JP6698477B2 - Analytical apparatus, mercury removal method, incinerator system, and program - Google Patents

Description

  The present invention relates to an analyzer that calculates information about the presence of mercury, a method for removing mercury contained in exhaust gas, and an incinerator system that includes an incinerator that burns waste.

Conventionally, an incinerator that incinerates waste, a measurement device that detects mercury contained in the exhaust gas from the incinerator, and a mercury removal device that puts a substance that removes mercury (for example, activated carbon) into the exhaust gas flue Known incinerator systems are provided.
As a measuring device for mercury in exhaust gas, for example, the measuring device disclosed in Patent Document 1 is known. In this measuring device, mercury is detected using the characteristic that zero-valent mercury absorbs ultraviolet light.

JP, 2007-268426, A

  In exhaust gas, mercury is known to exist in the form of 0-valent mercury, 2-valent mercury, and/or particulate mercury, but the exhaust gas is measured by the above-mentioned measuring device without any treatment. Even so, it was believed that no information could be obtained about the presence of divalent mercury. This is because divalent mercury does not interact with ultraviolet light (for example, neither absorbs nor fluoresces light).

  An object of the present invention is to obtain information relating to the abundance ratio of 0-valent mercury and 2-valent mercury in exhaust gas only by detecting 0-valent mercury contained in exhaust gas.

An analysis apparatus according to one aspect of the present invention includes a light source, a detector, and a calculation unit. The light source irradiates the measurement space with measurement light that includes at least a wavelength range that interacts with zero-valent mercury. The detector detects the measurement light that has passed through the measurement space. The calculation unit, based on a time change pattern representing a temporal change in the detection intensity of the measurement light detected by the detector when the measurement target gas is present in the measurement space, a zero valence contained in the measurement target gas. Calculate information related to the proportion of mercury and divalent mercury present.
This makes it possible to obtain information about the abundance ratios of zero-valent mercury and divalent mercury in the measurement target gas simply by measuring the interaction between the zero-valent mercury contained in the measurement target gas and the measurement light as the detection intensity. it can.

  The time change pattern may include a first pattern in which the detection intensity largely changes in a short time. This makes it possible to obtain information relating to the abundance ratios of 0-valent mercury and 2-valent mercury from a sudden change in the detection intensity.

  When it is determined that the time change pattern is the first pattern, the calculation unit may output a first signal indicating that the proportion of zero-valent mercury contained in the measurement target gas is high. This makes it possible to notify the outside that the proportion of zero-valent mercury in the measurement target gas is high.

  The time change pattern may include a second pattern in which a state in which the amount of change in detected intensity from the intensity when zero-valent mercury is not detected is equal to or more than the first threshold value and equal to or less than the second threshold value continues for a predetermined period. As a result, when the amount of change in the detected intensity from the intensity when zero-valent mercury is not detected is equal to or higher than the first threshold value and equal to or lower than the second threshold value for a predetermined period, the detected intensity changes with time to 0-valent mercury and 2 It is possible to obtain information related to the proportion of valence mercury present.

  When it is determined that the time change pattern is the second pattern, the calculation unit may output a second signal indicating that the proportion of divalent mercury contained in the measurement target gas is high. This makes it possible to notify the outside that the proportion of divalent mercury in the measurement target gas is high.

Dust collected in the filter by injecting blowback gas into the filter housing and a probe housing that captures the measurement target gas in which the dust is removed into the measurement space with a filter that collects the dust contained in the measurement target gas And a blowback device for removing.
Thus, the measurement target gas containing almost no dust can be introduced into the measurement space at high speed, and zero-valent mercury contained in the measurement target gas can be detected at high speed. Further, the analyzer can be used even in an environment in which the measurement target gas contains a large amount of dust.

A first flow path for introducing the measurement target gas into the measurement space, and a second flow path having one end branched from the first flow path and the other end connected to the measurement space via a scrubber for removing mercury from the measurement target gas. And a switching unit that alternately switches the first flow path and the second flow path.
At this time, the calculation unit removes mercury from the measurement target gas by passing through the second flow channel and the measurement intensity that is the intensity of the measurement light when the measurement target gas is introduced into the measurement space from the first flow channel. The detected intensity is calculated based on the difference between the reference intensity, which is the intensity of the measurement light when the reference gas thus introduced is introduced into the measurement space.
Thus, by removing the influence of the interference component that interacts with the measurement light in the wavelength range that interacts with the zero-valent mercury, only the interaction of the zero-valent mercury with the measurement light is detected, and the detection intensity of the zero-valent mercury is detected. It can be calculated accurately.

  The measurement target gas may be a gas that has not undergone a reduction process for converting divalent mercury contained in the measurement target gas into zero-valent mercury. Thereby, zero-valent mercury can be detected at high speed.

The calculation unit calculates the detected concentration of zero-valent mercury based on the detected intensity, and based on the concentration-time change pattern representing the temporal change in the detected concentration, the zero-valent mercury and the divalent mercury contained in the gas to be measured. Information related to the proportion of mercury present may be calculated.
This makes it possible to calculate information relating to the abundance ratios of zero-valent mercury and divalent mercury contained in the gas to be measured from the information based on the detected amount of zero-valent mercury based on the existing amount of zero-valent mercury.

A mercury removal method according to another aspect of the present invention includes the following steps.
A step of irradiating the measurement space with measurement light including at least a wavelength range that interacts with zero-valent mercury.
◎The step of detecting the measurement light that has passed through the measurement space.
◎ Based on the time change pattern showing the temporal change in the detection intensity of the measurement light detected when the measurement target gas is present in the measurement space, the zero-valent mercury and the divalent mercury contained in the measurement target gas Calculating information relating to the abundance ratio.
A step of determining a mercury removal method based on information related to the abundance ratios of 0-valent mercury and 2-valent mercury.
With this, only by measuring the interaction between the zero-valent mercury contained in the measurement target gas and the measurement light as the detection intensity, information about the existence ratios of the zero-valent mercury and divalent mercury in the measurement target gas is obtained, The mercury removal method can be determined.

The step of calculating the information relating to the abundance ratio of zero-valent mercury and divalent mercury is included in the measurement target gas when it is determined that the temporal change pattern is the first pattern in which the detection intensity fluctuates greatly in a short time. The step of outputting a first signal indicating that the proportion of zero-valent mercury is high, and the change amount of the detected intensity from the intensity when the time-varying pattern does not detect zero-valent mercury is not less than the first threshold value and not more than the second threshold value. If it is determined that the certain state is the second pattern that continues for a predetermined period, a step of outputting a second signal indicating that the proportion of divalent mercury contained in the measurement target gas is high may be included.
As a result, it is possible to notify the outside of information regarding whether the measurement target gas has a high proportion of zero-valent mercury or a high proportion of divalent mercury.

An incinerator system according to still another aspect of the present invention includes an incinerator, a mercury removing device, and an analyzing device. The incinerator incinerates garbage. The mercury removing device removes mercury contained in the exhaust gas discharged from the incinerator. The analyzer samples and analyzes the exhaust gas.
The analysis device has a light source, a detector, and a calculation unit. The light source irradiates the measurement space with measurement light including at least a wavelength range that interacts with zero-valent mercury. The detector detects the measurement light that has passed through the measurement space. The calculation unit is based on a time change pattern that represents a change over time in the detection intensity of the measurement light detected by the detector when exhaust gas exists in the measurement space. Calculate information related to the proportion of mercury.
This makes it possible to obtain information about the abundance ratios of 0-valent mercury and 2-valent mercury in the exhaust gas only by measuring the interaction between the 0-valent mercury contained in the exhaust gas and the measurement light as the detection intensity.

When the calculation unit determines that the time change pattern is the first pattern in which the detection intensity largely changes in a short time, the calculation unit outputs the first signal indicating that the proportion of zero-valent mercury contained in the measurement target gas is high. Is determined to be the second pattern in which the state in which the amount of change in the detected intensity from the intensity when the zero-valent mercury is not detected is not less than the first threshold value and not more than the second threshold value continues for a predetermined period. Then, a second signal indicating that the proportion of divalent mercury contained in the measurement target gas is high may be output to the mercury removing device.
Thereby, the analysis device can notify the mercury removal device of information regarding whether the proportion of zero-valent mercury or the proportion of divalent mercury in the exhaust gas is high.

A program according to still another aspect of the present invention is a program for causing a computer to execute the following steps.
A step of irradiating the measurement space with measurement light including at least a wavelength range that interacts with zero-valent mercury.
◎Detecting the measurement light that has passed through the measurement space.
◎The presence of zero-valent mercury and divalent mercury contained in the measurement target gas based on a time change pattern that represents a temporal change in the detection intensity of the measurement light detected when the measurement target gas exists in the measurement space. Calculating information related to the percentage.

  Only by detecting zero-valent mercury contained in the exhaust gas, it is possible to obtain information relating to the abundance ratios of zero-valent mercury and divalent mercury in the exhaust gas.

The figure which shows the structure of an incinerator system. The figure which shows the structure of a 1st analyzer. The figure which shows an example of the time change pattern of the detection density of 0 value mercury. The flowchart which shows the mercury removal operation|movement in an incinerator system. The figure which shows typically the determination method of the density time change pattern based on the rising speed of detected density. The figure which shows typically the determination method of the density time change pattern based on the maximum value of detected density. The figure which shows typically the determination method of the concentration time change pattern based on the time until the detected concentration rises from a predetermined value and returns.

1. 1st Embodiment (1) Incinerator system Below, the incinerator system 100 which concerns on 1st Embodiment is demonstrated using FIG. FIG. 1 is a diagram showing a configuration of an incinerator system. The incinerator system 100 is a system for incinerating refuse such as waste, and includes a refuse incinerator 1, a system operation control unit 3, and a first analyzer 5.
In addition, as shown in FIG. 1, the incinerator system 100 includes a second analysis device 7, a third analysis device 9, and a second analysis device 7 in a second exhaust gas pipe R2 that connects a bag filter 12 (described later) and a chimney 14. May be further provided. With these analyzers, the mercury in the exhaust gas discharged from the bag filter 12 and the mercury in the exhaust gas immediately before being discharged from the chimney 14 can be analyzed.

(2) Waste incineration facility The waste incineration facility 1 is a facility that incinerates waste and discharges exhaust gas generated. The refuse incineration facility 1 includes an incinerator 11, a first mercury removing device 13, and a bag filter 12. The incinerator 11 is a furnace for incinerating waste such as waste. The incinerator 11 is connected to a first exhaust gas pipeline R1 for discharging exhaust gas generated by incinerating waste. The bag filter 12 is connected to the end of the first exhaust gas pipe R1 opposite to the side to which the incinerator 11 is connected, removes dust from the exhaust gas, and removes the exhaust gas from the exhaust gas via the second exhaust gas pipe R2. Then, it is discharged from the chimney 14 to the outside.

  The first mercury removing device 13 is connected to the first exhaust gas pipe R1 just before the bag filter 12, and introduces a mercury removing agent (for example, activated carbon or a chelating agent) into the first exhaust gas pipe R1. It is a device for removing mercury in exhaust gas immediately before entering 12. The first mercury removing device 13 determines which kind of mercury removing agent and how to add the mercury removing agent based on the information related to the existence ratios of 0-valent mercury and 2-valent mercury calculated in the first analyzer 5. select.

  With the above configuration, the refuse incineration facility 1 selects an appropriate mercury removal method based on the analysis result of the first analyzer 5 to efficiently remove mercury from exhaust gas and remove mercury and dust. The exhaust gas can be discharged from the chimney 14 to the outside.

In one embodiment, the refuse incineration facility 1 may include the second mercury removing device 15 in the middle of the second exhaust gas pipeline R2. The second mercury removing device 15 is a device that removes mercury in the exhaust gas by passing the exhaust gas through water containing activated carbon or ammonia and/or a chelating agent, for example. By having the second mercury removing device 15, the mercury in the exhaust gas from the incinerator 11 can be removed more reliably.
In one embodiment, the refuse incineration facility 1 may include a temperature reducing tower 16 immediately before the first mercury removing device 13 in the first exhaust gas pipeline R1. The temperature of the exhaust gas from the incinerator 11 can be reduced by including the temperature reducing tower 16.

(3) System operation control unit The system operation control unit 3 is a system having a CPU, a RAM, a ROM, other storage devices, various interfaces, an operation panel, and the like for controlling the refuse incineration facility 1. The system operation control unit 3 controls each component of the refuse incineration facility 1.

(4) First analysis device (4-1) Overview of first analysis device The first analysis device 5 is a device for measuring zero-valent mercury contained in the exhaust gas sampled from the first exhaust gas pipe R1 (an example of a measurement target gas). This is an apparatus for measuring the concentration using the characteristic that zero-valent mercury absorbs ultraviolet light. Specifically, as shown in FIG. 2, the first analysis device 5 includes a probe unit 51, an analyzer unit 53, and a calculation control unit 55. FIG. 2 is a diagram showing the configuration of the first analyzer.

(4-2) Probe Unit The probe unit 51 samples the exhaust gas discharged from the incinerator 11 immediately before the bag filter 12 in the first exhaust gas pipe R1 and introduces it into the analyzer unit 53. The probe unit 51 has a probe housing 511, a probe 513, a primary filter 515, and a blowback tube 517.
The probe housing 511 has an internal space having one end connected to the first pump P1 and the other end connected to the probe 513 which is a hollow tube. The primary filter 515 is arranged on the side close to the probe 513 in the internal space of the probe housing 511.

  When the first pump P1 is operated in the above configuration, the suction causes the exhaust gas flowing in the first exhaust gas conduit R1 to pass through the probe 513 and the primary filter 515 and be taken into the internal space of the probe housing 511. Be done. By allowing the exhaust gas to pass through the primary filter 515, fine particles such as dust can be removed from the exhaust gas, and the exhaust gas containing almost no dust can be introduced into the analyzer unit 53.

The blowback pipe 517 is a hollow pipe member whose one end is arranged immediately before the primary filter 515 and whose other end is connected to a blowback gas supply device GS1 (for example, a supply device for air, nitrogen gas, etc.).
When blowback gas (for example, air, nitrogen gas, etc.) is supplied from the blowback gas supply device GS1, the blowback pipe 517 injects the blowback gas to the primary filter 515 and is collected by the primary filter 515. Remove fine particles such as dust.
The blowback pipe 517 and the blowback gas supply device GS1 are collectively referred to as a "blowback device".

  By having the blowback device, it is possible to prevent the primary filter 515 from being clogged and maintain the exhaust gas sampling flow rate at a high state. As a result, the first analyzer 5 can quickly introduce the exhaust gas containing almost no dust into the measurement space M and detect the zero-valent mercury in the exhaust gas at high speed.

  Since the probe unit 51 has the above-described configuration, the first analyzer 5 can be operated in an environment in which exhaust gas containing a large amount of dust flows, such as exhaust gas discharged from the incinerator 11 (before passing through the bag filter 12). Can be used.

In the present embodiment, the probe unit 51 samples the exhaust gas before the bag filter 12, but the probe unit 51 may be attached to the incinerator 11 to sample the exhaust gas in the incinerator 11, for example.
When the refuse incinerator 1 has the temperature reducing tower 16, the probe unit 51 may be attached between the incinerator 11 and the temperature reducing tower 16 of the first exhaust gas pipeline R1 as shown in FIG. 1. It may be installed between the temperature reducing tower 16 and the bag filter 12.

(4-3) Analyzer Unit The analyzer unit 53 is a device for detecting mercury in the sampled exhaust gas. Specifically, the analyzer unit 53 mainly has a cell 531, a light source 532, and a detector 533. The cell 531 is a member that has the measurement space M and two gas ports that can flow therethrough. One gas port of the cell 531 is connected to the gas port b1 of the first switching valve 534 (described later), and the other gas port is connected to the exhaust pump EP.

With the above configuration, the exhaust gas sampled by the first pump P1 and the second pump P2 arranged between the first pump P1 and the cell 531 of the first flow path FR1 extending from the probe unit 51 is the first It is introduced into the measurement space M through the flow path FR1. After that, the exhaust gas remains in the measurement space M for a predetermined time, and then is exhausted to the outside from the exhaust port E by the suction of the exhaust pump EP. In order to introduce the exhaust gas into the measurement space M at a constant flow rate, the pressure in the measurement space M is adjusted to a predetermined constant pressure.
In this embodiment, two pumps, a first pump P1 and a second pump P2, are provided to increase the sampling flow rate of exhaust gas. Alternatively, the exhaust gas may be sampled from the probe unit 51 by suction of one pump capable of sucking the exhaust gas at a high sampling flow rate.

  A first scrubber SC1 (for example, activated carbon) for removing mercury contained in the exhaust gas discharged from the measurement space M is attached between the exhaust side of the exhaust pump EP and the exhaust port E.

  The light source 532 is attached to one end of the cell 531 and measures the measurement light LM including at least a wavelength range (for example, a predetermined range of wavelength around 253 nm) that is absorbed (an example of interaction) by zero-valent mercury. It is, for example, a mercury lamp, a xenon lamp, an LED or a laser diode (LD) capable of generating light in the ultraviolet region, which irradiates M.

  The detector 533 is a photodiode or a photomultiplier tube that is attached to the cell 531 so as to face the light source 532 and that detects the measurement light LM that has passed through the measurement space M, for example, that is capable of detecting light in the ultraviolet region.

The analyzer unit 53 of the present embodiment further includes a first switching valve 534 (an example of a switching unit) having three gas ports a1, b1, and c1, one end of which branches from the first flow path FR1 and the other end of which extends. The second flow path FR2 connected to the gas port c1 of the first switching valve.
The gas port a1 of the first switching valve 534 is connected to the first flow path, and the gas port b1 is connected to the cell 531 (measurement space M). The first switching valve 534 switches between the gas port a1 and the gas port b1 or the gas port c1 and the gas port b1 according to a command from the arithmetic control unit 55.

The second flow passage FR2 has a second scrubber SC2 having one end connected to the side branched from the first flow passage FR1 and the other end connected to the gas port c1. The second scrubber SC2 is, for example, a column filled with diatomaceous earth impregnated with gold. In addition, the second scrubber SC2 is heated to a predetermined temperature so as not to capture an interference component (for example, SO ₂ , hydrocarbon, etc.) other than zero-valent mercury that interacts with light in the wavelength range absorbed by zero-valent mercury. I have to.

When the first switching valve 534 circulates the gas port c1 and the gas port b1, the exhaust gas passes from the second flow passage FR2 to the second scrubber SC2, passes through the gas port c1 and the gas port b1, and enters the measurement space M. be introduced.
The exhaust gas introduced into the measurement space M via the second flow path FR2 is in a state where interference components other than mercury contained in the exhaust gas before passing through the second scrubber SC2 remain. Therefore, the exhaust gas that has passed through the second flow path FR2 will be referred to as a “reference gas” that is a gas in which only mercury has been removed.

  On the other hand, when the gas ports a1 and b1 are circulated, the exhaust gas is introduced into the measurement space M without passing through the scrubber.

  When mercury is detected by the analyzer unit 53 having the second flow path FR2, the first switching valve 534 allows the gas port a1 and the gas port b1 to flow at a predetermined cycle (for example, 1 Hz), or The exhaust gas and the reference gas are alternately introduced into the measurement space M by switching whether the gas port c1 and the gas port b1 are circulated (fluid modulation method).

In one embodiment, the analyzer unit 53 branches from a flow rate adjusting valve 535 (for example, a needle valve) that adjusts the sampling flow rate of the exhaust gas from the probe unit 51, and from the outlet side of the second pump P2 of the first flow path FR1. And a third flow path FR3 that bypasses the cell 531 and is connected to the exhaust port E.
The flow rate adjusting valve 535 can adjust the sampling flow rate of the exhaust gas from the probe unit 51. Further, by the third flow passage FR3, a part of the sampled exhaust gas can be introduced into the third flow passage FR3 to bypass the cell 531. As a result, it is possible to avoid introducing excessive exhaust gas into the cell 531 while sampling the exhaust gas at high speed.

  The third flow passage FR3 has a third scrubber SC3 on the side closer to the exhaust port E. Thereby, the mercury contained in the exhaust gas that bypassed the cell 531 can be removed before being discharged. Further, the third flow passage FR3 may have a flow meter FM in the vicinity of the branch point from the first flow passage FR1. Thereby, the flow rate of the exhaust gas that bypasses the cell 531 can be monitored.

  In one embodiment, the analyzer unit 53 has three gas ports a2, b2, and c2 and passes the gas port a2 and the gas port b2, or the gas port c2 and the gas port b2. It may have the 2nd switching valve 536 which switches, and the calibration gas supply apparatus GS2 connected to the gas port c2. The calibration of the analyzer unit 53 can be performed by introducing the calibration gas from the calibration gas supply device GS2 with the second switching valve 536 opening the gas port c2 and the gas port b2.

  In one embodiment, the analyzer unit 53 may arrange the filter 537 between the cell 531 of the first flow path FR1 and the second pump P2. As a result, fine particles such as dust that could not be captured by the primary filter 515 can be further captured by the filter 537, and a more dust-free exhaust gas can be introduced into the measurement space M.

(4-4) Arithmetic Control Unit The arithmetic control unit 55 (an example of an arithmetic unit) has a CPU, a RAM, a ROM, other storage devices, various interfaces, and controls each component of the first analyzer 5. It is a computer system that processes a signal input from the analyzer unit 53.
As information processing of the signal input from the analyzer unit 53, the arithmetic control unit 55 introduces the exhaust gas into the measurement space M when the exhaust gas and the reference gas are alternately introduced into the measurement space M at a predetermined cycle. Difference between the measurement intensity that is the intensity of the measurement light acquired while the reference gas is the intensity of the measurement light LM that is acquired when the reference gas is introduced into the measurement space M (for example, these two The detection intensity of the measurement light LM affected by the presence of zero-valent mercury is calculated based on the signal difference or ratio). Then, the detected concentration of zero-valent mercury is calculated based on the detected intensity. As a result, it is possible to remove the influence of the above-mentioned interference component contained in the exhaust gas on the detection concentration (detection intensity of the measurement light LM) and detect only the interaction (absorption) of zero-valent mercury with respect to the measurement light LM. As a result, the detected concentration of zero-valent mercury can be calculated accurately.

Further, the arithmetic control unit 55 calculates information related to the existing ratios of 0-valent mercury and 2-valent mercury contained in the exhaust gas, based on the calculated concentration-time change pattern of the detected concentration of 0-valent mercury. A method of calculating the information from the concentration temporal change pattern of the detected concentration of zero-valent mercury will be described in detail later.
Various information processing executed by the arithmetic control unit 55 may be realized by a program stored in the RAM, the ROM, and/or the storage device.

As described above, in the first analyzer 5 of the present embodiment, the scrubber is not provided in the first flow path FR1 from the probe unit 51. That is, the exhaust gas introduced into the measurement space M for detecting mercury does not go through a reduction process for converting divalent mercury contained in the exhaust gas into zerovalent mercury.
By not providing the scrubber in the first flow path FR1 (and/or the probe unit 51), the flow rate when introducing the exhaust gas into the measurement space M can be increased. As a result, zero-valent mercury in exhaust gas can be detected at high speed.

  In one embodiment, as shown in FIG. 2, the first analyzer 5 may be provided with a water removing unit 57 in the first flow path FR1. The water removing unit 57 is composed of a drain separator and an electronic cooler (neither is shown), and can remove water contained in the exhaust gas and introduce it into the analyzer unit 53.

(5) Concentration Time Change Pattern of Detected Concentration of Zero-valent Mercury Hereinafter, the result of detecting the zero-valent mercury by sampling the exhaust gas from the first exhaust gas pipe R1 by the first analyzer 5 will be described.
In the first analyzer 5 described above, exhaust gas was continuously sampled from the first exhaust gas pipe R1 for a predetermined time, and the detection concentration of 0-valent mercury in the exhaust gas was continuously measured. As a result, 0-valent mercury was detected. It was found that the concentration exhibits two types of characteristic temporal changes (concentration time change pattern) as shown in FIG. FIG. 3 is a diagram showing an example of a temporal change pattern of the detected concentration of zero-valent mercury.
As shown in FIG. 3, the concentration-time change pattern in the present embodiment is a time-dependent change in the detected concentration of zero-valent mercury that occurs within a predetermined time range (for example, within a time range of several seconds to several tens of minutes). is there.

  The first type is a pattern (referred to as a first pattern) in which the detected concentration largely changes in a short time, as shown in FIG. As a result of continuously measuring the concentrations of other components in the exhaust gas together with the concentration of zero-valent mercury, when the first pattern was generated, a drastic change in the concentration of carbon monoxide was also observed. From this, the first pattern indicates that the incinerator 11 is in an incomplete combustion state.

  When exhaust gas is in a reducing atmosphere (a state containing a reducing component) due to incomplete combustion in the incinerator 11, divalent mercury (mercury compound) is easily reduced to zero-valent mercury, and generation of divalent mercury is also suppressed. To be done. Generally, the proportion of zero-valent mercury and divalent mercury in the exhaust gas discharged from the incinerator 11 is larger than that of divalent mercury (for example, zero-valent mercury:divalent mercury=1. It is known that the ratio of zero-valent mercury increases in the exhaust gas in the reducing atmosphere (for example, zero-valent mercury:divalent mercury=1:1). Therefore, the first pattern is an index indicating that the proportion of zero-valent mercury in the exhaust gas is high.

The second type is, as shown in FIG. 3B, a pattern (referred to as a second pattern) in which the detected concentration exceeds a predetermined threshold value and remains small for a predetermined period. When the second pattern was generated, generation of carbon monocarbide was not observed. Therefore, the second pattern shows that the incinerator 11 is in the complete combustion state and the exhaust gas is in an oxidizing atmosphere (for example, containing a large amount of SO ₂ and HCl).
In the exhaust gas in an oxidizing atmosphere, the existing proportions of zero-valent mercury and divalent mercury in the exhaust gas are such that the above-mentioned generally known proportion of divalent mercury is higher than that of zero-valent mercury (for example, zero-valent mercury). The ratio is mercury:divalent mercury=1:9). Therefore, the second pattern is an index indicating that the proportion of divalent mercury in the exhaust gas is high.

  As described above, the presence of zero-valent mercury and divalent mercury contained in the exhaust gas is detected only by detecting the temporal change in the detected concentration of zero-valent mercury (or the absorption intensity of the measured light LM) using the measurement light LM. You can get information related to the ratio. This is the first time that the knowledge that information relating to the abundance ratios of 0-valent mercury and 2-valent mercury can be obtained only by detecting 0-valent mercury is obtained.

(6) Mercury Removal Operation in Incinerator System Next, the mercury removal operation in the incinerator system 100 using the detection result of zero-valent mercury of the first analyzer will be described with reference to FIG. FIG. 4 is a flowchart showing a mercury removing operation in the incinerator system.
During operation of the refuse incineration facility 1, the system arithmetic control unit 3 instructs the first analyzer 5 to perform mercury analysis at each stage of the refuse incineration facility 1.

  The arithmetic control unit 55 of the first analyzer 5 which receives the command operates the first pump P1, the second pump P2, and the exhaust pump EP to sample the exhaust gas from the probe unit 51. After that, the arithmetic control unit 55 alternately introduces the exhaust gas and the reference gas into the measurement space M, and irradiates the measurement space LM with the measurement light LM from the light source 532. Furthermore, the detected concentration of zero-valent mercury is calculated based on the measurement intensity of the measurement light LM when the exhaust gas exists in the measurement space M and the reference intensity of the measurement light LM when the reference gas exists in the measurement space. (Steps S1 to S4).

  Next, the arithmetic control unit 55 confirms the temporal change in the detected concentration of 0-valent mercury for each predetermined time range (for example, a time range of several seconds to several tens of minutes) and confirms the two zero values described above. Information relating to the abundance ratios of 0-valent mercury and 2-valent mercury contained in the exhaust gas is calculated by determining which pattern the concentration-time change pattern of the detected concentration of valent mercury is (step S5). As for which pattern the density temporal change pattern of the detected density is, the determination method by the following three methods can be mentioned, for example.

The first is the rising speed of the detected concentration of zero-valent mercury (for example, the data for a predetermined period from the time when the portion surrounded by the dotted line of the concentration time change pattern of FIG. 5A (a predetermined value (Cs in FIG. 5A) is exceeded). This is a method of determining that the first pattern is generated when the inclination of the straight line of) is equal to or larger than a predetermined value, and the second pattern is generated when the inclination is smaller than the predetermined value. The rising speed of the detected concentration can be calculated, for example, as a slope of a straight line formula obtained by data fitting a plurality of detected concentrations calculated from the past (for example, 5 seconds before) to the present.
This makes it possible to determine which of the 0-valent mercury and the 2-valent mercury is higher at an early stage after detecting the generation of 0-valent mercury and/or divalent mercury.

  Secondly, as shown in FIG. 5B, if the maximum value (peak value) of the detected concentration is equal to or higher than a predetermined value (Cs1 in FIG. 5B), the first pattern is generated, and the maximum value of the detected concentration is the predetermined value. It is a method of determining that the second pattern has occurred, if it is smaller than the value of, but is equal to or larger than a predetermined threshold value (Cs2 in FIG. 5B). The maximum value of the detected concentration can be calculated as, for example, the maximum value of the detected concentration during the period from the increasing tendency of the detected concentration to the decreasing tendency (via a constant value) (for example, Cm and Cm′ in FIG. 5B). ).

  In this case, among the plurality of detected densities from the time when the detected densities tend to increase (after passing a certain value) to the tendency to decrease, detected densities that become noise components (for example, a tendency that a plurality of detected densities have , A decreasing tendency, or a detected density) that largely deviates from the tendency of being maintained at a constant value), the detected density that is the noise component is not used for determining whether or not it is the maximum value.

  In one embodiment, the arithmetic and control unit 55 constantly monitors the detected concentration, and the maximum value of the detected concentration generated during the time when the detected concentration changes from the increasing tendency to the decreasing tendency (through a constant value) is a predetermined value. If the value is equal to or larger than the value, it may be determined that the first pattern has occurred, and if the maximum value is smaller than the predetermined value but equal to or larger than the predetermined threshold, it may be determined that the second pattern has occurred.

  The peak value of the first pattern becomes higher than the peak value of the second pattern by determining whether the density temporal change pattern of the detected density is the first pattern or the second pattern based on the maximum value of the detected density. By using the characteristics (since the proportion of zero-valent mercury is high when the first pattern is generated), it is possible to determine which of the zero-valent mercury and the divalent mercury is higher.

Thirdly, as shown in FIG. 5C, after the detected concentration becomes equal to or higher than a predetermined value (for example, half of the maximum value of the detected concentration) (Ca, Ca′ in FIG. 5C), it returns to the predetermined value. This is a method of determining that the first pattern has occurred when the time (t1, t2 in FIG. 5) before the arrival comes to a predetermined time or less and the second pattern has occurred when the time is equal to or more than the predetermined time.
This makes it possible to determine which of 0-valent mercury and divalent mercury is higher, based on the length of the change in the concentration-time change pattern.

As a result of the above determination, when it is determined that the concentration temporal change pattern of the detected concentration of zero-valent mercury is the first pattern (in the case of the “first pattern” in step S4), the calculation control unit 55 is included in the exhaust gas. A first signal indicating that the proportion of zero-valent mercury is high is output to the first mercury removing device 13 via the system operation control unit 3 (step S6).
The first mercury removing device 13, which has received the first signal, inputs, for example, activated carbon impregnated with halogen into the first exhaust gas pipeline R1 in order to more efficiently remove zero-valent mercury in the exhaust gas (step S7). ).

On the other hand, when it is determined that the concentration temporal change pattern of the detected concentration of zero-valent mercury is the second pattern (in the case of the “second pattern” in step S4), the calculation control unit 55 determines that the proportion of the divalent mercury in the exhaust gas is The second signal indicating the high level is output to the first mercury removing device 13 (step S8).
The first mercury removing apparatus 13, which has received the second signal, inputs more activated carbon into the first exhaust gas pipeline R1, for example, in order to remove the divalent mercury in the exhaust gas more efficiently (step S9).

  By executing the above steps S1 to S9, the first mercury removing apparatus 13 has a high signal (first signal) indicating that the proportion of zero-valent mercury contained in the exhaust gas is high, or the proportion of divalent mercury is high. Of the signal (second signal) indicating that the removal method for efficiently removing zero-valent mercury or the removal method for efficiently removing divalent mercury is determined. It can be decided early after the outbreak. As a result, mercury can be more reliably removed from the exhaust gas.

  The above steps S1 to S9 are continuously executed while the incinerator system 100 is in operation. Further, when the incinerator system 100 is stopped for maintenance or the like, the execution of steps S1 to S9 may be stopped.

2. Other Embodiments One embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment, and various modifications can be made without departing from the gist of the invention. In particular, the plurality of embodiments and modifications described in the present specification can be arbitrarily combined as needed.
(A) For example, no zero-valent mercury is detected by the first analyzer 5 (or a very small amount of zero-valent mercury cannot be detected due to the set range), while 0 is not detected by the second analyzer 7 or the third analyzer 9. If valent mercury is detected, it may be determined that the proportion of divalent mercury is extremely high.

  (B) The first signal and the second signal from the first analyzer 5 may be input to the second mercury removing device 15. As a result, the second mercury removing apparatus 15 accurately grasps the generation timing of mercury and whether the proportion of zero-valent mercury in the exhaust gas is high or the amount of divalent mercury is high, and removes necessary mercury as necessary. Agents can be introduced.

  (C) Since 0-valent mercury has fluorescence of ultraviolet light, the fluorescence of ultraviolet light of 0-valent mercury is detected in the first analyzer 5 (second analyzer 7, third analyzer 9). Zero-valent mercury may be analyzed based on the intensity of the fluorescence.

  (D) The first analyzer 5 is, for example, zero-valent mercury and/or 2 in order to remove mercury in the exhaust gas from a high temperature process plant (for example, a plant having a combustion process such as a petroleum refining process). It may also be used for the purpose of detecting valent mercury at high speed.

  (E) In the first analyzer 5, the calculation control unit 55 calculates the zero-valent mercury and the two-valent mercury based on the temporal change pattern of the detection intensity of the measurement light LM without calculating the detected concentration of the zero-valent mercury. The information related to the existence ratio of may be calculated.

In this case, the temporal change pattern of the detection intensity when the first pattern is obtained as the concentration temporal change pattern is either the detection intensity largely decreases or increases in a short time. Whether the detection intensity decreases or increases due to the detection of zero-valent mercury depends on how to take the difference between the background intensity and the measured intensity.
On the other hand, in the time change pattern of the detection intensity when the second pattern is obtained as the concentration time change pattern, the change amount of the detection intensity from the intensity when zero-valent mercury is not detected is not less than the first threshold value and not more than the second threshold value ( That is, a pattern in which the change amount of the detected intensity is within a predetermined range smaller than that in the first pattern) continues for a predetermined period.

  Based on the fact that the temporal change pattern of the detected intensity indicates two types of patterns as described above, the arithmetic control unit 55 uses the same method as that described in the first embodiment to perform the temporal change pattern of the detected intensity. It is possible to determine which pattern is.

  The calculation control unit 55 calculates the information at a higher speed by calculating the information related to the existence ratio of the 0-valent mercury and the 2-valent mercury based on the temporal change pattern of the detected intensity without calculating the detected concentration. it can.

  INDUSTRIAL APPLICABILITY The present invention can be widely applied to an analyzer that calculates information regarding the presence of mercury, and an incinerator system that includes an incinerator that burns garbage.

100 Incinerator System 1 Waste Incinerator 11 Incinerator 12 Bag Filter 13 First Mercury Removal Device 14 Chimney 15 Second Mercury Removal Device 16 Dehumidification Tower 3 System Calculation Control Unit 5 First Analysis Device 51 Probe Unit 511 Probe Housing 513 Probe 515 Primary filter 517 Blowback pipe GS1 Blowback gas supply device 53 Analyzer unit 531 Cell 532 Light source 533 Detector 534 First switching valve 535 Flow rate adjusting valve 536 Second switching valve 537 Filter EP Exhaust pump FR1 First flow path FR2 Second flow path FR3 Third flow path GS2 Calibration gas supply device LM Measuring light M Measuring space P1 First pump P2 Second pump R1 First exhaust gas line R2 Second exhaust gas line SC1 First scrubber SC2 Second scrubber SC3 3 Scrubber E Exhaust port FM Flowmeters a1, b1, c1, a2, b2, c2 Gas port 55 Calculation control unit 57 Moisture removal unit 7 Second analysis device 9 Third analysis device

Claims (13)

A light source for irradiating a measurement space with measurement light including at least a wavelength range that interacts with zero-valent mercury,
A detector for detecting the measurement light passing through the measurement space,
Based on a temporal change pattern that represents a temporal change in the detection intensity of the measurement light detected by the detector when a measurement target gas is present in the measurement space, a zero valence contained in the measurement target gas An arithmetic unit that calculates information related to the abundance ratios of mercury and divalent mercury,
Equipped with
The time change pattern is
A first pattern in which the detection intensity largely fluctuates in a short time, a rising speed of the detection intensity is a first value or more, or a peak value of the detection intensity is a second value or more, and/or
A state in which the amount of change in the detected intensity from the intensity when zero-valent mercury is not detected is equal to or higher than the first threshold value and equal to or lower than the second threshold value continues for a predetermined period, and the rising speed of the detected intensity is higher than the first value. A small value, or a second pattern in which the peak value of the detected intensity is less than the second value,
Analytical apparatus including . When the time variation pattern is determined to be the first pattern, the arithmetic unit outputs a first signal indicating that the percentage of zero-valent mercury contained in the measurement target gas is high, according to claim 1 Analyzer. When the time variation pattern is determined to be the second pattern, the arithmetic unit outputs a second signal indicating that the percentage of divalent mercury contained in the measurement target gas is high, according to claim 1 or 2 The analyzer according to 1. A probe housing having a filter for collecting dust contained in the measurement target gas, and incorporating the measurement target gas from which the dust has been removed into the measurement space,
By injecting blowback gas to the filter, a blowback device for removing the dust collected in the filter,
The analyzer according to claim 1, further comprising: A first flow path for introducing the measurement target gas into the measurement space,
A second flow path, one end of which branches from the first flow path and the other end of which is connected to the measurement space via a scrubber that removes mercury from the measurement target gas;
A switching unit that alternately switches the first flow path and the second flow path;
Further equipped with,
The calculation unit is a measurement intensity that is the intensity of the measurement light when the measurement target gas is introduced into the measurement space from the first flow path, and the measurement target gas by passing through the second flow path. From the reference intensity, which is the intensity of the measurement light when the reference gas from which mercury has been removed is introduced into the measurement space, and the detection intensity is calculated based on the difference between
Analysis device according to any one of claims 1 to 4. The measurement target gas, the divalent mercury contained in the measurement target gas is a gas that does not undergo a reduction process of converting the zero-valent mercury analyzer according to claim 1. The calculation unit calculates a detected concentration of zero-valent mercury based on the detected intensity, and based on a concentration-time change pattern representing a temporal change in the detected concentration, zero-valent mercury contained in the measurement target gas. The analyzer according to any one of claims 1 to 6 , which calculates information relating to the presence ratio of divalent mercury. Irradiating the measurement space with measurement light including at least a wavelength range that interacts with zero-valent mercury,
Detecting the measurement light passed through the measurement space,
Zero-valent mercury and divalent mercury contained in the measurement target gas based on a time change pattern representing a temporal change in the detection intensity of the measurement light detected when the measurement target gas exists in the measurement space. Calculating the information related to the existence ratio of
Determining a mercury removal method based on information related to the abundance ratios of 0-valent mercury and 2-valent mercury;
Only including,
The time change pattern is
A first pattern in which the detection intensity largely fluctuates in a short time, a rising speed of the detection intensity is a first value or more, or a peak value of the detection intensity is a second value or more, and/or
A state in which the amount of change in the detected intensity from the intensity when zero-valent mercury is not detected is equal to or higher than the first threshold value and equal to or lower than the second threshold value continues for a predetermined period, and the rising speed of the detected intensity is higher than the first value. A small value, or a second pattern in which the peak value of the detected intensity is less than the second value,
Method of removing mercury containing . The step of calculating the information relating to the abundance ratio of the 0-valent mercury and the 2-valent mercury is
When the time change pattern is determined to be the first pattern, outputting a first signal indicating that the proportion of zero-valent mercury contained in the measurement target gas is high,
When the time variation pattern is determined to be the second pattern, and outputting a second signal indicating that the percentage of divalent mercury contained in the measurement target gas is high,
The method for removing mercury according to claim 8 , which comprises: An incinerator that incinerates garbage,
A mercury removing device for removing mercury contained in the exhaust gas discharged from the incinerator,
An analyzer for sampling and analyzing the exhaust gas,
The analyzer is
A light source for irradiating a measurement space with measurement light including at least a wavelength range that interacts with zero-valent mercury,
A detector for detecting the measurement light passing through the measurement space,
Zero-valent mercury and 2 contained in the exhaust gas are included based on a time change pattern indicating a time change of the detection intensity of the measurement light detected by the detector when the exhaust gas is present in the measurement space. A calculation unit that calculates information related to the existence ratio with valence mercury,
Have a,
The time change pattern is
A first pattern in which the detection intensity largely fluctuates in a short time, a rising speed of the detection intensity is a first value or more, or a peak value of the detection intensity is a second value or more, and/or
A state in which the amount of change in the detected intensity from the intensity when zero-valent mercury is not detected is equal to or higher than the first threshold value and equal to or lower than the second threshold value continues for a predetermined period, and the rising speed of the detected intensity is higher than the first value. A small value, or a second pattern in which the peak value of the detected intensity is less than the second value,
Incinerator system including . The arithmetic unit is
When the time variation pattern is determined to be the first pattern, and outputs a first signal indicating that the percentage of zero-valent mercury contained in exhaust gas is high the mercury removal device,
When the time variation pattern is determined to be the second pattern, and outputs a second signal indicating that the percentage of divalent mercury contained in exhaust gas is high the mercury removal device,
The incinerator system according to claim 10 . A mercury removing device that removes mercury contained in the gas to be measured,
An analyzer for sampling and analyzing the measurement target gas;
The analyzer is
A light source for irradiating a measurement space with measurement light including at least a wavelength range that interacts with zero-valent mercury,
A detector for detecting the measurement light passing through the measurement space,
Have
The mercury removing device measures the activated carbon based on a time change pattern representing a time change of the detection intensity of the measurement light detected by the detector when the measurement target gas is present in the measurement space. Charge the target gas,
The time change pattern is
A first pattern in which the detection intensity largely fluctuates in a short time, a rising speed of the detection intensity is a first value or more, or a peak value of the detection intensity is a second value or more, and/or
A state in which the amount of change in the detected intensity from the intensity when zero-valent mercury is not detected is equal to or higher than the first threshold value and equal to or lower than the second threshold value continues for a predetermined period, and the rising speed of the detected intensity is higher than the first value. A small value, or a second pattern in which the peak value of the detected intensity is less than the second value,
Incinerator system including. Irradiating the measurement space with measurement light including at least a wavelength range that interacts with zero-valent mercury,
Detecting the measurement light passed through the measurement space,
Zero-valent mercury and divalent mercury contained in the measurement target gas based on a time change pattern representing a temporal change in the detection intensity of the measurement light detected when the measurement target gas exists in the measurement space. Calculating the information related to the existence ratio of
A program for causing a computer to execute ,
The time change pattern is
A first pattern in which the detection intensity largely fluctuates in a short time, a rising speed of the detection intensity is a first value or more, or a peak value of the detection intensity is a second value or more, and/or
A state in which the amount of change in the detected intensity from the intensity when zero-valent mercury is not detected is equal to or higher than the first threshold value and equal to or lower than the second threshold value continues for a predetermined period, and the rising speed of the detected intensity is higher than the first value. A small value, or a second pattern in which the peak value of the detected intensity is less than the second value,
Programs that include .

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