JP2005255475A - Synthetic gas producing apparatus and method for operating the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a synthetic gas producing apparatus in which an oxygen permeation ceramic film tube is easily replaced or repaired by limiting a deficiency part even when the tube is deteriorated or damaged. <P>SOLUTION: The synthetic gas producing apparatus has a plurality of module reaction furnaces 1. Each of the module reaction furnaces 1 has the oxygen permeation type ceramic film tube 21, a reforming catalyst part 20, one vessel 15 housing the oxygen permeation type ceramic film tubes 21 and the reforming catalyst parts 20 in common, a raw material air supply port 3 for supplying raw material air to the vessel 15, a raw material gas supply port 2 for supplying a raw material gas to the vessel 15, a synthetic gas discharge port 4 for discharging a synthetic gas produced in the vessel 15 and an oxygen deficient air outlet 5 for discharging oxygen deficient air produced in the vessel 15. The raw material gas supply ports 2, the raw material air supply ports 3, the synthetic gas discharge ports 4 and the oxygen deficient air outlets 5 in the plurality of module reaction furnaces 1 are respectively connected to each other in common parts. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a synthesis gas production apparatus and an operation method thereof, and more particularly, to a synthesis gas production apparatus having an oxygen permeable ceramic membrane tube and a reforming catalyst section and an operation method thereof.

  Methods for producing a product gas (target gas or desired gas) such as synthesis gas or unsaturated hydrocarbon using a combination of an exothermic partial oxidation reaction and an endothermic steam reforming reaction are known. In particular, in a reactor having an oxygen-permeable ceramic membrane (oxygen ion mobility) that causes an exothermic reaction with oxygen from an oxygen-containing gas such as air, the required heat quantity of the endothermic reaction is satisfied by the exothermic reaction. In addition, a product gas generation method in a reaction furnace in which an exothermic reaction and an endothermic reaction are thermally combined is known.

Natural gas and methane, which is the main component of natural gas, are usually converted into synthesis gas, which is an intermediate of conversion from methane to liquid fuel, so that various utilization forms can be realized. The synthesis gas is a mixture of hydrogen and carbon monoxide having a H ₂ / CO molar ratio of about 0.6 to about 6.

  One method for converting methane to synthesis gas is by steam reforming. That is, methane is reacted with steam and converted into a mixture of hydrogen and carbon monoxide by an endothermic reaction. Heat for maintaining this endothermic reaction is given from outside the reforming reaction region. The steam reforming reaction is represented by the formula (1).

CH ₄ + H ₂ O → CO + 3H ₂ (1)
In the partial oxidation reaction method, methane reacts with oxygen in an exothermic reaction and is converted to synthesis gas. The partial oxidation reaction is represented by the following formula.

CH ₄ + 1 / 2O ₂ → 2H ₂ + CO (2)
As a method for realizing these basic synthesis gas generation reactions, the basic configuration of the reactor and the basic configuration of the elements are disclosed in, for example, Patent Documents 1 and 2.

  In order to efficiently generate synthesis gas, the performance of the oxygen permeable ceramic membrane, the supply path of methane as a raw material gas, the supply path of high-temperature air, the exothermic reaction amount and endothermic reaction amount of the above basic chemical reaction In order to realize the balance, it is necessary to devise the shape, the flow path of various gas components, the outflow path of oxygen-deficient air, and the synthesis gas extraction flow path.

  In the ceramic membrane type synthesis gas reactor, heat required for the reforming reaction shown in the formula (1) is converted into enthalpy due to the temperature rise of the mixed gas of the synthesis gas and the raw material gas generated by the partial oxidation reaction shown in the formula (2). By replenishing by ascending, it becomes an autonomous system. For this purpose, it is necessary to optimize the number of ceramic membrane tubes, the length of the reaction portion, the capacity and flow rate of the reforming tube, and the like.

The oxygen permeable ceramic membrane is a solid electrolyte membrane that permeates and transfers oxygen ions in preference to other elements and their ions. It includes mobile oxygen ion vacancies that provide a conduction field for the selective transport of oxygen ions through the material (membrane). The transport through the membrane element is driven by the ratio of oxygen partial pressure (P _O2 ) between both sides of the membrane element. O ^- flows from the high side of the surface of the oxygen partial pressure P _O2 of the membrane elements to the lower side surface.

Of O ₂ O ^- ionization to takes place at the cathode side of the membrane elements, their ions are transported across the membrane element. Next, O 2 ^— bonds to oxygen molecules, or reacts with the catalyst layer material with the source gas to release electrons e ⁻ .

  The transfer of oxygen ions generates a molecular oxygen gradient in the ceramic film, and this molecular oxygen reacts with part of the film material to change the structure in the composition. This may be enhanced by a manufacturing defect of the ceramic film. The ceramic film partially expands and contracts, and changes occur in the operation that generates stress in the ceramic film. This phenomenon is described, for example, in Non-Patent Document 1 as ceramic stress fields.

  This is because the ceramic membrane tube is generated in the ceramic membrane by replacing the ceramic membrane tube periodically within a predetermined period in the operation of the practical oxygen permeable ceramic membrane type synthesis gas production reactor. It is necessary to realize a situation in which the above-described stress in the ceramic can be expected to be a predetermined level or less.

  When it is detected that the ceramic membrane tube is broken regularly or unexpectedly, it is necessary to replace the ceramic membrane tube in order to ensure the performance of the synthesis gas component and the safety of operation. Efficient and planned replacement of the ceramic membrane tube is important in the operation of the synthesis gas reactor.

  Since the synthesis gas reactor of interest here may use hundreds to thousands of ceramic membrane tubes in the practical application stage, it is possible to efficiently replace the ceramic membrane tubes. It becomes a problem in plant operation.

However, the arrangement and basic specifications of components that are effective for exchanging a large number of ceramic membrane tubes have not been studied. Patent Documents 1 and 2 also do not describe replacement of the ceramic membrane tube.
JP 2000-26103 A JP 2002-85946 A TJ Mazance et. Al., “Oxygen Transport Membranes for Syngas Production”, 2001 Elsevier Science BV

  Oxygen permeable ceramic membrane reactors can usually operate at pressures of 10 to 20 atmospheres or higher, in a temperature range of 600 ° C. to 1100 ° C., and absorb heat and oxygen during operating and transition times. There is also a need for a synthesis gas and unsaturated hydrocarbon production reactor with means to compensate for dimensional variations due to emissions. This type of reactor also allows the membrane element to have a specified temperature limit due to a good balance between reaction heat and other heat sinks (heat dissipation or endothermic), and efficient heat transfer from the exothermic reaction to the endothermic reaction. It is desirable that it can be maintained within.

  Furthermore, it is desirable that the reactor can be made more secure by minimizing the risk of flammable process gas or product gas leaking under high pressure into the oxygen-containing stream. In addition, for example, it is desirable that an efficient operation can be performed by quickly responding to a case where one or a plurality of oxygen permeable ceramic membrane tubes of a module is deteriorated or damaged.

  An object of the present invention is to provide a synthesis gas that can be easily replaced or repaired by limiting the defective portion even when, for example, one or a plurality of oxygen permeable ceramic membrane tubes have a defect such as deterioration or breakage. It is in providing a manufacturing apparatus and its operating method.

  The present invention achieves the above object, and the invention according to claim 1 is a syngas production apparatus having a plurality of module reactors, each of the module reactors having at least one oxygen permeation. Type ceramic membrane tube, at least one reforming catalyst unit, one vessel that commonly accommodates these oxygen-permeable ceramic membrane tube and reforming catalyst unit, and source gas for supplying source gas into the vessel A supply port, a raw material air supply port for supplying raw material air into the vessel, a synthetic gas discharge port for discharging synthetic gas generated in the vessel, and an oxygen-deficient air generated in the vessel are discharged. An oxygen-deficient air outlet, and at least one of the source gas supply port, source air supply port, synthesis gas discharge port, and oxygen-deficient air outlet of the plurality of module reactors Also that one is connected to a common part with each other, and wherein.

  The invention described in claim 11 is a method for operating a synthesis gas production apparatus having a plurality of module reactors, each of the module reactors comprising at least one oxygen permeable ceramic membrane tube and at least one One reforming catalyst section, one vessel that accommodates the oxygen permeable ceramic membrane tube and the reforming catalyst section in common, a source gas supply port for supplying a source gas into the vessel, and the vessel A raw material air supply port for supplying raw material air, a synthetic gas discharge port for discharging the synthetic gas generated in the vessel, and an oxygen-deficient air outlet for discharging oxygen-deficient air generated in the vessel , At least one of the source gas supply port, the source air supply port, the synthesis gas discharge port, and the oxygen-deficient air outlet of the plurality of module reactors is common to each other The module reaction is detected when at least one of the component concentration and temperature of the synthesis gas is detected at the synthesis gas outlet of the module reactor and the component concentration or temperature exceeds a predetermined range. The furnace is stopped.

  The invention described in claim 12 is a method for operating a synthesis gas production apparatus having a plurality of module reactors, wherein each of the module reactors includes at least one oxygen-permeable ceramic membrane tube and at least one One reforming catalyst section, one vessel that accommodates the oxygen permeable ceramic membrane tube and the reforming catalyst section in common, a source gas supply port for supplying a source gas into the vessel, and the vessel A raw material air supply port for supplying raw material air, a synthetic gas discharge port for discharging the synthetic gas generated in the vessel, and an oxygen-deficient air outlet for discharging oxygen-deficient air generated in the vessel , At least one of the source gas supply port, the source air supply port, the synthesis gas discharge port, and the oxygen-deficient air outlet of the plurality of module reactors is common to each other And when the component concentration or temperature of the gas is detected at the oxygen-deficient air outlet of the module reactor and the component concentration or temperature exceeds a predetermined range, the module reactor Stopping.

  The invention as set forth in claim 14 is a method of operating a synthesis gas production apparatus having a plurality of module reactors, each of the module reactors comprising at least one oxygen permeable ceramic membrane tube and at least one One reforming catalyst section, one vessel that accommodates the oxygen permeable ceramic membrane tube and the reforming catalyst section in common, a source gas supply port for supplying a source gas into the vessel, and the vessel A raw material air supply port for supplying raw material air, a synthetic gas discharge port for discharging the synthetic gas generated in the vessel, and an oxygen-deficient air outlet for discharging oxygen-deficient air generated in the vessel , At least one of the source gas supply port, the source air supply port, the synthesis gas discharge port, and the oxygen-deficient air outlet of the plurality of module reactors is common to each other And when stopping a part of the plurality of module reactors, the supply of at least one of the source gas and source air of the target module reactor to be stopped is stopped, When detecting the pressure difference between the source gas supply port and the source air supply port of each module reactor or the pressure difference between the synthesis gas outlet and the oxygen-deficient air outlet and stopping the supply of the source gas or source air, The supply stop of the source gas and source air is controlled so that the pressure difference of the module reactor falls within a predetermined range.

  According to the present invention, even when the oxygen permeable ceramic membrane tube of the synthesis gas production apparatus is deteriorated or damaged, only the relevant module reactor can be separated from the whole and replaced or repaired. Operation becomes possible. Moreover, since the plant scale can be easily expanded by increasing the number of oxygen permeable ceramic membrane tubes and reforming catalyst sections of the module, a plant having a scale corresponding to various applications can be obtained.

  First, an outline of the best mode of a synthesis gas production apparatus and an operation method thereof according to the present invention will be described. This syngas production apparatus has a configuration in which a combination of an oxygen-permeable ceramic membrane and its support membrane and a reforming catalyst column are combined, and a module configuration in which a synthesis gas reactor is divided into a plurality of parts. These module reactors have, for example, a structure in which the upper lid portion of the upper part of the vessel can be removed, and a plurality of oxygen permeable ceramic membrane tubes regularly arranged in the reactor are handled from the upper part by a loading / unloading device. The oxygen permeable ceramic membrane tube has a structure in which high-temperature air can be supplied, and a region in which methane is supplied with the oxygen permeable ceramic membrane as a boundary and a gas generated by a partial oxidation reaction is supplied to the reforming catalyst column. . Means for achieving a seal structure between the tube plate and the structure supplied to the chamber for discharging the synthesis gas generated in the reforming catalyst column is provided.

  A plurality of oxygen permeable ceramic membrane tubes are arranged in each reaction furnace, and further, a flow path of a raw material gas supplied to the periphery of the ceramic membrane tube and the inside of the oxygen permeable ceramic membrane tube are supplied. Houses hot air flow path components. Furthermore, at least one reforming catalyst column for completely reforming the raw material gas component still mixed in addition to the synthesis gas reformed on the ceramic membrane tube is accommodated. These constituent elements / housing bodies constitute a support structure provided on the reactor vessel wall and a seal structure capable of maintaining airtightness.

  In the first preferred embodiment, specifications are selected for each module reactor so that the exothermic reaction and endothermic reaction achieve a predetermined balance (a situation where the exothermic reaction slightly exceeds the endothermic reaction).

  For this purpose, in a modular reactor, a tube made of a reforming catalyst that performs an endothermic reaction is arranged at the center of a plurality of ceramic membrane tubes that undergo an exothermic reaction. In this ceramic membrane tube, a thin tube for supplying raw material air from below is arranged. Air flows along the inside of the ceramic membrane tube from the top of the capillary tube, and oxygen is supplied to the membrane. The upper end of the ceramic membrane tube is closed to restrict the air flow path.

  In the second embodiment, in the arrangement of the ceramic membrane tube bundle and the reforming catalyst region in the modularized reactor, the reforming catalyst region is arranged above the ceramic membrane tube region.

  In any of these embodiments, loading and unloading of the ceramic membrane tube and the reforming catalyst region is performed as a whole modular reactor. Basically, one module reactor is periodically stopped and replaced by a predetermined replacement pattern. During this replacement period, the other modular reactors in the same plant continue to operate, thereby maintaining the plant syngas production performance.

  On the other hand, the specifications of oxygen permeable ceramic membranes are selected in consideration of manufacturing stability, but many ceramic membrane tubes have manufacturing variations, etc., and change over time due to differences in operating temperature conditions. It can be considered to vary. In addition, performance degradation of all tubes is not the same due to factors such as variations in plant operations and pressure fluctuations. In order to detect unscheduled performance degradation, ceramic membrane tube breakage, leakage from the seal, etc., a gas component detection area and detector are placed at the outlet from the module reactor to monitor online. Do.

  Reflecting the results of these on-line gas analysis changes, feedback is given to the operation of the modular reactor. The feedback is to stop the supply of raw material gas and high temperature air to a specific module reactor when it deviates from the limit level and the part related to steady operation such as raw material gas supply amount / temperature and high temperature air supply amount / temperature. Can do.

  Such a storage body is assembled in advance with a ceramic membrane tube and a reforming catalyst region and stored in the plant, and the used storage body after replacement is temporarily stored in the plant and then discarded.

  Next, embodiments of the synthesis gas production apparatus and the operation method thereof according to the present invention will be described more specifically with reference to the drawings.

  First, a first embodiment of a synthesis gas production apparatus according to the present invention will be described with reference to FIGS. 1 and 2 show an example of a hydrogen production plant having a modular reactor structure in the present embodiment, and FIGS. 3 to 5 show a specific structure of one modular reactor 1.

FIG. 1 is a plan view of an embodiment of the synthesis gas production apparatus, and FIG. 2 is a schematic longitudinal sectional view taken along line AA in FIG. In the synthesis gas production apparatus shown in FIGS. 1 and 2, four module reactors 1 are combined. The vessel 15 of each module reactor 1 is provided with a source gas (such as CH ₄ ) supply port 2 at the upper end, a source air supply port 3 at the lower end, and a synthesis gas discharge port 4 and an oxygen deficiency on the side surface. An air outlet 5 is provided.

  The source gas supply port 2 of each module reactor 1 is connected to a common source gas supply source 7 via a source gas supply valve 6. Similarly, the raw material air supply port 3 of each module reactor 1 is connected to a common raw material air supply source 9 via a raw material air supply valve 8. Further, the synthesis gas discharge port 4 of each module reactor 1 is connected to a common synthesis gas recovery device 11 via a synthesis gas discharge valve 10. Similarly, the oxygen-deficient air discharge port 5 of each module reactor 1 is connected to a common oxygen-deficient air recovery device 13 via an oxygen-deficient air discharge valve 12. The raw material gas supply valve 6, the raw material air supply valve 8, the synthesis gas discharge valve 10, and the oxygen-deficient air discharge valve 12 are all preferably solenoid valves.

  As described above, the module effect can be obtained by sharing the supply control device and operation of the raw material gas and high temperature air. The modularization effect, especially in the process of establishing new production technologies, ensures flexibility in investment choices and elemental technology developments related to investment in expanding the scale of synthesis gas production. Therefore, it is possible to systematically stop the plant for and to contribute to an increase in the overall plant operation rate.

  In addition, the synthesis gas produced from each module reactor is collected as a whole, and the synthesis gas recovery device 9 for transporting the synthesis gas to the next step is transported to the next step. Can be processed. Similarly, the oxygen-deficient air discharged as high-temperature air can also be recovered as a whole by collecting all the air discharged from each module reactor 1, thereby improving the efficiency of heat recovery / utilization of the discharged high-temperature air.

  3 to 5 show the structure of the module reactor 1, FIG. 3 is a perspective view of the module reactor 1 of FIG. 2, FIG. 4 is a longitudinal sectional view of the module reactor 1 of FIG. [Fig. 5] Fig. 5 is a cross-sectional plan view taken along line BB in Fig. 4.

  The vessel 15 is a substantially cylindrical container whose axis is vertical, and one reforming catalyst unit 20 is disposed at the center along the axis, and six oxygen permeable ceramic membrane tubes are disposed so as to surround the container. 21 are arranged, and these are accommodated in the vessel 15.

  The inside of the vessel 15 is partitioned into a plurality of cells, and partition walls 23 to 29 and annular outer walls 32 to 37 that partition these cells are stacked in the vertical direction. The partition walls 23 to 29 and the outer walls 32 to 37 are connected to each other by a flange 40. Thus, an air orifice cell 50, an oxygen-deficient air discharge cell 51, a synthesis gas passage cell 52, a synthesis gas generation cell 53, and a raw material gas orifice cell 54 are formed in this order from the bottom of the vessel 15. Each cell is structured to communicate only with a tube.

  A source gas such as methane enters the top 60 of the vessel 15 from the source gas supply port 2 and descends through the orifice pipe 61 of the source gas orifice cell 54 from here along the outer periphery of the ceramic membrane tube 21. Descent. The upper end of the ceramic membrane tube 21 is closed. On the other hand, the raw air enters the bottom 63 of the vessel 15 from the raw air supply port 3, and rises from here through the orifice pipe 64 of the air orifice cell 32. The upper part of the orifice pipe 64 is inserted into the ceramic membrane tube 21. The raw material air rises through the orifice tube 64 and then collides with the inner wall of the ceramic membrane tube 21 at the upper end thereof, and then descends along the annular portion between the inner wall of the ceramic membrane tube 21 and the outer wall of the orifice tube 64. While the source gas and the source air flow in parallel across the ceramic membrane tube 21, oxygen in the source air permeates the ceramic membrane tube 21, and the partial oxidation reaction represented by the formula (2) proceeds. Then, synthesis gas is generated.

  Thereafter, the synthesis gas passes upward from the lower end portion of the reforming catalyst portion 20, and here, the reforming reaction represented by the formula (1) occurs. Thereafter, the synthesis gas goes out of the vessel 15 from the synthesis gas generation cell 53 through the synthesis gas outlet 4.

  On the other hand, the raw material air descends along the annular portion between the inner wall of the ceramic membrane tube 21 and the outer wall of the orifice tube 64 to become oxygen-deficient air, and passes from the oxygen-deficient air discharge cell 51 through the oxygen-deficient air discharge port 5 to the outside of the vessel 15. Go out.

  4 and 5, as an example of the arrangement of the ceramic membrane tube and the reforming catalyst unit, an example of the arrangement of six ceramic membrane tubes and one reforming catalyst unit has been shown. Is optimized by the size of each reactor.

  The orifice pipes 61 and 64 are for equalizing the amounts of source gas (methane) and source air supplied to the six ceramic membrane tubes as much as possible, and are basically equally distributed. However, the flow distribution can be freely changed by adjusting the diameters of the orifice pipes 61 and 64. The ceramic membrane tube 21 and the reforming catalyst unit 20 are in contact with each other in part, thereby having a structure that promotes heat conduction.

  Since the outlet of the synthesis gas passage cell 52 is only the reforming catalyst unit 20, the gas inevitably goes to the reforming catalyst unit 20, and a methane conversion rate of 90% or more is obtained at the synthesis gas outlet 4. Further, by sealing the heat generating part, the temperature and the injection amount of the heat transfer medium between the outer wall and the methane flow path block are adjusted, so that the heat control is easily performed.

  6 to 8 show a second embodiment of the synthesis gas production apparatus according to the present invention. FIG. 1 is common to the first and second embodiments. In addition, parts common or similar to those in the first embodiment are denoted by common reference numerals, and redundant description is omitted.

  FIG. 6 shows a schematic longitudinal sectional view of the synthesis gas production apparatus of this embodiment. In this embodiment, the source gas supply port 2 and the source air supply port 3 of each module reactor 101 are provided on the side surface of the vessel 15 of the module reactor 101, and the synthesis gas outlet 4 is provided at the upper end of the vessel 15. The oxygen-deficient air discharge port 5 is provided at the lower end of the vessel 15.

  FIG. 7 is a longitudinal sectional view showing the inside of the module reactor 101 of FIG. 6, and shows the flow path and the flow distribution mechanism concept of the raw material gas, generated synthesis gas, and high-temperature air. Here, the oxygen permeable ceramic membrane tube, the upper and lower lids for replacement of the reforming catalyst part, the sealing mechanism between the flow paths, and the like, which are common elements regardless of the presence or absence of the modular configuration, are not illustrated. 8 is a cross-sectional view taken along the line CC of FIG.

  Pipes 72 and 73 provided with orifices 70 and 71 are arranged in the flow paths on the raw material (methane) gas and air sides, respectively, whereby flow distribution is performed. While the methane and air supplied from the upper part and the lower part respectively flow upward in parallel along the outer surface and the inner surface of the ceramic membrane tube 21 whose upper end is closed, the reaction of Formula (2) proceeds. The outlets of the reacted gas and unreacted gas are directly connected to the reforming catalyst layer 75. An oxygen-deficient air discharge pipe 90 is provided inside the ceramic membrane tube 21 and guides the oxygen-deficient air that has flowed up along the inner surface of the ceramic membrane tube 21 to the oxygen-deficient air discharge port 5.

  The heat generated in the vicinity of the ceramic membrane tube 21 exchanges heat with the reforming catalyst layer 75 by contact heat conduction or by air between the outer wall of the vessel 15 and the methane passage block.

  As shown in FIG. 8, also in this second embodiment, the number of ceramic membrane tubes 21 per block is six. The feature of this structure is that the flow along the wall surface of the ceramic membrane tube 21 is upward. Since the gas whose temperature has increased due to the combustion reaction has become lighter, it goes upward. Therefore, heat can be efficiently transferred to the reforming catalyst layer 75 which is an endothermic reaction layer. The reforming catalyst layer 75 is arranged on the upper part of the oxygen permeable ceramic membrane tube 21 region, and the raw material gas that has not reacted in the oxygen permeable ceramic membrane tube 21 region is made available by utilizing the heat of the synthesis gas that has been heated. This is a method of completely reforming to synthesis gas. It is possible to optimize the thickness of the reforming catalyst layer 75 and the like.

  FIG. 9 shows the characteristics of the synthesis gas discharged from the synthesis gas discharge port 4 and the oxygen-deficient air discharged from the oxygen-deficient air discharge port 5 of each module reactor 1 of the first embodiment (see FIG. 2 and the like). Indicates the mounting position of the detector to be measured / detected. That is, as indicated by D and E circled in FIG. 9, the detector is connected between the synthesis gas outlet 4 and the synthesis gas recovery device 11 of each module reactor 1 and between the oxygen-deficient air outlet 5 and the oxygen. It arrange | positions between the deficient air collection | recovery apparatuses 13. FIG.

  Items to be measured / detected as characteristics of synthesis gas or oxygen-deficient air are, for example, temperature, pressure, and gas components. Some of these items may be used. The gas component is an object of detection of hydrogen, carbon monoxide, carbon dioxide, methane, oxygen, etc., or a part thereof, or a combination of those parts.

  FIG. 10 shows an example of the structure of such a detector portion. In the illustrated example, a detector mounting portion 80 is provided in the middle of the piping between the synthesis gas discharge port 4 and the synthesis gas discharge valve 10. The detector mounting portion 80 has a structure in which a pipe having a large diameter is connected by a flange 81. By increasing the flow path area in this part, the flow velocity is reduced, and the extraction time for component detection can be obtained. The illustrated detector mounting portion 80 is provided with a thermocouple 82 for measuring temperature, a pressure gauge 83, and a component detector 84.

  Although measurement of the raw material gas or raw material air supplied to each module reactor 1 is not shown in FIG. 9, it is possible to similarly arrange detectors for measuring characteristics on the supply side. The measurement on the supply side as a whole is before the distribution to each module reactor 1 or after the distribution, on the downstream side of the source gas supply valve 6 and the source air supply valve 8 (module reactor 1 side) may be sufficient.

  By monitoring the gas and component characteristics of the inlet / outlet part online, gas / air leakage due to deterioration over time of the oxygen permeable ceramic membrane tube performance or aging due to plant operation, etc. In addition, it is possible to detect a change in the gas component due to breakage of the ceramic membrane tube or the seal portion. As a detection method, fluctuations during steady operation, differences in measured values due to local arrangement of measuring instruments and average composition passing through, etc. shall be adjusted separately.

  FIG. 11 shows an example of correspondence between signals and equipment when one of the module reactors is stopped and operation is continued in the other module reactors when these measurement results are fed back and an abnormality is detected. Yes. An abnormal signal obtained from the thermocouple 82 and the component detector 84 is detected by the measuring devices 110 and 111, and a stop signal is sent to the inlet side electromagnetic valve 112 and the outlet side electromagnetic valve 113 communicating with the corresponding module reactor. At that time, the pressure difference is monitored by the differential pressure gauge 114 based on the syngas side pressure gauge 83 and the oxygen-deficient air side pressure gauge 83a, and the inlet side solenoid valve 112 and the outlet side electromagnetic valve are set so that the pressure difference does not become excessively high. A timing signal for closing the valve 113 is sent. At this time, a signal is also sent to the solenoid valves installed at the source gas inlet and the source air inlet.

  For example, if a temperature change on the oxygen-deficient air side or a mixture of methane or hydrogen on the oxygen-deficient air side is detected and the set level is below the combustion limit, the pressure difference through the ceramic membrane tube is maintained. While reducing the pressure at the same time. Further, the raw material gas supply valve 6 and the raw material air supply valve 8 to this module are closed, and the synthetic gas discharge valve 10 and the oxygen-deficient air discharge valve 12 are closed to supply the synthetic gas / oxygen-deficient air to the recovery device. Feedback to operations that realize predetermined procedures and characteristics, such as stopping the flow, to minimize the spread of abnormalities to other module reactors.

  In the module reactor, gas transportation to an isolation safety relief valve and a buffer tank (not shown) is performed to stop the module reactor safely. After that, it is possible to shift to work such as element replacement or repair in the module reactor.

  In the description of the above embodiment, the pressure difference between the synthesis gas outlet 4 and the oxygen-deficient air outlet 5 is controlled. As another embodiment, the pressure difference between the source gas supply port 2 and the source air supply port 3 can be controlled. The raw material gas supply port 2 and the synthesis gas discharge port 4 are connected to each other through a relatively large gas flow path, and the raw material air supply port 3 and the oxygen-deficient air discharge port 5 are connected to each other through a relatively large air flow path. Because.

  As described above, according to a preferred embodiment of the present invention, the complexity of flow around the oxygen permeable ceramic membrane tube due to buoyancy, convection, etc. can be reduced, and disassembly and assembly can be performed by using a flange-connected cell structure. Since it can be made easy, it is possible to obtain a flow channel structure in consideration of efficient heat flow and exchangeability.

  In addition, by adopting a multi-module reactor structure, if one or a plurality of oxygen permeable ceramic membrane tubes of a module is deteriorated or damaged, it can be replaced or repaired without stopping the entire reactor. A plant capable of efficient operation can be obtained. Moreover, since the plant scale can be easily expanded by increasing the number of oxygen permeable ceramic membrane tubes and reforming catalyst sections of the module, a plant having a scale corresponding to various applications can be obtained.

The top view of 1st Embodiment of the synthesis gas manufacturing apparatus which concerns on this invention. FIG. 2 is a schematic longitudinal sectional view taken along line AA in FIG. 1. FIG. 3 is a perspective view of one of the module reactors in FIG. 2. The longitudinal cross-sectional view of the module reactor of FIG. FIG. 5 is a cross-sectional plan view taken along line B-B in FIG. 4. The typical longitudinal cross-sectional view of 2nd Embodiment of the synthesis gas manufacturing apparatus which concerns on this invention. FIG. 7 is a longitudinal sectional view of one of the module reactors of FIG. 6. The CC sectional view taken on the line of FIG. FIG. 3 is a schematic longitudinal sectional view showing a detector mounting position of the synthesis gas production apparatus of FIG. 2. FIG. 10 is an enlarged vertical cross-sectional view showing a detector mounting state at one of the detector mounting positions in FIG. 9. The block diagram which shows one Embodiment of the measurement and control system of the synthesis gas manufacturing apparatus which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Module reactor, 2 ... Raw material gas supply port, 3 ... Raw material air supply port, 4 ... Syngas discharge port, 5 ... Oxygen-deficient air discharge port, 6 ... Raw material gas supply valve, 7 ... Raw material gas supply source, 8 ... Raw material air supply valve, 9 ... Raw material air supply source, 10 ... Syngas exhaust valve, 11 ... Syngas recovery device, 12 ... Oxygen deficient air exhaust valve, 13 ... Oxygen deficient air recovery device, 15 ... Vessel, 20 ... Kai Catalyst part, 21 ... oxygen permeable ceramic membrane tube, 23-29 ... partition, 32-37 ... outer wall, 40 ... flange, 50 ... air orifice cell, 51 ... oxygen-deficient air discharge cell, 52 ... synthesis gas passage cell, 53 ... Syngas production cell, 54 ... Raw gas orifice cell, 60 ... Top, 61 ... Orifice pipe, 63 ... Bottom, 64 ... Orifice pipe, 70, 71 ... Orifice, 72, 73 ... Pipe, 75 ... Reforming catalyst layer , 8 DESCRIPTION OF SYMBOLS ... Detector attachment part, 81 ... Flange, 82 ... Thermocouple, 83, 83a ... Pressure gauge, 84 ... Component detector, 90 ... Oxygen-deficient air discharge pipe, 110, 111 ... Measuring instrument, 112 ... Inlet side solenoid valve, 113 ... Outlet side solenoid valve, 114 ... Differential pressure gauge

Claims (14)

A synthesis gas production apparatus having a plurality of module reactors,
Each of the module reactors includes at least one oxygen permeable ceramic membrane tube, at least one reforming catalyst portion, and one vessel that commonly accommodates the oxygen permeable ceramic membrane tube and the reforming catalyst portion. A raw material gas supply port for supplying raw material gas into the vessel, a raw material air supply port for supplying raw material air into the vessel, and a synthetic gas discharge port for discharging the synthetic gas generated in the vessel, An oxygen-deficient air outlet for discharging the oxygen-deficient air generated in the vessel,
At least one of a raw material gas supply port, a raw material air supply port, a synthetic gas discharge port, and an oxygen-deficient air outlet of the plurality of module reactors is connected to a common part;
A synthesis gas production apparatus characterized by the above. The synthesis gas production apparatus according to claim 1,
The oxygen permeable ceramic membrane tube includes a ceramic membrane tube having an oxygen permeable function,
The reforming catalyst portion includes a reforming catalyst tube for flowing a product gas generated by a partial oxidation reaction,
In each of the vessels, the ceramic membrane tube and the reforming catalyst unit are regularly arranged,
A synthesis gas production apparatus characterized by the above.   The synthesis gas production apparatus according to claim 1, further comprising a synthesis gas detector for measuring at least one of a component concentration and a temperature of the synthesis gas at each synthesis gas outlet of the module reactor. Gas production equipment.   4. The synthesis gas production apparatus according to claim 3, wherein at least one of the component concentration and the temperature of the synthesis gas detected by the synthesis gas detector of the module reactor exceeds a predetermined range. A syngas production apparatus characterized by comprising means for stopping the operation.   The synthesis gas production apparatus according to claim 1, further comprising an oxygen-deficient air detector that detects at least one of a gas component and a temperature at each oxygen-deficient air outlet of the module reactor. apparatus.   6. The syngas production apparatus according to claim 5, wherein the oxygen-deficient air detector detects at least one gas component of hydrogen, methane, carbon monoxide, and carbon dioxide. Syngas production equipment.   The synthesis gas production apparatus according to claim 5 or 6, wherein when at least one of the component concentration and the temperature of the gas detected by the oxygen-deficient air detector of the module reactor exceeds a predetermined range, the module A synthesis gas production apparatus comprising means for stopping a reaction furnace.   The synthesis gas production apparatus according to claim 4 or 7, wherein the means for stopping the module reactor stops supply of at least one of the source gas and source air of the module reactor. Syngas production equipment. The syngas production apparatus according to claim 8,
A pressure difference detecting means for detecting a pressure difference between a raw material gas supply port and a raw material air supply port of each module reactor or a pressure difference between a synthesis gas discharge port and an oxygen-deficient air discharge port;
A control means for controlling the supply gas source and the air supply stop so that the pressure difference of the module reactor falls within a predetermined range when the supply of the source gas or the source air is stopped;
And further comprising a synthesis gas production apparatus.   The synthesis gas production apparatus according to any one of claims 1 to 9, further comprising means for individually shutting off the module reactor from the common part. A method for operating a syngas production apparatus having a plurality of module reactors,
Each of the module reactors includes at least one oxygen permeable ceramic membrane tube, at least one reforming catalyst portion, and one vessel that commonly accommodates the oxygen permeable ceramic membrane tube and the reforming catalyst portion. A raw material gas supply port for supplying raw material gas into the vessel, a raw material air supply port for supplying raw material air into the vessel, and a synthetic gas discharge port for discharging the synthetic gas generated in the vessel, An oxygen-deficient air outlet for discharging the oxygen-deficient air generated in the vessel,
At least one of the source gas supply port, the source air supply port, the synthesis gas discharge port, and the oxygen-deficient air outlet of the plurality of module reactors is connected to a common part,
Detecting at least one of the component concentration and temperature of the synthesis gas at the synthesis gas outlet of the module reactor, and stopping the module reactor when the component concentration or temperature exceeds a predetermined range;
A method for operating a synthesis gas production apparatus. A method for operating a syngas production apparatus having a plurality of module reactors,
Each of the module reactors includes at least one oxygen permeable ceramic membrane tube, at least one reforming catalyst portion, and one vessel that commonly accommodates the oxygen permeable ceramic membrane tube and the reforming catalyst portion. A raw material gas supply port for supplying raw material gas into the vessel, a raw material air supply port for supplying raw material air into the vessel, and a synthetic gas discharge port for discharging the synthetic gas generated in the vessel, An oxygen-deficient air outlet for discharging the oxygen-deficient air generated in the vessel,
At least one of the source gas supply port, the source air supply port, the synthesis gas discharge port, and the oxygen-deficient air outlet of the plurality of module reactors is connected to a common part,
Detecting at least one of the gas component concentration and temperature at the oxygen-deficient air outlet of the module reactor, and stopping the module reactor when the component concentration or temperature exceeds a predetermined range;
A method for operating a synthesis gas production apparatus.   The method for operating a syngas production apparatus according to claim 11 or 12, wherein the module reactor is shut off from the common portion and stopped, and then the stopped module reactor is repaired to replace the common reactor. A method for operating a syngas production apparatus, comprising: connecting to a part, and then operating all the module reactors connected to the common part. A method for operating a syngas production apparatus having a plurality of module reactors,
Each of the module reactors includes at least one oxygen permeable ceramic membrane tube, at least one reforming catalyst portion, and one vessel that commonly accommodates the oxygen permeable ceramic membrane tube and the reforming catalyst portion. A raw material gas supply port for supplying raw material gas into the vessel, a raw material air supply port for supplying raw material air into the vessel, and a synthetic gas discharge port for discharging the synthetic gas generated in the vessel, An oxygen-deficient air outlet for discharging the oxygen-deficient air generated in the vessel,
At least one of the source gas supply port, the source air supply port, the synthesis gas discharge port, and the oxygen-deficient air outlet of the plurality of module reactors is connected to a common part,
When stopping a part of the plurality of module reactors, the supply of at least one of the source gas and source air of the module reactor to be stopped is stopped,
Detecting a pressure difference between a raw material gas supply port and a raw material air supply port of each module reactor or a pressure difference between a synthesis gas discharge port and an oxygen-deficient air discharge port;
When stopping the supply of the source gas or the source air, controlling the supply gas and source air supply stop so that the pressure difference of the module reactor falls within a predetermined range;
A method for operating a synthesis gas production apparatus.

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