JP3244415B2 - Conversion efficiency inspection device in the converter from sulfur oxides to sulfur dioxide gas - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inspection method and an inspection apparatus for converting a sulfur oxide to a sulfur dioxide gas, and more particularly to a method for converting the sulfur oxide to a sulfur dioxide gas which can accurately inspect the conversion efficiency. The present invention relates to an inspection device for a conversion device.

[0002]

2. Description of the Related Art Sulfur contained in light oil as fuel for a diesel engine of a vehicle or the like is discharged from the diesel engine as sulfur dioxide SO ₂ . In the development and evaluation of diesel oxidation catalysts corresponding to the strengthening of the diesel exhaust gas regulations, measures to reduce sulfuric acid mist which SO _x and water in the diesel exhaust gas is produced by reacting with the catalyst of the exhaust system is important. Therefore, the reaction of the SO _x containing sulfuric acid mist, recent SO _x for the generation and analysis
Analyzers have been developed and used. Note that this SO _x
The analyzer measures the concentration of SO _x by converting SO _x into SO ₂ and detecting the concentration of SO ₂ .
Therefore the calibration of the SO _x analyzer, to generate a predetermined concentration of the SO _x, it is necessary to measure the concentration led to the SO _x to SO _x analyzer.

[0003]

[SUMMARY OF THE INVENTION However, in the conventional example described above, generating the concentration of the SO _x is because it is calculated on the assumption that the efficiency of the catalyst in the generator is 100%, of the long-term occurs concentration of the sO _x when the catalyst is deteriorated becomes a problem because drops. In this case, the SO _x generation concentration does not match the indication of the SO _x analyzer, but the cause is SO _x
It is difficult to determine whether the conversion efficiency of SO _x to SO ₂ is deteriorated on the analyzer side or the catalyst is deteriorated on the SO _x generator side. In order to maintain the accuracy of the SO _x analyzer even if there is catalyst deterioration in the SO _x generator, the SO _x
It is necessary to control the accuracy of the conversion efficiency of the converter to O ₂ .
This conversion efficiency needs to be regularly managed to be always 90% or more. However, if the activated carbon inside the conversion device is deteriorated, the conversion efficiency is reduced.
There was a disadvantage that the measurement of _x concentration could not be performed. Therefore, an object of the present invention is to eliminate the above-mentioned disadvantages of the conventional example and accurately measure the conversion efficiency from SO _x to SO ₂ .
It is to provide a device that can .

[0004]

Means for Solving the Problems In order to solve the above problems, the first invention of the present application is directed to a method for converting sulfur dioxide gas to sulfur dioxide.
A sulfur oxide generator for producing yellow oxide, and the sulfur acid
Sulfur oxides located downstream of the chloride generator
A conversion device for converting to gas, and a conversion device disposed downstream of the conversion device.
A detector for detecting the concentration of sulfur dioxide gas;
Supply the gas on the outlet side of the oxide generator to the converter
By the SO _x mode line to the processing, the conversion device
Turn off converter to switch to SO ₂ mode line to pass
A conversion valve for detecting the conversion efficiency of the conversion device.
Is a conversion efficiency inspection device,
Mixing gas that is a mixture of yellow gas and gas with moisture added to oxygen
For supplying and treating the sulfur oxides to the sulfur oxide generator
Bypass the mode line and the sulfur oxide generator
Switching valve to switch to bypass mode line
A conversion efficiency inspection apparatus characterized in that:

[0005] With the configuration of the first invention, the conversion device
Water to sulfur dioxide gas and oxygen gas
Reacts with the mixed gas
And the same concentration of sulfur dioxide as the sulfur dioxide gas.
Switchable between supplying sulfur gas to converter
The sulfur of the converter according to claim 1
Testing the conversion efficiency of oxides to sulfur dioxide gas
Can be.

Further, a second aspect of the present invention is a sulfur dioxide
A sulfur oxide generation device for generating sulfur oxide from
Sulfur oxide is disposed downstream of the sulfur oxide generator.
A conversion device for converting to sulfur oxide gas, and a downstream of the conversion device
A detector for detecting the concentration of sulfur dioxide gas ,
The gas on the outlet side of the sulfur oxide generation device is supplied to the conversion device.
And SO _x mode line to be processed is supplied to the location, the conversion instrumentation
Variable switching to the SO ₂ mode line to bypass location
And a conversion device switching valve.
A conversion efficiency inspection device for inspecting the efficiency
Mix sulfur dioxide gas with oxygen-added gas
Mixed gas passed through the sulfur oxide generator
A catalyst mode line to be supplied to the converter,
Over the outside of the converter through the oxide generator
First switching bar for switching to the line to be supplied to the flow outlet
And the mixed gas with the sulfur oxide generator.
Bypass mode for bypassing and supplying to the converter side
Line and bypassing the sulfur oxide generator
A line to supply to the overflow outlet outside the converter
And a second switching valve for switching to
Is a conversion efficiency inspection device.

[0007] According to the configuration of the second aspect, the first aspect.
Supply of sulfur dioxide gas to the converter
Sulfur oxides are generated as described above even when supplying
Supply sulfur dioxide gas to the converter.
From the state to the state to supply sulfur oxides to the converter
When it comes to a stable state in a short time.

[0008]

Next, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is an explanatory diagram of the first embodiment. Note that the first embodiment corresponds to claims 1 and 2. In FIG. 1, the input side of the analyzer 30 is connected to the output side of the conversion efficiency checker 10. The conversion efficiency checker 10 checks the conversion efficiency of the conversion device 32 in the analyzer 30 from the sulfur oxide SO _x (including sulfuric acid mist but not including sulfur dioxide gas (SO ₂ )) to SO ₂ , Its main parts are first and second filters 11, 14, first and second flow control valves 12, 15,
It comprises first and second mass flow controllers 13, 16, a bubbler 17, a switching valve 18, a heating furnace 19, a pipe 20, and heating pipes 20a, 20b, 20c. The first filter 11 removes dust and the like of the supplied SO ₂ . The first flow rate adjustment valve 12 roughly adjusts the flow rate of SO ₂ , and the first mass flow controller 13 precisely adjusts the flow rate of SO ₂ .

The second filter 14 removes dust and the like from the supplied oxygen gas (O ₂ ). The second flow control valve 15 roughly adjusts the flow rate of O ₂ , and the second mass flow controller 16 precisely adjusts the flow rate of O ₂ . The bubbler 17 saturates the output O ₂ of the mass flow controller 16 with moisture (H ₂ O). The output side (downstream side) of the bubbler 17
The heating pipes 20a, 20b, and 20c (the pipe 2 in FIG. 1)
(A solid line indicating 0 is sandwiched between broken lines). The heating pipe 20b is for bypassing the heating furnace 19, the heating pipe 20c is for connecting a trapper 33 to be described later so as to bypass the converter 32, and the heating pipe 20a is for all but the heating pipes 20a and 20b. Heating pipe. Heating pipes 20a, 20b, 20
c is a heater in which a heater is provided outside a pipe of stainless steel or the like via an insulator, and when heated by the heater, water (water vapor) contained in the gas in the heating pipes 20a, 20b, and 20c is removed. It is possible to prevent the temperature of the sulfuric acid mist from dropping and adhering to the inner wall of the pipe. The switching valve 18 is connected to the output S of the first mass flow controller 13.
The supply destination of the mixed gas of O ₂ and the output gas of the bubbler 17 is switched to the heating furnace 19 in the catalyst mode, and to the heating pipe 20 b bypassing the heating furnace 19 in the bypass mode.

The heating furnace 19 has an oxidation catalyst 19a inside and a heating means 19b (for example, a heater) outside,
While heating the mixture gas supplied from the switching valve 18 by the heating means 19b, oxidized by contact with the oxidation catalyst 19a, it is intended to generate a predetermined concentration of SO _x. Reference numeral 21 denotes a gas outlet of the heating furnace 19 or a heating pipe 20 b that bypasses the heating furnace 19, and an overflow gas outlet 22 is connected to the gas outlet 21,
The gas pressure is adjusted. The analyzer 30 includes a pre-processing unit 30a and an analyzing unit 30b. The pre-processing unit 30a
The analysis unit 30b includes a switching valve 31, a conversion device 32, and a trapper 33. The analysis unit 30b includes a pump 34 and a detector 35.

The switching valve 31 has the same structure as the switching valve 18 and switches the output gas from the generated gas outlet 21 of the conversion efficiency checker 10 to the downstream conversion device 32 or trapper 33 to supply the gas. Conversion device 32
Is for converting SO _x to SO ₂ , and trapper 3
3 is a device to eliminate SO _x. The pump 34 sends out the gas discharged from the upstream conversion device 32 or the trapper 33 to the downstream detector 35.
5 is for measuring the concentration of SO ₂ . Incidentally, the switching valve 31 is connected to the converter 32 when the analyzer 30 is of the SO _x mode as the first mode, whereas, the switching valve 31 is connected to the trapper 33 when the SO ₂ mode as the second mode .

With the above structure, SO as the source gas
₂ is for removing dust and the like by the first filter 11, then roughly adjusting the flow rate by the first flow control valve 12,
The flow rate is precisely adjusted by the mass flow controller 13 and supplied to the input side of the switching valve 18. O ₂ is second
The dust and the like are removed by the filter 14, the flow rate is roughly adjusted by the second flow rate control valve 15, the flow rate is precisely adjusted by the second mass flow controller 16, and then the water is saturated by the bubbler 17, and switching is performed. It is supplied to the input side of the valve 18. The switching valve 18 supplies a mixed gas of the output SO ₂ of the first mass flow controller 13 and the output gas of the bubbler 17 to the heating furnace 19 in the catalyst mode, and a heating pipe for bypassing the heating furnace 19 in the bypass mode. 20b.

In the catalytic mode, the heating furnace 19 oxidizes the mixed gas supplied from the switching valve 18 by contacting it with the oxidation catalyst 19a while heating the mixed gas to 200 to 600 ° C. by the heating means 19b. _x is generated and sent to the generated gas outlet 21. In this case _{SO 2 + (1/2) O 2} → SO 3 SO 3 + 6H 2 O → H 2 SO 4 · 5H 2 O , _{where, H 2 SO 4 · 5H 2} O is equivalent to sulfuric acid mist.
On the other hand, in the bypass mode, the heating pipe 20 b bypassing the heating furnace 19 allows the mixed gas from the switching valve 18 to pass therethrough and sends it out to the generated gas outlet 21.

Next, the conversion efficiency of the converter 32 in the analyzer 30 from SO _x to SO ₂ can be determined as follows. FIG. 3A shows the detector 35 in each mode.
Shows the measured values. First, the flow rate of SO ₂ is set by the first mass flow controller 13, and the flow rate of O ₂ is set by the second mass flow controller 16. At this time, the gas concentration after mixing of SO ₂ and O ₂ is close to the full scale of the range of the detector 35 of the analyzer 30 to be tested, and further increases by about 1 liter / min from the sampling flow rate of the analyzer 30. The SO ₂ cylinder concentration and S
Determine the flow ratio of O ₂ and O ₂ . Next, the switching valve 18
Puts the conversion efficiency checker 10 into bypass mode,
The analyzer 30 is set to the SO ₂ mode by the switching valve 31. At this time, since SO ₂ flows through the detector 35, the concentration of this SO ₂ is measured by the detector 35. This measured value is A in FIG.

Next, the conversion efficiency checker 10 is set to the catalytic mode by the switching valve 18, and the analyzer 30 is kept in the SO ₂ mode. The measured value of the detector 35 at this time is B in FIG. In this case, SO _x is generated from the conversion efficiency checker 10, but since the analyzer 30 is in the SO ₂ mode,
SO _x is removed by trapper 33, it flows through the SO ₂ only detectors 35 contained slightly, the measured value of the detector 35 is significantly reduced as described above B. Next, the mode of the analyzer 30 to SO _x mode by the switching valve 31,
The conversion checker 10 remains in the catalytic mode. The measured value of the detector 35 at this time is shown in FIG. in this case,
In analyzer 30, SO _x is to be converted into SO _2, measurement value of the detector 35 is recovered significantly as the C in converter 32.

Next, the conversion efficiency checker 10 is set to the bypass mode by the switching valve 18, and the analyzer 30
Leave in _x mode. The measured value of the detector 35 at this time is D in FIG. In this case, the conversion efficiency checker 10
Side is only for SO ₂ generation and the converter 32 of the analyzer 30
Pass through the SO _{2 as it} is. Next, the conversion efficiency of the conversion device 32 is obtained as follows. Conversion efficiency (%) = (C−B) / (D−B) × 100── (1) Note that, in the measured values of FIG. Since the value is a value obtained when the light beam has passed, D is used in the above conversion efficiency calculation formula. However, A may be used instead of D in equation (1) .

In the above equation (1), B is the concentration of the remaining SO _{2 in} the catalyst mode, and C is the converter 32 which converts the B and the SO _x generated in the catalyst mode.
Is the sum with the concentration of what was converted to SO ₂ . Therefore, C-B is the concentration has been converted into SO ₂ and SO _x generated in the catalyst mode in converter 32. Further, since D is the concentration of SO ₂ supplied to the conversion device 32 in the bypass mode, DB is the concentration of SO ₂ converted to SO _x in the catalyst mode.
5 shows the concentration of SO _x supplied to the converter 32. Therefore, (CB) / (DB) is converted by the converter 32 into SO
_It will accurately represent the conversion efficiency from _x to SO ₂ . In this manner, the conversion efficiency from SO _x to SO ₂ can be accurately obtained, so that the detection of SO _x can be performed accurately.

FIG. 2 illustrates a second embodiment.
The second embodiment is a modification of the first embodiment, and corresponds to claims 1 and 3. The conversion efficiency checker 10a shown in FIG. 2 is different from the conversion efficiency checker 10 shown in FIG. 1 in that a first flow control valve 12a, a second flow control valve 15a, a first switching valve 18a, a second switching valve 18b, and an overflow. Gas outlets 22a, 22b
Is added, but the first flow control valve 1 of FIG.
Those corresponding to the second and second flow control valves 15 are omitted. Other parts are the same as those in FIG.
The same reference numerals are given as in FIG. The outlet side of the first mass flow controller 13 and the outlet side of the bubbler 17 are connected to the inlet side of the first flow control valve 12a and the inlet side of the second flow control valve 15a. The outlet side of the first flow control valve 12a is connected to the inlet side of the heating furnace 19, and the outlet side of the heating furnace 19 is connected to the inlet side of the first switching valve 18a. The outlet side of the second flow control valve 15a is connected to the inlet side of the second switching valve 18b.

One outlet side of the first switching valve 18a and one outlet side of the second switching valve 18b are connected to a gas outlet 21.
It is connected to the. Furthermore, the other outlet side of the first switching valve 18a is connected to the overflow gas outlet 22a,
The other outlet side of the second switching valve 18b is connected to the overflow outlet 22b. The first switching valve 18a and the second switching valve 18b are linked. That is, when the first switching valve 18a is flowed to SO _x gas in the gas outlet 21 side (the analyzer 30 side), the second switching valve 18b SO ₂
The gas flows to the overflow outlet 22b side. Meanwhile, the first
Overflow switching valve 18a is SO _x gas outlet 2
When flowing to the 2a side, the second switching valve 18b causes the SO ₂ gas to flow to the gas outlet 21 side (the analyzer 30 side). The connection of the other parts is the same as in FIG.

With the above configuration, the conversion efficiency checker 1
Since the gas flow is always present in both the bypass mode line and the catalyst mode line 0a, the gas always flows through the heating furnace 19 even in the bypass mode line, and the temperature of the gas is stable. are doing. Therefore, even if the mode is switched from the bypass mode to the catalyst mode,
No change in catalyst conditions occurs. As a result, the conversion to sulfuric acid mist is stable, and the analyzer 30
Side, and the support value of the detector 35 can be stabilized quickly (within several minutes). That is, the state of B in FIG. Therefore, it is possible to from the most important SO _x of the SO _x analyzer 30 easily check the converter 32 conversion efficiency into SO _2, can manage maintain accuracy at all times analyzer 30, reliable diesel catalyst Contribute to development evaluation work. In the first embodiment, when the conversion efficiency checker 10 is in the bypass mode, the catalyst 1
Since no gas flows through 9a, the temperature of catalyst 19a decreases. Therefore, when the conversion efficiency checker 10 is switched from the bypass mode to the catalyst mode, adsorption and desorption of the sulfuric acid mist occurs due to a decrease in the temperature of the catalyst 19a, so that it takes about 60 minutes to reach a stable state. . FIG. 3B illustrates this state.

[0021]

According to the first invention of the present application, SO _x to S
According to the inspection method of the conversion device to O ₂ , SO _x is converted to SO ₂
Conversion efficiency can be measured accurately.
By detecting the _second concentration, it is possible to accurately detect the concentration of SO _x. Therefore, in the development and evaluation of the diesel oxidation catalyst, more reliable test data can be obtained by the above-described inspection method, and the analysis for the sulfuric acid mist suppression measure can be performed with high accuracy. Furthermore, the SO _{x according} to the second invention
According to the inspection device of the conversion device from SO to SO ₂ ,
The inspection method of the invention can be easily implemented. Furthermore, according to the inspection device for the SO _x to SO ₂ conversion device according to the third invention, the effect of the second invention can be obtained, and
Since the measurement of the conversion efficiency from O _x to SO ₂ becomes easier, the accuracy of SO _x can be controlled and maintained at all times, and as a result, it can further contribute to the development of diesel catalysts.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a first embodiment of the present invention.

FIG. 2 is an explanatory diagram of a second embodiment of the present invention.

FIG. 3 is a graph for explaining characteristics of each of the embodiments.

[Explanation of symbols]

 10, 10a Conversion efficiency checker 12, 12a, 15, 15a Flow control valve 13, 16 Mass flow controller 17 Bubbler 18, 18a, 18b Switching valve 19 Heating furnace 19a Catalyst 19b Heating means 30 Analyzer 31 Switching valve 32 Converter 33 Trapper 35 Detector

──────────────────────────────────────────────────の Continuation of the front page Examiner Hiroshi Miyazawa (56) References JP-A-7-27755 (JP, A) JP-A-53-145691 (JP, A) JP-A 63-260 (JP, U) ( 58) Field surveyed (Int. Cl. ⁷ , DB name) G01N 31/00 G01N 33/00

Claims (2)

(57) [Claims] 1. A method for producing sulfur oxides from sulfur dioxide gas.
A sulfur oxide generating device to be
To convert sulfur oxides into sulfur dioxide gas
And a sulfur dioxide gas disposed downstream of the conversion device.
A detector for detecting the concentration of
SO at which the gas on the outlet side is supplied to the converter and processed.
and _x mode line, SO ₂ mode for bypassing the converter
And a conversion device switching valve for switching to a pipeline.
Conversion efficiency check for checking conversion efficiency in the conversion device
A gas containing sulfur dioxide gas of a predetermined concentration and moisture added to oxygen.
Is supplied to the sulfur oxide generator.
Catalyst mode line to feed and treat
Switch to bypass mode line to bypass the device
Conversion efficiency detection characterized by having a switching valve
Inspection equipment. 2. A method for producing sulfur oxides from sulfur dioxide gas.
A sulfur oxide generating device to be
To convert sulfur oxides into sulfur dioxide gas
And a sulfur dioxide gas disposed downstream of the conversion device.
A detector for detecting the concentration of
SO at which the gas on the outlet side is supplied to the converter and processed.
and _x mode line, SO ₂ mode for bypassing the converter
And a conversion device switching valve for switching to a pipeline.
Conversion efficiency check for checking conversion efficiency in the conversion device
A gas containing sulfur dioxide gas of a predetermined concentration and moisture added to oxygen.
And the mixed gas obtained by passing through the sulfur oxide generator.
Catalyst mode line supplied to the converter side
And the conversion device via the sulfur oxide generation device
Switch to supply line to outside overflow outlet
A first switching valve, and the mixed gas is bypassed to the sulfur oxide generator.
Mode line to be supplied to the converter side
The conversion by bypassing the sulfur oxide generator
Cut to the line to supply to the overflow outlet outside the device
Characterized in that a second Setsu換Ba Lube changing
Conversion efficiency inspection device.