakage rate k _i of the valve mechanism i. However, as described above, it is difficult to directly measure the _{leak flow rates Q c3 and i.}

Therefore, in the first embodiment and each of the embodiments described later, the leak flow rate Q _{c3, i} is calculated as a function of _{the catalyst layer temperature T c3, i} measured by the above measurement operation. In the first embodiment, this function is referred to as the following mathematical formula (4). In the first embodiment and other embodiments described later, the unit of temperature is ° C.

Q _{c3, i} = func (T _f −T _{c3, i} ) (4)
func (): A function with the inside of () as an independent variable

The meaning of the mathematical formula (4) will be described. The heat transfer along the flow direction of the non-reactive gas passing between the inflow collecting pipe 101 and the catalyst reactor i is modeled as follows. First, the coordinate of the gas flow direction in the conduit from the inflow collecting pipe 101 to the catalyst reactor i and the subsequent catalyst reactor i is x, and the starting point (x = 0) is the inflow in the inflow collecting pipe 101. temperature measurement point (the temperature at this point the inlet temperature T _in), the catalyst layer temperature measuring points of the endpoints catalytic reactor i (x = X _i, the temperature at this point the catalyst layer temperature T _i ), The reactor temperature _{is defined as T f} , and the representative temperature in the pipeline (for example, the cross-sectional average temperature) at the position x is defined as the pipeline temperature T.

By the second operation, the inflow temperature _{Tin 2} of the non-reactive gas is given a sufficient difference from the furnace temperature T _f. The pipeline system (specifically, the pipeline system from the inflow temperature measurement point to the catalyst layer temperature measurement point) up to the catalyst layer temperature measurement point in each catalyst reactor 2 depends on the furnace temperature _Tf . Since it is heated, if the gas flow rate in the pipeline system is 0, the gas temperature in the pipeline system is ideally the furnace temperature T _f . This state corresponds to a state in which the leak rate is 0 in the valve mechanism i closed by the measurement operation. _{If the catalyst layer temperature Ti is a value T f'that} does not exactly match the furnace temperature T _{f in a} steady state even if the gas flow rate is 0 due to the influence of axial heat transfer of the catalyst reactor, etc. , it is possible to improve the accuracy of the model by replacing the T _f in the above formula and T _{f '.} The method of obtaining the T f _', for example, previously obtained in advance a difference △ T _f from T _i of T _f at steady state of the test carried out tests with 0 feed gas flow rate, then the actual a value obtained by adding the △ T _f to the measured T _f in operation can be used as T _{f '.}

However, since a leak always exists in the actual valve mechanism i, the leak flow rate Q _{c3, i of} the valve mechanism i, that is, the flow rate of the gas flowing through the pipeline system becomes a value larger than 0.

Here, it is assumed that heat is transferred to the non-reactive gas locally in the conduit through the conduit, the wall surface of the catalyst reactor, and the catalyst layer based on the temperature difference between _{T f and T, and the heat flow.} The bundle q'' shall be expressed by the following equation (5) per unit tube length.
q'' = hL (T _f −T) (5)

Here, h is the thermal transmission coefficient, which is generally a function of the position x. For the sake of simplicity, in the first embodiment, it is assumed that h is a constant value in the specific catalytic reactor i during at least the period from the first operation to the measurement operation. Due to this heat flux, the temperature T (temperature of the non-reactive gas) in the conduit and the catalytic reactor i rises as it progresses in the flow direction when the gas flow is regarded as an incompressible fluid in this section. As a result, the gas temperature in the pipeline system approaches the furnace temperature T _{f from the inflow temperature Tin 2 as it goes downstream, and the catalyst layer temperature T c3, i} at the catalyst layer temperature measurement point in each catalyst reactor i becomes. Generally, the temperature is between the _{inflow temperature Tin 2} and the furnace _{temperature T f.} The larger the leak flow rate Q _{c3, i} , the greater the effect of the sensible heat brought in by the gas on the heat conduction from the furnace flowing through the pipeline system. Therefore, the catalyst layer temperature T _{c3, i} is closer to the inflow temperature _Tin2. Become. Then, the temperature rise rate can be expressed by the following mathematical formula (6) from the heat balance.
ρCpQ _{c3, i} dT / dx = hL (T _f −T) (6)
h: Thermal transmission rate (W / (m ² · K))
L: Perimeter of piping (m)
ρ: Density of non-reactive gas (kg / m ³ )
Cp: Specific heat of non-reactive gas (J / (kg · K))
Q _{c3, i} : Leakage flow rate of non-reactive gas in catalytic reactor i (m ³ / s)

Even when the pressure change of the raw material gas is large in the entire catalytic reaction apparatus 1 and the raw material gas is not an incompressible fluid, it is generally small to set a large flow rate change and density change in this section, so that the raw material In many cases, the gas can be regarded as a substantially incompressible fluid (generally, it is said that a gas can be treated as an incompressible fluid when the density change is 10% or less). Therefore, the non-reactive gas can be regarded as an incompressible gas here as well.

When the temperature change from the inflow collecting pipe 101 to the catalyst reactor 2 is relatively small and _{this differential equation is solved with ρ, Cp, Q c3, and i} being constant, the following mathematical formula (7) is obtained. ..

_{Q c3, i = (h i} LX i / ρCp) / Ln [(T f -T in2) / (T f -T c3, i)] (7)
However, T = _Tin2 (x = 0), T = T _{c3, i} (x = X _i )

Therefore, in the first embodiment, the mathematical formula (4) will be represented by the mathematical formula (7). The constants h _i , X _i , ρ, Cp, etc. are obtained in advance by measurement, etc., and by _{applying these measured values, the inflow temperature Tin 2} and the furnace _{temperature T f} to the mathematical formula (7), the leak flow rate Q _{c3 , I} are calculated. Further, by applying the leak flow rates Q _{c3 and i} to the mathematical formula (3), the leak rate ki of the valve mechanism _i is calculated. As a specific method for obtaining these constants, for example, for ρ and Cp, the values at the assumed gas composition and temperature are obtained by combining the values obtained from the public thermophysical property database of the pure substances constituting this gas. .. For X _i , for example, the length of the pipe on the drawing can be used. Regarding h _i , for example, a special test described later is performed to directly obtain the flow rate in the catalytic reactor, and further, it is substituted into the mathematical formula (7) together with _{the predetermined constant values of X i, ρ, and Cp.} You can find _i. h _i is because it is a value which can constantly change during operation, it is possible to use a representative value of the average value or the like in the operation as a constant.

Alternatively, the following mathematical formula (7') can be obtained by performing a linear approximation on the assumption that the range of _{(T f} −T _{c3, i) does not fluctuate significantly during operation.}
Q _{c3, i} = a _1. (T _f −T _{c3, i} ) (7')
a ₁ : Model coefficient

_{Therefore, the leak flow rate Q c3, i} may be calculated using the mathematical formula (7'). In this case, it is necessary to identify the model constants a ₁ advance. The model constant a ₁ is the heat transfer characteristics of the pipeline system corresponding to each catalyst reactor 2, for example, the pipeline diameter, the pipeline length, the thermal transmission rate of the pipeline outer wall, and the heat transfer of the catalyst in the catalyst reactor. It is a coefficient determined by characteristics and the like. Obtaining these heat transfer characteristic values individually and accurately is useful for generalizing the model, but it requires considerable effort and cost.

Therefore, in a system in which the fluctuation range of operating conditions is limited, some special test (for example, a disposable flow meter is installed in a specific catalytic reactor 2 and the leak flow rate Q _{c3 in a hot closed state is obtained. the} measure, etc.) _i was performed once may be obtained a ₁ is a single model constants directly. _{That is, while obtaining the leak flow rates Q c3 and i} using a disposable flow meter, the above-mentioned first to third operations are performed. Then, Equation (7 '), the leakage flow rate _{Q c3, i,} based on furnace temperature Tf, and the catalyst layer temperature _{T c3, i,} may be calculated model constants _{a 1.} The model constants a ₁ by applying the following operation as a representative value of the total catalyst reactor 2, while satisfying the required accuracy, it is possible to reduce the labor and cost of the model constant adjusting. Examples of the disposable flow meter include an orifice type flow meter and the like. As described above, the differential pressure generated before and after the orifice is extremely small, so that the flow meter is required to have a certain degree of accuracy. However, since it is used only once, the cost increase due to the use of the flow meter can be suppressed.

Further, heat transfer characteristics of the model constants a ₁ generally often differ for each catalytic reactor 2 (for example, the distance between the inlet collecting pipe 101 and the catalytic reactor 2 (more specifically, the X _i The value) is often designed differently for each catalyst reactor 2). Therefore, the model constant a ₁ may be calculated individually for each catalyst reactor 2 as in the model constants a _{1, i and the like.}

According to the first embodiment, first, the leak flow rate Q _{c3, i} is calculated as a function of the catalyst layer temperature T _{c3, i.} Then, by applying the leakage flow rate _{Q c3, i} in equation (3) to calculate the leak rate _{k i.} Therefore, the change in the temperature distribution in the catalyst layer is placed in the catalytic reactor i (i.e., changes in the catalyst layer temperature T _{c3, i)} by a relatively easy measure of the leakage rate k _i of each of the valve mechanism 4 It can be easily measured online. The catalyst layer temperatures T _{c3 and i} can be measured inexpensively and easily by a temperature measuring device such as a thermoelectric pair. Therefore, without providing a costly measurement apparatus to the individual catalytic reactor i, inexpensive, and it can measure the leakage rate k _i of the valve mechanism i online easily.

The first to third operations described above may be artificially performed by an operator, or may be performed by the valve mechanism leak rate measuring device 1000 shown in FIG. The valve mechanism leak rate measuring device 1000 has, for example, a hardware configuration such as a CPU, a ROM, a RAM, a hard disk, and a communication device. A program capable of realizing the first means to the third means for performing the first operation to the third operation is recorded in the ROM, and the CPU reads and executes this program. As a result, the first to third means are realized. The communication device receives the measured values transmitted from each measuring device (for example, flow meter 112, inflow pressure meter 113, etc.) provided in the heating furnace device A1. The measured value is used for calculation by the CPU. The communication device transmits various control signals generated by the CPU to each drive device (for example, a fluid switching device 110, a gas preheating device 111, a deposit removing device 3 in the catalyst layer, etc.). These drive devices are driven based on control signals. When the first to third operations are performed artificially, the valve mechanism leak rate measuring device 1000 may be omitted.

<2. Second embodiment>
Next, the second embodiment will be described. In the second embodiment, the above-mentioned second to third operations are different from the first embodiment. Other than this, it is the same as that of the first embodiment. Therefore, the second to third operations will be described.

(2-1. Second operation)
In a second operation, by adjusting the gas preheater 111, is set to a different second inlet temperature T _in2 is the inlet temperature to the first inlet temperature T _in1 above. Then, it waits until the catalytic reaction apparatus 1 becomes a steady state. During this time, the furnace temperature T _f is kept constant. Then, after the catalyst reaction device 1 is in a steady state, the catalyst layer temperatures T _{2 and i} are recorded. Further, the differential pressure ΔP ₂ (that is, the difference between the gas pressure in the inflow collecting pipe 102 and the gas pressure in the outflow collecting pipe 103) is measured.

(2-2. Third operation)
Of the third operation, the leak rate calculation operation is different from that of the first embodiment. Therefore, the operation of calculating the leak rate will be described. Applying the formula (7) shown in the first embodiment to the gas flow rate Q2 _{, i} (in this case, the gas flow rate Q2 _{, i} means the gas flow rate in the open state), the following formula (8) Is obtained.

_{Q 2, i = (h i} LX i / ρCp) / Ln [(T f -T in2) / (T f -T 2, i)] (8)

Therefore, the ratio of the gas flow rate Q2 _{, i} and the leak flow rate _{Qc3, i} is expressed by the following mathematical formula (9).
Q _{c3, i} / Q _{2, i} = Ln [(T _f −T in ₂ ) / (T _f −T _{2, i} )]
/ Ln [(T _f −T _in2 ) / (T _f −T _{c3, i} )] (9)

Leak rate k _i is the ratio of the leakage flow rate during the closed state gas flow rate during the open state (reference flow) when given a differential pressure (reference pressure difference) before and after the valve mechanism 4. Therefore, by performing the correction so that the pressure difference when measuring the gas flow rate _{Q 2, i} and the leakage flow rate _{Q c3, i} are the _same, determining the leakage rate _{k i} from _{Q c3, i / Q 2,} i Can be done. That is, the leak rate _{k i} is given by the following equation (10).

k _i = a ₂ Q _{c3, i} / Q _{2, i}
= A ₂ Ln [(T _f −T in ₂ ) / (T _f −T _{2, i} )]
/ Ln [(T _f −T _in2 ) / (T _f −T _{c3, i} )] (10)
a ₂ : Model constant

Here, the model constant a ₂ is a pressure correction term, and when the differential pressures ΔP _{2 and ΔP 3} are sufficiently smaller than the absolute pressure before and after the valve mechanism 4, for example, the following equation (11) is used. Shown.
a ₂ = (ΔP ₂ / ΔP ₃ ) ^1/2 (11)

Therefore, the mathematical formula (10) is replaced with the following mathematical formula (10'). The reference flow rate is the gas flow rate Q2 _{, i} at the time of the second operation.
_{k i = Ln [(T f} -T in2) / (T f -T 2, i)]
/ Ln [(T _f −T _in2 ) / (T _f −T _{c3, i} )]
* (△ P ₂ / △ P ₃ ) ^1/2 (10')

Thus, equation (10 ') and on the basis of the measured values described above, the leak rate k _i is calculated. The advantage of the second embodiment is that the valve mechanism 4 is opened in a system in which the ventilation resistance changes when the valve mechanism 4 is opened (for example, a system in which by-products such as cork are deposited in the catalyst layer). it is to be calculated the leak rate k _i in consideration of the influence of a change in ventilation resistance in the state.

Therefore, the second embodiment is particularly useful in a catalytic reaction apparatus system in which coke or the like is produced as a by-product during the reforming of the raw material gas, and the by-product changes the aeration resistance of the catalyst layer every moment. This is because, in such a system, even if the leak flow rate Q _{c3, i can be measured, the leak flow rate Q c3, i} increases and the ventilation resistance of the catalyst layer increases due to the deterioration of the sealing property of the valve mechanism 4. This is because it is difficult to quantitatively isolate the decrease in the leak flow rate due to the above, and it is difficult to evaluate the performance deterioration (increase in the leak rate) of the valve mechanism 4. That, in fact, despite the leakage rate k _i is increased, there is a possibility to decrease an apparent leak flow Q _{c3, i} by an increase in the ventilation resistance of the catalyst layer. In the second embodiment, the leak flow rate Q _{c3, i} can be calculated in consideration of such an increase in ventilation resistance.

Another advantage of the second embodiment, in calculating the leak rate k _i, [rho, is that it does not Cp, h _i, requiring heat transfer characteristics values such as X _i. It takes time and money to obtain these values accurately in the heat.

When it is necessary to obtain the leak rate of the valve mechanism 4 based on the air permeability when the valve mechanism 4 is in the open state without being affected by the ventilation resistance due to the by-products such as cork. For example, it may be as follows. The time when the first and second operations described above are carried out is set as the initial stage of the operation before sufficient by-products such as cork are deposited, and the necessary data described above are measured here. The third operation may be performed at any time including after the cork is deposited. The period between the second and third operations is not particularly limited, and the reforming operation may be performed during this period. However, when the reforming operation is performed during this period, it is necessary to perform at least the operation of supplying the non-reactive gas and changing the inflow temperature again among the first and second operations before the third operation. (There is no need to record the data, because the data is recorded during the first and second operations).

<3. Third Embodiment>
In the third embodiment, the third operation is different from the first embodiment described above. Other than this, it is the same as that of the first embodiment. Therefore, the third operation will be described below.

(3-1. Outline of the third operation)
In a third operation, inlet temperature _T different from any inflow temperature _in the inlet temperature _{T in1, T in2 T in4} (Here, for convenience using a 4 subscript description) is set to a catalytic reactor 1 Wait until it reaches a steady state. _{Then, the catalyst layer temperature T c4,} i of the catalyst reactor i at this time is recorded, and the leak flow rate Q _{c3, i} is calculated based on the following mathematical formula (12). Thereafter, as in the first embodiment to calculate the leak rate k _i.
Q _{c3, i} = func (T _{c4, i} −T _{c3, i} ) (12)

(3-2. Measurement operation)
In the measurement operation, first, by performing the same operation as in the first embodiment, the catalytic reactor 2 corresponding to the valve mechanism 4 in which the _{differential pressure ΔP 3} in the steady state, the furnace temperature T _{f, and the closed state is set.} Record the catalyst layer temperatures T _{c3, i.}

Then, set the inlet temperature _{T in} the inlet temperature _{T in1, T} different from any inlet temperature _{T in4} of _in2, catalytic reactor 1 waits until a steady state. Then, the catalyst layer temperature T _{c4, i} at this time is recorded. The flow rate Q _T through the period of the first to the measuring operation is controlled to be constant. After the measurement operation is completed, the operation may be returned to the normal catalytic reaction operation.

(3-3. Leak rate calculation operation)
In the leak rate calculation operation, the leak flow rates Q _{c3 and i} in each catalytic reactor 2 are calculated by the following procedure using the measurement data obtained by the measurement operation. First, in the catalyst reactor i, the model constant β _i defined by the following mathematical formula (13) is introduced. Considering the unit of each parameter, the model constant β _i has a unit (m ³ / s) equivalent to the flow rate.
β _i = hLX _i / (ρC _p ) (13)
h: Thermal transmission rate (W / (m ² · K))
L: Perimeter of piping (m)
ρ: Gas density (kg / m ³ )
Cp: Specific heat of gas (J / (kg · K))
X _i : Length of the pipe between the inflow pipe and the catalyst reactor (m), specifically, the distance from the inflow temperature measurement point in the inflow collecting pipe 101 to the catalyst layer temperature measurement point of the catalyst reactor i.

The mathematical formula (13) is obtained by the above-mentioned mathematical formula (6). That is, when the temperature change from the inflow collecting tube 101 to the catalyst reactor 2 is relatively small and _{this differential equation is solved with ρ, Cp, Q c3, and i} being constant, the flow path to be examined the catalyst layer temperature T _i at the catalyst layer temperature measuring point is the end point (x = X _i) is expressed by the following equation (14).
_{T i = T f - (T} f -T in) exp [-hLX i / (ρCpQ c3, i)] (14)
X _i: x-coordinate of the catalyst layer temperature measuring points in the catalytic reactor i _{where, T = T in (x =} 0)
T = _Ti (x = X _i )

Here, in the mathematical formula (14), hLX _i / (ρCp) is defined _{as β i.} As a result, the model constant β _i is obtained. Further, the mathematical formula (14) is expressed as follows using _{β i.}
T _i = T _f- (T _f- T _in ) exp [-β _i / Q _{c3, i} )] (15)

The inlet temperature _T in2 obtained by the above _{procedure, T in4,} the catalyst layer temperature _T c3, _i, when the _{T c4, i} is substituted into equation (15), the following equation (15-1), (15 2) is obtained.
_{T c3, i = T f -} (T f -T in2) exp [-β i / Q c3, i)] (15-1)
_{T c4, i = T f -} (T f -T in4) exp [-β i / Q c3, i)] (15-2)

By subtracting the formula (15-1) from the formula (15-2) and further _{rearranging the leak flow rates Q c3 and i} , the following formula (16) is obtained.
Q _{c3, i} = −β _i / Ln [(T _{c4, i} −T _{c3, i} ) / (T _in4- T in ₂ )] (16)

Therefore, in the leak rate calculation operation, the leak flow rates Q _{c3 and i} in the catalyst reactor i are calculated using the mathematical formula (16). Thereafter, the same processing as that in the first embodiment, calculates the leak rate k _i.

Here, although the model constant β _i is defined by the mathematical formula (13), it is necessary to individually obtain the physical property value and the heat transfer characteristic value on the right side of the mathematical formula (13) and substitute them into the mathematical formula (13) in order to obtain _{the β i.} Is not always.

In the third embodiment, a fixed value is _{used for β i} used in the mathematical formula (16). A _{method for determining the value of β i} is obtained, for example, by the following test (hereinafter, this test is also referred to as a “β i calculation test”). Specifically, the first operation to the measurement operation are performed with a resistor having a known flow resistance coefficient, for example, an orifice having a resistance coefficient sufficiently higher than that of the catalyst layer, mounted on each catalyst reactor 2. .. Thus, inlet temperature described above in the catalytic reactor i _{T in2, T in4,} the catalyst layer temperature _T c3, _i, measure the _{T c4, i.} Further, the differential pressure before and after the orifice is measured when the catalyst layer temperatures T _{c3 and i are measured.} For the measurement of the differential pressure, a pressure gauge similar to each of the above-mentioned pressure gauges may be used. From this differential pressure, the flow rate distribution in the catalyst reactor i can be calculated. As described above, the flow velocity in the catalyst reactor is usually set to an extremely small value, for example, about several tens of cm / s in order to secure the contact time between the passing gas and the catalyst. .. On the other hand, in a catalytic reactor with the valve closed, the flow velocity is usually smaller, several cm / s or less. If valve-open and valve-closed catalytic reactors coexist in the catalytic reactor in the catalytic reactor, most of the gas will pass through the valve-open catalytic reactor, effectively opening the valve. The differential pressure before and after the catalytic reactor (common to all catalytic reactors) will be determined based only on the pressure loss coefficient of the catalytic reactor. This is because the flow rate flowing through the valve-opened catalytic reactor is almost constant at the value of [supply flow rate] / [number of valve-opened catalytic reactors], and the leak flow rate in the catalytic reactor when the valve is closed is a little. Even if it changes, the ratio of the flow rate change to the flow rate flowing through the valve opening catalytic reactor is small, so the change in differential pressure is also small, and it is difficult to quantitatively measure the leak flow rate change. Therefore, in the βi calculation test, it is conceivable to install an orifice having a resistance coefficient corresponding to the assumed resistance coefficient when the valve is closed for all catalytic reactors. In this case, the average flow rate of each catalytic reactor is equivalent to the leak flow rate when the valve is closed, and the relationship between the flow rate when the valve is closed, the pressure loss, and the temperature difference in the system is obtained by measuring the supply flow rate and the pressure difference. Can be done. The leak flow rates Q _{c3 and i} can be calculated based on this flow rate distribution and the flow rate Q _T. The inlet temperature _{T in2, T in4,} the catalyst layer temperature _{T c3, i, T c4,} i, leakage flow rate _{Q c3, i,} and on the basis of the equation (16) can determine the value of the model constants beta _i. The β _i thus obtained may be used in actual operation. In addition, β _i may be obtained for all catalyst reactors 2, or may be obtained only for one of the catalyst reactors 2, and this may be applied to other catalyst reactors 2. Moreover, as is clear from FIG. 3, β _i fluctuates from moment to moment during normal operation. Therefore, it is preferable to update _{β i at an arbitrary timing.}

<4. Fourth Embodiment>
Next, a fourth embodiment will be described. In the fourth embodiment, the operation for calculating the leak rate is different from that in the third embodiment. Other than this, it is the same as that of the third embodiment. Therefore, here, the operation of calculating the leak rate will be described.

In the fourth embodiment, the drag coefficient η _i in the catalytic reactor i is defined by the following mathematical formula (17).
η _i = ΔP / Q _i ² (17)

Here, △ P is the differential pressure between the inlet collector pipe and outlet collecting pipe, that is, the pressure loss, Q _i is the gas flow rate in the catalytic reactor i. Therefore, when the valve mechanism 4 in the catalyst reactor i is closed, the gas flow rate Q _i becomes the leak flow rate Q _{c3, i} .

As described above, the present inventors have found that there is a positive correlation between the _{resistance coefficient η i} and the model constant β _i. The physical meaning of this correlation _{is that both the increase in the value of the drag coefficient η i} and the increase in the value of the model constant β _i are caused by the increase in the amount of cork deposited in the catalyst layer. Specifically, when cork is deposited in the catalyst layer, the flow path in the catalyst layer is substantially narrowed by the deposited cork, so that the leak flow rates Q _{c3 and i} are reduced. On the other hand, the pressure loss ΔP hardly fluctuates. As described above, in the catalyst reactor 1 according to the third embodiment, a plurality of catalyst reactors 2 are arranged in parallel. In this case, even if one of the catalytic reactors i is closed, the gas that cannot pass through the catalyst layer of the catalytic reaction easily bypasses the other catalytic reactor 2. Therefore, the differential pressure between the inlet side and the outlet side of the closed catalyst layer does not change so much, and the leak flow rates Q _{c3 and i in} the closed catalyst reactor i decrease. Therefore, the leak flow rates Q _{c3 and} i of the catalyst reactor i are reduced, but the pressure loss ΔP hardly fluctuates. Therefore, the value of the _{drag coefficient η i} increases from the equation (17).

On the other hand, the thermal conductivity of cork is generally higher than the thermal conductivity of the raw material gas, reforming gas or catalyst particles that fill the space. Therefore, when cork powder is deposited in the space between the catalyst particles in the catalyst layer, the deposited cork powder is deposited. Through this, heat is easily transferred in the catalyst layer, and the thermal conductivity of the catalyst layer is increased. The heat transmission coefficient h in the formula (13) is the heat conduction of the gas flowing in the catalyst layer on the surface of the catalyst particles, the heat conduction of the catalyst layer, the heat conduction of the outer wall of the catalyst reactor, and the outer wall of the catalyst reactor of the gas in the heating furnace. It is a coefficient showing the total heat transfer property of the above heat conduction. When any of these heat transfer elements is promoted, the value of thermal transmission rate h increases. Therefore, when the thermal conductivity of the catalyst layer increases due to the increase in the deposited cork powder, the thermal transmissivity h increases, and β _i increases according to the equation (13).

Therefore, in the fourth embodiment, _{the relationship between the drag coefficient η i} and the model constant β _i is modeled by the following mathematical formula (18).
β _i = β _{0, i} · (η _i / η _{0, i} ) ^ai (18)
β _{0, i} : Initial value of _{β i a i} : Model constant ( _ai ≧ 0)

_{When η i} of the mathematical formula (17) is changed _{to η 3, i} and the mathematical formula (17) is substituted into the mathematical formula (18), the following mathematical formula (19) is obtained.

By substituting this mathematical formula (19) into the mathematical formula (16) and _{rearranging the leak flow rates Q c3 and i} , the following mathematical formula (20) can be obtained.

Therefore, in the leak rate calculation operation, the leak flow rates Q _{c3 and i} of the catalyst reactor i are calculated based on the mathematical formula (20). Then, to calculate the leak rate k _i by using the same method as the third embodiment.

Here, the model constant ai, the initial value β _{0, i of} the model constant, and the initial value η _{0, i} of the drag coefficient are obtained in the same manner as in the βi calculation test of the third embodiment. _{That is, the β i} calculation test is performed in a state where there is no cork accumulation (a state before the start of normal operation). As a result, the initial values β _{0, i} of the model constant are calculated. Further, the initial value η _{0, i of the} resistance coefficient is also calculated from the differential pressure ΔP ₃ and the leak flow rate Q _{c3, i. After that, a β i} calculation test is performed at an arbitrary timing during normal operation. As a result, the model constant β _i is calculated. Further, the resistance coefficient η _i is calculated from the differential pressure ΔP ₃ and the leak flow rate Q _{c3, i when the model constant β i is calculated.} Then, the obtained values are plotted on a plane with the horizontal axis as _{the logarithmic axis of ηi / η 0, i} and the vertical axis as the logarithmic _{axis of βi / β 0, i} , and the approximate straight line of each point is the least squares method. Calculate by etc. Then, the slope of this approximate straight line may be set as the model constant ai. The model constant ai may be applied to each catalyst reactor 2, or the model constant ai calculated for any of the catalyst reactors 2 may be diverted to the other catalyst reactor 2.

In the fourth embodiment, the following effects can be obtained. As is clear from FIG. 3, the model constant β _{i fluctuates from moment to moment.} Therefore, in the third embodiment, when the leak flow rate Q _{c3, i is} to be calculated accurately, it is necessary to _{frequently update the model constant β i.} Furthermore, the model constant β _i may fluctuate depending on the operating conditions. However, it takes time to calculate the model constant β _i. On the other hand, the mathematical formula (20) is a mathematical formula in consideration of _{β i, which fluctuates from moment to moment.} Therefore, once even calculated model constants ai, so can be calculated by considering the model constants beta _i varying from moment to moment the leakage flow rate Q _{c3, i} after the leakage flow rate Q _c3 easier and _{accurate, i} Can be calculated.

<1. Example 1>
In Example 1, a catalytic reactor 1 having seven catalytic reactors 2 (ie, N = 7) was prepared. Then, a coke oven gas containing tar as a raw material gas was supplied to each catalytic reactor i, and the reforming operation was performed under normal operating conditions in which the heating furnace temperature was maintained at about 800 ° C. After that, the supply gas was switched to nitrogen gas, which is a non-reactive gas, nitrogen gas was supplied to each catalytic reactor 2 at a flow rate of ^{40 Nm 3} _{/ h, and the furnace temperature T f} was set to 780 ° C. (first). operation).

Then, the gas preheating device 111 was adjusted to set the target value of the _{nitrogen gas inflow temperature Tin 2 to 750 ° C.} After that, it waited until the catalytic reaction device 1 became a steady state (second operation). Then, the valve mechanism 4 corresponding to the third and fourth catalyst reactors 2 (i = 3, 4) was closed, and the catalyst reactor 1 waited until it became a steady state. After the catalyst reactor 1 was in a steady state, the catalyst layer temperatures T _{c3 and i} were recorded (measurement operation). The catalyst layer temperature (catalyst reactor temperature) T _{c3 and i} are as shown in Table 1. _{During this series of operations, the differential pressure ΔP 3} between the gas pressure in the inflow collecting pipe and the gas pressure in the outflow collecting pipe is constant within the detection accuracy of the inflow pressure gauge 113 and the outflow pressure gauge 116. The value was 61 Pa.

Then, the third by the calculation operation of the by leak rate according to the first embodiment, to calculate the fourth catalytic reactor 2 of the leak rate k _{i. Specifically, the leak flow rates Q c3 and i} were calculated based on the mathematical formula (7'). Here, the value of the model coefficients a _1, using 3 × 10 ^-4 is a value measured in advance by the method described above. Then, the leak rate ki was calculated by applying the calculated leak flow rates Q _{c3 and i to the mathematical formula (3).} Here, as the value of the model constant α ₁ , 0.4, which is a value investigated and adjusted in advance, was used. The pressure at which the reference flow rate in the open state of the valve mechanism 4 is defined, that is, the reference pressure is set to 1 kPa. The results are shown in Table 2.

<2. Example 2>
In Example 2, the third by the calculation operation of the by leak rate according to the second embodiment, to calculate the fourth catalytic reactor 2 of the leak rate k _i. Specifically, the same processing as in Example 1 was performed except for the operations shown below. In the second operation, _{the target value of the flow rate temperature Tin 2} was set to 790 ° C., and the catalyst reaction device 1 waited until it became a steady state. Further, after the catalyst reactor 1 became a steady state, the catalyst layer temperatures T2 _{and i} of the third and fourth catalyst reactors 2 (i = 3, 4) were recorded. In the measurement operation, the valve mechanism 4 corresponding to the third and fourth catalyst reactors 2 was closed, and the catalyst reactor 1 was kept in a steady state. After the catalyst reactor 1 was in a steady state, the catalyst layer temperatures T _{c3 and i} were recorded. Table 3 shows the catalyst layer temperatures T _{2, i} , T _{c 3, i} , the inflow temperature _{Tin 2} , and the furnace temperature T _f . While performing the above operation, the differential pressure of the gas pressure in the inlet collection pipe and the gas pressure in the outlet collection tube (i.e., the differential pressure △ P _2, △ P ₃₎ is flowing pressure gauge 113 and outlet pressure gauge 116 It was constant within the range of the detection accuracy of 29 Pa.

Then, based on the equation (10 '), to calculate the leak rate _{k i.} Here, the model constant a2 is set to (ΔP ₂ / ΔP ₃ ) ^1/2 = 1. Although not directly used in calculating the leak rate k _i, the reference flow rate here is the gas flow rate Q _{2, i} of the catalytic reactor 2 in the differential pressure △ P _{2 =} 29 Pa. The results are shown in Table 4.

<3. Example 3>
In Example 3, the third by the calculation operation of the leak rate as described in the third embodiment, to calculate the fourth catalytic reactor 2 of the leak rate k _i. Specifically, the same processing as in Example 1 was performed except for the operations shown below.

Specifically, a coke oven gas containing tar as a raw material gas was supplied to each catalytic reactor 2, and the reforming operation was performed under normal operating conditions in which the heating oven temperature was maintained at about 800 ° C. Then, the supply gas was switched to nitrogen gas, which is a non-reactive gas, and nitrogen gas preheated to 800 ° C. was supplied to each catalytic reactor 2 at a flow rate of ^{40 Nm 3 / h (first operation).}

Then, the gas preheating device 111 was adjusted to _{set the target value of the nitrogen gas inflow temperature Tin 2} to 750 ° C. (second operation).

Then, the valve mechanism 4 corresponding to the third catalytic reactor 2 (i = 3) was closed, and the catalytic reactor 1 waited until it became a steady state. After the catalyst reactor 1 became a steady state, the catalyst layer temperatures T _{c3 and i} of the third catalyst reactor 2 were recorded. Then, the gas preheating device 111 was adjusted to _{set the target value of the nitrogen gas inflow temperature Tin4} to 710 ° C., and the catalyst reaction device 1 waited until it became a steady state. After the catalyst reactor 1 became a steady state, the catalyst layer temperatures T _{c4 and i} of the third catalyst reactor 2 were recorded. Table 5 shows the inflow temperatures T in ₂ , _{Tin 4} , and the catalyst layer temperatures T _{c3, i} , and T _{c4, i.} During these series of operations, the differential pressure between the gas pressure in the inflow collecting pipe and the gas pressure in the outflow collecting pipe is constant within the detection accuracy of the inflow pressure gauge 113 and the outflow pressure gauge 116, and is 25 Pa. there were.

Then, based on equation (16), to calculate the third leak flow rate k _i of the catalytic reactor 2. Specifically, the model constant β _i was calculated by the β i calculation test. The βi calculation test was performed in a state where no cork was deposited on the third catalytic reactor 2. As a result, the model constant β _i was 6.7. _{Then, when the leak flow rate Q c3, i} (catalyst reactor flow rate Q _i ) was calculated based on this value and the mathematical formula (16), ^{it was 1.3 Nm 3} / h. Then, based on the equation (3), calculation of the leak rate _{k i,} the leakage rate _{k i} was calculated to 4.7 × ^{10 -3.} The results are shown in Table 6. Table 6 also shows the model constant β _i and the leak flow rate Q _{c3, i} .

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 such examples. It is clear that a person having ordinary knowledge in the field of technology to which the present invention belongs can come up with various modifications or modifications within the scope of the technical idea described in the claims. , These are also naturally understood to belong to the technical scope of the present invention.

1 Catalyst reactor 2 Catalyst reactor 3 Catalyst layer deposit removal device 4 Valve mechanism 10, 40 Reaction vessel 11, 41 Inflow passage 12, 42 Outflow passage 13, 43 Catalyst layer 14, 44 Catalyst cage 15 Valve seat 16 Pore 17 Valve body 18, 48 Mandrel 21, 49 Drive device 101 Inflow collecting tube 102 Outflow collecting tube 110 Fluid switching device 111 Gas preheating device 112 Flow meter 113 Inflow pressure meter 114 Inflow thermometer 115 Catalyst layer thermometer 116 Outflow pressure meter

Claims (6)

It is a method of measuring the leak rate of a valve mechanism that measures the leak rate of a plurality of valve mechanisms arranged in parallel in a catalytic reaction device.
The catalytic reaction device is
N units are arranged in parallel, a catalytic reactor that treats the raw material fluid with a catalyst layer that is a fixed bed, an inflow collecting pipe that is a collecting pipe for supplying fluid to all the catalytic reactors, and each catalyst reactor. The valve mechanism, which is provided and can be independently set to either an open state for flowing fluid into the catalyst reactor or a closed state for blocking the flow of fluid to the catalyst reactor, all the catalysts. outlet collecting pipe is a collector pipe for causing the off downstream collect fluid flowing from the reactor, respectively provided in all of the catalytic reactor of the catalyst layer, the catalyst layer thermometer for measuring the temperature of the catalyst layer T _i , And an inflow reactor device equipped with an inflow thermometer for measuring the inflow temperature, which is the fluid temperature of the inflow collecting pipe, and arranged in a heating reactor in which the reactor temperature can be adjusted.
A fluid preheating device that preheats the fluid supplied to the inflow collecting pipe, and
A fluid switching device for switching the fluid supplied to the inflow collecting pipe between the raw material fluid and the non-reactive fluid, and
A flow meter that measures the flow rate passing through the inflow collecting pipe and
A differential pressure measuring device for measuring the differential pressure between the inflow collecting pipe and the outflow collecting pipe is provided.
The method for measuring the leak rate is
The first operation of setting the fluid switching device so that the non-reactive fluid passes through the inflow collecting pipe with all the valve mechanisms open.
A second operation of adjusting the fluid preheater so that the inflow thermometer shows a predetermined inflow temperature.
After the valve mechanism corresponding to a predetermined n _c stand catalytic reactor in the n-number and a closed state, to maintain the operating state until a steady state, the differential pressure △ P ₃ in the steady _state, and the n _c stand catalytic reactor of the catalyst layer temperature _{T c3, i} was recorded,
k _i = α ₁ , Q _{c3, i}・ (ΔP ₃ ) ^{-1 / 2}
Q _{c3, i:} leakage flow rate of the valve mechanism in a closed state alpha _1: leakage rate k _i of i-th of the valve mechanism to be defined in the model constants becomes equation, as a function using the catalyst layer temperature T _{c3, i} A method for measuring the leak rate of a valve mechanism, which comprises a third operation for calculating. The in-heating furnace apparatus further includes a furnace thermometer for measuring the furnace temperature of the heating furnace.
In the third operation,
Further, the furnace temperature T _f of the heating furnace is recorded, and the furnace temperature T f is recorded.
_{The leak flow rate Q c3, i} of the valve mechanism in the closed state is
Q _{c3, i} = a ₁ · (T _f −T _{c3, i} )
a ₁ : The method for measuring the leak rate of the valve mechanism according to claim 1, wherein the model coefficient is calculated by an equation. The in-heating furnace apparatus further includes a furnace thermometer for measuring the furnace temperature of the heating furnace.
In the second operation,
While recording the _{inflow temperature Tin2} , which is the predetermined inflow temperature,
The catalyst layer temperature T _i of the i-th of said catalytic reactor to maintain the operating state until a steady state, recording the catalyst layer temperature T _i at steady state as a catalyst layer temperature T _{2, i,}
In the third operation,
Further, the furnace temperature T _f of the heating furnace is recorded, and the furnace temperature T f is recorded.
k _i = a ₂ Ln [(T _f −T in ₂ ) / (T _f −T _{2, i} )]
/ Ln [(T _f −T _in2 ) / (T _f −T _{c3, i} )]
a _2: using the model coefficients becomes equation and calculates a leak rate k _i, the measuring method of the leak rate of the valve mechanism according to claim 1. In the second operation,
While recording the _{inflow temperature Tin2} , which is the predetermined inflow temperature,
In the third operation,
It said inlet thermometer and adjust the fluid preheating apparatus as shown different inlet temperature T _in4 from said inlet temperature T _in2, the catalyst layer temperature T _i maintains operations until a steady state, the steady state the catalyst layer temperature _{T i} is recorded as the catalyst layer temperature _{T c4, i,
The leak flow rate Q c3, i} of the valve mechanism in the closed state is
Q _{c3, i} = −β _i / Ln [(T _{c4, i} −T _{c3, i} ) / (T _in4- T in ₂ )]
β _i : The method for measuring the leak rate of the valve mechanism according to claim 1, wherein the model coefficient is calculated using an equation. The method for measuring a leak rate of a valve mechanism according to any one of claims 1 to 4, wherein the raw material fluid contains a hydrocarbon. A catalytic reaction device that measures the leak rate of multiple valve mechanisms arranged in parallel.
N units are arranged in parallel, a catalytic reactor that treats the raw material fluid with a catalyst layer that is a fixed bed, an inflow collecting pipe that is a collecting pipe for supplying fluid to all the catalytic reactors, and each catalyst reactor. The valve mechanism, which is provided and can be independently set to either an open state for flowing fluid into the catalyst reactor or a closed state for blocking the flow of fluid to the catalyst reactor, all the catalysts. outlet collecting pipe is a collector pipe for causing the off downstream collect fluid flowing from the reactor, respectively provided in all of the catalytic reactor of the catalyst layer, the catalyst layer thermometer for measuring the temperature of the catalyst layer T _i , And an inflow reactor device equipped with an inflow thermometer for measuring the inflow temperature, which is the fluid temperature of the inflow collecting pipe, and arranged in a heating reactor in which the reactor temperature can be adjusted.
A fluid preheating device that preheats the fluid supplied to the inflow collecting pipe, and
A fluid switching device for switching the fluid supplied to the inflow collecting pipe between the raw material fluid and the non-reactive fluid, and
A flow meter that measures the flow rate passing through the inflow collecting pipe and
A differential pressure measuring device for measuring the differential pressure between the inflow collecting pipe and the outflow collecting pipe is provided.
In addition
A first means of setting the fluid switching device so that the non-reactive fluid passes through the inflow collecting pipe with all the valve mechanisms open.
A second means of adjusting the fluid preheater so that the inflow thermometer shows a predetermined inflow temperature, and
After the valve mechanism corresponding to a predetermined n _c stand catalytic reactor in the n-number and a closed state, to maintain the operating state until a steady state, the differential pressure △ P ₃ in the steady _state, and the n _c stand catalytic reactor of the catalyst layer temperature _{T c3, i} was recorded,
k _i = α ₁ , Q _{c3, i}・ (ΔP ₃ ) ^{-1 / 2}
Q _{c3, i:} leakage flow rate of the valve mechanism in a closed state alpha _1: leakage rate k _i of i-th of the valve mechanism to be defined in the model constants becomes equation, as a function using the catalyst layer temperature T _{c3, i} A catalytic reaction apparatus comprising a third means for calculating and a valve mechanism leak rate measuring apparatus for executing the calculation.

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