JPH0824576A - Deodorizing method in gas engine and device therefor - Google Patents

Abstract

PURPOSE:To suppress the corrosion of a combustion chamber, an evacuation passage and a lubricating part by using plural catalysts capable of removing at least one kind of a malodor component among malodor components in accordance with the kinds of the malodor components to remove the malodor components before a gaseous fuel containing at least two kinds of the malodor components is introduced into a gas engine. CONSTITUTION:The malodor components are removed by using the plural catalysts (e.g. Cu-H ion exchange zeolite-based catalyst, Mn oxide-ceramic- -based catalyst) capable of removing at least one kind of the malodor component among the components in accordance with the kinds of the malodor components before the gaseous fuel containing at least two kinds of malodor components (e.g. mercaptanes, linear sulfides) is introduced into the gas engine. As a result, the formation of oxides in the gas engine is prevented, the corrosion of the combustion chamber, the evacuation passage and the lubricating part is suppressed and the durability of the engine is improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorizing method and a deodorizing device in a gas engine which uses a gas such as city gas or propane gas to which an odorant is added as a measure against gas leakage as a fuel.

[0002]

2. Description of the Related Art Conventionally, as a deodorizing device used in this type of gas engine, Japanese Patent Application No. 5-5 previously proposed by the applicant of the present invention has been proposed.
There is one disclosed in No. 6497. In this conventional deodorizing device, a catalyst is interposed in the fuel supply passage of the gas engine,
This catalyst has a structure for removing the odorous component (odorant) in the gas fuel. However, if the catalyst is simply provided in the fuel supply passage as described above, it may not be possible to sufficiently deodorize when using a gas fuel mixed with a plurality of types of odorants.

When the gas fuel mixed with the odorant is supplied to the gas engine as described above, SO _X is generated in the combustion chamber and is combined with water vapor to cause corrosion of the combustion chamber or the exhaust path. Cause corrosion. Also, when SO _X due to the odorant is mixed in the blow-by gas that leaks into the crank chamber, it combines with the water vapor in the blow-by gas to form an acid, which is sent to the lubrication part of each part together with the oil in the crank chamber, Corrodes the lubricated part. Furthermore, if a three-way catalyst is used to purify the exhaust gas, the SO _x
Since it becomes a negative catalyst, there is a problem that exhaust gas cannot be purified using the catalyst.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to remove more odorant from a gas fuel so that a combustion chamber, an exhaust passage and a lubrication part are less likely to be corroded, and a three-way catalyst and an oxidizer are used. It is to be able to purify the exhaust gas by using a catalyst or the like.

[0005]

As a result of intensive studies in view of the above problems, the present inventors have found that even when a gas fuel containing two or more odorous components is used, each odorous component is individually treated. By combining a catalyst that can be removed, virtually all types of odorous components can be removed, corrosion of the engine combustion chamber, exhaust path, lubrication part, etc. can be prevented, and a three-way catalyst or oxidation The inventors have found that exhaust gas can be purified using a catalyst or the like, and completed the present invention.

That is, according to the present invention, before introducing a gas fuel containing at least two kinds of odorous components to a gas engine, a catalyst capable of removing at least one kind of odorous components from the odorous components is added to the catalyst. A deodorizing method in a gas engine, characterized in that the odorous component is removed by using a plurality of types according to the type.

The present invention also provides a deodorizing method for a gas engine, which is characterized by removing odorous components as described above and purifying exhaust gas by using a three-way catalyst, an oxidation catalyst or a reduction catalyst. is there. Further, the present invention provides
While removing the odorous components as described above, the exhaust gas is purified using an oxidation catalyst, and a solid and / or an alkaline aqueous solution that exhibits alkalinity when dissolved in water is used.
A deodorizing method in a gas engine, which is characterized by removing an irritating odor. Furthermore, the present invention provides a fuel supply path for introducing a gas fuel containing at least two kinds of odorous components to a gas engine.
A deodorizing device for a gas engine, comprising a plurality of catalysts capable of removing different types of odor components according to the types of odor components.

The present invention will be described in detail below. In the present invention, for a gas fuel containing two or more odorous components,
By using a combination of catalysts capable of removing each odor component individually, substantially all types of odor components can be removed. As gas fuel,
Generally, city gas or propane gas is used, but these gas fuels usually contain a trace amount of the following two types of odorants. These two types of odorants have the following chemical formula (1)

[0009]

Embedded image

Mercaptans having the structure shown by (for example, tert-butyl mercaptan, i-propyl mercaptan, n-propyl mercaptan, 3-methyl-3-pentanethiol, etc.) Odorant) and the following chemical formula (2)

[0011]

[Chemical 6]

A chain sulfide having the structure shown by, a cyclic sulfide, a chain dimethyl sulfide, a chain methyl ethyl sulfide, a cyclic tetrahydrothiophene, etc. (hereinafter, simply referred to as a second odorant) Is.

As the catalyst capable of removing the first odorant (hereinafter referred to simply as the first catalyst), Cu
-H ion-exchanged zeolite-based catalyst, Mn oxide-ceramic-based catalyst, Cu-Mn catalyst, hopcalite catalyst, Mn
The —Fe-based catalyst, the Fe—Cu-based composite oxide catalyst and the like can be used alone or in appropriate combination. Cu-
As the H ion-exchanged zeolite-based catalyst, for example, HCYZ manufactured by Nippon Steel Co., Ltd. can be used, and as the Mn oxide-ceramic-based catalyst, for example, SAP manufactured by Sakai Chemical Industry Co., Ltd.
-1 can be used, and as the hopcalite catalyst,
For example, Hopcalite II manufactured by GL Science can be used.

The catalyst capable of removing the second odorant (hereinafter, simply referred to as the second catalyst) is Mn.
Oxide-ceramic catalysts, Cu-Mn catalysts, hopcalite catalysts, Mn-Fe catalysts, Fe-Cu compound oxide catalysts, etc. can be used alone or in appropriate combination. As the Mn oxide-ceramic based catalyst, for example, SAP-10 manufactured by Sakai Chemical Industry can be used, and as the hopcalite catalyst, for example, Hopcalite I manufactured by GL Science can be used.

The first catalyst and the second catalyst are preferably used in combination in series. Particularly, the first catalyst is located upstream in the gas fuel flow direction and the second catalyst is located downstream in the gas fuel flow direction. It is preferable to use it after arranging it. Further, the first catalyst and the second catalyst specifically described above can be used in an appropriate combination. For example, a Mn oxide-ceramic based catalyst having a small specific surface area is used as the first catalyst,
A Mn oxide-ceramic catalyst having a large specific surface area can be used as the second catalyst. Specifically, when the specific surface area of the Mn oxide-ceramic catalyst is 10 to 150 M ² / g as the first catalyst, the specific surface area of the Mn oxide-ceramic catalyst is 50 to 200 M ² / g. Some can be used as the second catalyst.

By using an appropriate combination of the first catalyst and the second catalyst, the odorant which is easy to be chemically structurally removed by the upstream catalyst is removed, and then the downstream catalyst is chemically structurally removed. Remove difficult odorants. The reason why this is preferable is as follows.

1. The odorant represented by the chemical formula (1) is easily decomposed in terms of chemical structure. 2. The odorant represented by the chemical formula (2) is more stable in chemical structure than the odorant represented by the chemical formula (1). 3. The odorant represented by the chemical formula (2) is a fuel gas, for example, propane represented by the chemical formula (3) below.

[0018]

[Chemical 7]

Since the structure is close to, it is necessary for the catalyst to be able to distinguish between a large amount of propane and the odorant represented by the chemical formula (2). When the first catalyst is arranged on the downstream side and the second catalyst is arranged on the upstream side, both the first odorant and the second odorant in the gas fuel are on the upstream side. It flows into the second catalyst and is adsorbed by it,
When both the first odorant and the second odorant are adsorbed by the second catalyst, the second odorant cannot be completely removed, and this flows out to the downstream side. . That is, at this time, the removal of the second odorant is not completely carried out, and this slightly flows into the first catalyst on the downstream side.
Since the second odorant cannot be removed by the first catalyst, the second odorant is eventually supplied to the gas engine.
Therefore, as described above, it is preferable to arrange the first catalyst on the upstream side in the gas fuel flow direction and the second catalyst on the downstream side in the gas fuel flow direction.

The catalyst is used at a temperature below 80 ° C. It is preferably used at 30 ° C or lower. If it is used in a condition out of the above temperature range, the catalytic activity is lowered and it becomes difficult to remove the odorant. To use the catalyst at such a temperature, it can be cooled by cooling water of the engine. In addition, it is preferable to use a separate cooling device because it has further effects. The catalyst may be used in any form as long as it can remove the odorant, but a honeycomb structure is preferable in consideration of the efficiency of removing the odorant.
The catalyst is used at an SV value of 10 ² to 10 ⁵ H ^-1 , preferably 10 ² to 10 ³ H ^-1 .

The deodorizing method using the gas fuel containing two types of odorants has been described above. Next, the deodorizing method using the gas fuel containing three types of odorants will be described. To do.

Among gas fuels, for example, different city gas manufacturing companies may contain three kinds of odorants, that is, mercaptan odorants, sulfide odorants and thiophene odorants. When such a gas fuel is used, the catalyst (catalyst a) for the mercaptan odorant is a Cu-H ion-exchange zeolite catalyst, a Mn oxide-ceramic catalyst, a Cu-Mn catalyst, a hopcalite catalyst, and a Mn catalyst. As a catalyst (catalyst b) for a sulfide-based odorant such as —Fe catalyst, a catalyst for a thiophene-based odorant such as a Mn oxide-ceramic catalyst, a Cu—Mn catalyst, a hopcalite catalyst, and a Mn—Fe catalyst ( As the catalyst c), it is preferable to use a Mn oxide-ceramic catalyst, a Cu-Mn catalyst, a hopcalite catalyst, a Mn-Fe catalyst, etc., and to remove both the sulfide odorant and the thiophene odorant. As a possible catalyst (catalyst d),
Mn oxide-ceramic based catalyst, hopcalite catalyst, M
It is also possible to use an n-Fe-based catalyst or the like.

When using the catalysts a, b and c, it is preferable to arrange the catalysts a, b and c in series in this order from the upstream side in the flow direction of the gas fuel. When using the catalysts a and d,
The catalysts a and d are preferably arranged in series from the upstream side in the flow direction of the gas fuel. Next, the deodorizing method in the gas engine of the present invention will be described with reference to the flowchart.

FIG. 1 is a flow chart showing a deodorizing method according to the first embodiment of the present invention. In FIG. 1, A is a zero governor, B is an odorant removing device, C is a mixer, D is an engine, and E is a catalyst. In this embodiment, the pressure of the fuel gas is adjusted by the zero governor A, the odorant is removed by the odorant removal device B, and the fuel gas is mixed with air by the mixer C. Then, it burns in the engine D and becomes exhaust gas, and then CO, HC, NO _{x is} generated by the catalyst E.
Etc. are removed and purified. As the odorant removal device B, a combination of a plurality of the aforementioned catalysts may be used.

Any kind of catalyst may be used as the catalyst E as long as it can purify the exhaust gas, but usually a three-way catalyst, an oxidation catalyst or a reduction catalyst can be used. There is a problem that SO _X generated in the combustion chamber becomes a negative catalyst when the fuel gas from which the odorant is not removed is used as in the past, but the odorant is removed as in the present invention. Thus, the catalyst can be used.

As the three-way catalyst, for example, Pt / Pd /
Rh-based catalyst, Pt / Pd-based catalyst, Pt / Rh-based catalyst, P
Examples include d / Rh-based catalysts. Examples of the oxidation catalyst include zeolite catalyst, Al ₂ O ₃ catalyst, Pt catalyst, Pd
Examples thereof include catalysts, Pt / Pd-based catalysts, Au-based catalysts, and the like.
As the reduction catalyst, for example, Pt / Al ₂ O ₃ catalyst, Cu
-ZSM-5 catalyst, perovskite catalyst, Au catalyst and the like. The concentration of the odorous component in the fuel gas is much higher than the concentration of the odorous component in the air-fuel mixture (assuming that the combustible air-fuel mixture ratio is fuel 1: air 14, the concentration of the odorous component in the air-fuel mixture is It becomes 1/15 of that before mixing)
Therefore, as in the present embodiment, by arranging the odorant removal device B before mixing the air and the fuel gas, that is, upstream of the mixer C, it is more efficient than the case of arranging the odorant removal device B downstream of the mixer C. It is possible to remove odorous components (odorants).

FIG. 2 is a flow chart showing a deodorizing method according to the second embodiment of the present invention. In this embodiment, the pressure of the fuel gas is adjusted by the zero governor A, then mixed with air by the mixer C, and then the odorant is removed by the odorant removal device B. Then, it burns in the engine D and becomes exhaust gas, and then CO, H by the catalyst E.
C, NO _x, etc. are removed and purified. Thus, the odorant in the fuel gas can be removed even after being mixed with air.

FIG. 3 is a flow chart showing a deodorizing method according to the third embodiment of the present invention. In FIG. 3, F represents a heat exchanger and G represents an irritating odor removing device. In this embodiment,
The pressure of the fuel gas is adjusted by the zero governor A, the odorant is removed by the odorant removal device B, and the fuel gas is mixed with air by the mixer C. Then, it burns in the engine D to become exhaust gas, and is then purified by the catalyst E '. Then, it is cooled by the heat exchanger F, and the irritating odor is removed by the irritating odor removing device G. By cooling the exhaust gas as in this embodiment, it is possible to reduce the thermal stress in the exhaust pipe and the like. This cooling can be performed by cooling water of the engine. In addition, the exhaust gas normally contains NO
_Since acidic substances such as _x and organic acids that cause an irritating odor are contained, these substances are removed in this embodiment. In order to remove these acidic substances, a solid that exhibits alkalinity when dissolved in water, an alkaline aqueous solution, or a combination thereof may be used.

Examples of the solid that exhibits alkalinity when dissolved in water include potassium hydroxide, sodium hydroxide, calcium hydroxide, calcium carbonate, sodium carbonate, etc. Examples of the calcium carbonate include calcite, limestone, coral, etc. Can be used. As the alkaline aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, calcium hydroxide aqueous solution, calcium carbonate aqueous solution, sodium carbonate aqueous solution or the like can be used.

When the above solid is used, it may be used in a desired shape such as a powder, a spherical body, or a honeycomb shape. In the case of a powder, which may be diffused by the passage of gas, A filter or the like may be used as appropriate. On the other hand, when an aqueous solution is used, exhaust gas may be directly passed through the aqueous solution. By performing such a treatment, the pungent odor of exhaust gas can be removed.

FIG. 4 is a flow chart showing a deodorizing method according to the fourth embodiment of the present invention. In this embodiment, the pressure of the fuel gas is adjusted by the zero governor A, then mixed with air by the mixer C, and then the odorant is removed by the odorant removal device B. Then, it burns in the engine D to become exhaust gas, and is then purified by the catalyst E '. Then, it is cooled by the heat exchanger F, and the irritating odor is removed by the irritating odor removing device G.

Also in this embodiment, as in the second embodiment, the odorant in the fuel gas can be removed even after being mixed with air. Next, the deodorizing device in the gas engine of the present invention will be described. FIG. 5 is a configuration diagram showing an embodiment of a gas engine type air conditioner adopting the deodorizing device according to the present invention, and FIG. 6 is a graph showing how the odorant is removed.

In FIG. 5, reference numeral 1 is a water-cooled 4-cycle type gas engine, and 2 is an air conditioner constituted by using the gas engine 1 as a power source. The gas engine 1 burns and explodes gas fuel such as city gas and propane gas supplied from the gas fuel supply pipe 3 in the cylinder 4 to generate an exhaust pipe 5.
The air conditioner 2 is connected to the crankshaft 6.

Reference numeral 7 is a piston of the gas engine 1, 8 is a valve operating device for driving intake / exhaust valves, 9 is an ignition plug, and 10 is an oil pan for storing lubricating oil in the crank chamber. The lubricating oil stored in the oil pan 10 is
After being sucked out by the oil pump 11 and foreign matter removed by the oil filter 12, the foreign matter is supplied to the bearing portion of the crankshaft 6, the valve operating device 9 and the like. Further, the exhaust gas discharged from the gas engine 1 is discharged into the atmosphere via the exhaust heat exchanger 5a connected to the exhaust pipe 5.

The exhaust heat exchanger 5a has a structure for cooling the exhaust gas with engine cooling water, which will be described later. A neutralizer 5c is connected to the exhaust heat exchanger 5a via a drain water passage 5b, and the acidic drain water accumulated in the exhaust heat exchanger 5a is neutralized by the neutralizer 5c and then discharged. It is configured to be.

The gas engine type air conditioner 2 is driven by a crankshaft 6 to compress a refrigerant such as Freon, ammonia, hydrocarbon, etc., a condenser 14, an expansion valve 15, and an evaporator 16. Is provided with a refrigerant circuit. In this refrigerant circuit, the refrigerant is compressed by the compressor 13 into high-pressure gas, which is condensed and liquefied in the condenser 14 to radiate the heat of condensation. The refrigerant liquefied by heat dissipation is expanded in the expansion valve 15 and partially becomes gasified low-pressure low-temperature refrigerant, which absorbs heat from the outside air forcedly blown by the fan 16a in the evaporator 16 and cools it. . The refrigerant gasified by the endotherm,
Returning to the compressor 13 again, the above cycle is repeated.

The fuel supply device for supplying the gas fuel to the gas engine 1 includes a gas main plug 22 connected to a gas supply pipe 21.
And a pressure regulator for reducing the pressure of the gas fuel flowing out from the gas main plug 22 to the gas engine 1 to an optimum pressure, that is, the zero governor 23, and between the pressure regulator 23 and the gas fuel supply pipe 3 in the previous period. Deodorizing device 24 installed in
It consists of and.

The gas tap 22 has a gas leak detector 26.
Is connected to the emergency gas shutoff device 25, and when a gas leak occurs in the engine room 27, the emergency gas shutoff device 2
5 is configured to be closed. In addition,
The gas leak detector 26 is composed of a gas sensor, and the engine room 2
7 and is arranged in the vicinity of the deodorizing device 24. The gas sensor has been conventionally used generally such as an infrared absorption type, an optical interference type, a semiconductor type, and a heat conduction type. The gas fuel that can be used in the present invention is as described above, but in the present example, tertiary butyl mercaptan is contained as the first odorant and dimethyl sulfide is contained as the second odorant. An example using gas fuel will be described.

The deodorizing device 24 has a double pipe structure including an inner cylinder 31 having a gas fuel passage inside and an outer cylinder 32 covering the outer peripheral portion of the inner cylinder 31. Then, the first catalyst 33 and the second catalyst 34 are loaded in the inner cylinder 31, the upstream end of the inner cylinder 31 is communicated with the pressure regulator 23, and the downstream end thereof is the gas fuel. It is fitted and fixed to the feed pipe 3.

The catalysts 33 and 34 each have a honeycomb structure, and are loaded in the inner cylinder 31 in a state where the first catalyst 33 is positioned upstream and arranged in series. Of these catalysts 33, 34, the first catalyst 33 located on the upstream side is a Cu—H ion-exchanged zeolite-based catalyst in this embodiment, and is capable of removing the first odorant.

The second catalyst 34 located on the downstream side is a Mn oxide-ceramic type catalyst in this embodiment. The second catalyst 34 is capable of removing both the first odorant and the second odorant. That is, in the deodorizing device 24 of the present embodiment, the first catalyst 33 that can remove only one type of deodorant is arranged on the upstream side, and the second catalyst 34 that can remove two types of deodorant. Is arranged on the downstream side. A space between the inner cylinder 31 and the outer cylinder 32 is configured to circulate engine cooling water. That is, the first and second catalysts 33 and 34 are cooled by the engine cooling water from the outer peripheral side to the entire circumference. Here, the configuration of the cooling system of the gas engine 1 will be described.

When the gas engine 1 is in operation, the engine cooling water cooled by the radiator 35 or cooled by the double-tube heat exchanger 90 which is a heat exchanger with the refrigerant first flows to the deodorizing device 24. After cooling the deodorizing device 24, it is supplied to the cooling water passage 4a in the cylinder 4 by the cooling water pump 36. And
After cooling the cylinder 4, it is sent to the thermostat 37. At this time, the engine cooling water is returned to the suction port of the cooling water pump 36 when the temperature is lower than a predetermined temperature,
When the temperature is equal to or higher than a predetermined temperature, it is sent to the cooling passage in the exhaust heat exchanger 5a and then branched or switched in the linear three-way valve 91, the inlet of the radiator 35 or the inlet of the radiator 35 and the double pipe heat exchanger 90. To return to.

That is, the engine cooling water circulates in the gas engine 1 until the engine cooling water temperature reaches the set temperature in the thermostat 37, and when it reaches or exceeds the set temperature, the radiator 35 → the deodorizing device 24 → the cooling water pump. 36 → inside cylinder 4 → thermostat 37 → exhaust heat exchanger 5a → linear three-way valve 91 → radiator 35 or →
It follows the circulation path of the double tube heat exchanger 90.
The linear three-way valve 91 is adjusted so that as the load on the condenser 14 or the evaporator 16 increases, more hot water flows to the double-tube heat exchanger 90, while reducing the amount of hot water to the radiator 35. To do.

When the deodorizing device 24 thus constructed is provided, the two kinds of odorants contained in the gas fuel supplied through the gas tap 22 and the pressure regulator 23 pass through the deodorizing device 24. At times, it is almost removed by the catalysts 33 and 34. That is, as shown in FIG. 6, substantially all of the first odorant is removed when passing through the upstream first catalyst 33, and the first odorant is passed when passing through the second catalyst 34. And the second odorant are all removed.

The gas fuel from which the total amount of the odorant has been removed in this way is mixed with air in the mixer 102. Specifically, the air that has passed through the intake passage 100 and is cleaned by the air cleaner 101 with the silencer function and the gas fuel injected from the fuel gas nozzle 102b are mixed in the venturi portion 102a. After the flow rate of this mixed gas is adjusted by the throttle valve 102c, the mixed gas passes through the intake passage 103, and then from the intake port 104 to the gas engine 1.
Flows into the cylinder 4. The mixed gas burned in the cylinder 4 is discharged to the exhaust pipe 5 as exhaust gas.

Between the cylinder 4 and the piston 7 during combustion
The blow-by gas blown through (indicated by the arrow L in the figure)
When the media 33 and 34 are not provided, CO₂, CO, H₂O,
NO _x， SO in addition to mist of lubricating oil_xIt is included
However, as in this example, the catalyst is made to correspond to the type of odorant.
SO when placed in series_xThe ingredients are extremely small
Become so. Therefore, oxides are generated in the crank chamber.
Lubrication accumulated in the oil pan 10 is difficult to achieve
Ensures that oxides will dissolve in the oil and the lubrication point will be corroded
Can be prevented.

Further, since the first and first catalysts 33 and 34 are cooled from the outer peripheral portion by the engine cooling water during the engine operation, the temperature may rise due to the heat of the gas engine 1 or the heat of reaction. It can be suppressed. Therefore, the efficiency of removing the odorant does not decrease. It should be noted that, in the above-described embodiment, an example in which two kinds of catalysts are interposed in series in the gas fuel passage is shown, but as shown in FIG. 7, the gas fuel passages are provided in parallel and the catalyst is arranged in one side. You can also FIG. 7 is a configuration diagram showing another example of the gas fuel passage, in which the same or equivalent members as those described in FIG. 5 are designated by the same reference numerals and detailed description thereof will be omitted.

In FIG. 7, reference numeral 41 is an auxiliary fuel passage,
This sub fuel passage 41 is provided in parallel with the gas fuel passage in which the deodorizing device 24 is interposed, and is connected to the upstream side and the downstream side of the deodorizing device 24. A throttle 42 is provided in the sub fuel passage 41 so that the flow rate of the gas fuel is smaller than that in the gas fuel passage on the deodorizing device 24 side.
In order to keep the flow rate low, an on-off valve may be used instead of the throttle 42.

In this embodiment, the odorous component cannot be completely removed, but the corrosion of the lubricated portion can be reduced to a level at which there is no practical problem. Further, although the passage resistance of the gas fuel passage is increased by disposing the catalyst, the passage resistance can be reduced by the sub fuel passage 41, and, for example, the transient response of the engine can be improved. it can.

Further, in each of the above-mentioned embodiments, an example in which two kinds of catalysts are provided so as to correspond to two kinds of odorants is shown. However, when using a gas fuel in which three kinds of odorants are mixed, It is configured as shown in FIGS. 8 and 9.

FIG. 8 is a block diagram showing another embodiment in which three types of catalysts are arranged in series, and FIG. 9 is a block diagram showing another embodiment in which only the catalyst on the gas engine side can be cooled. In these figures, the same or equivalent members as those described in FIGS. 5 and 7 are designated by the same reference numerals, and detailed description thereof will be omitted. In FIG. 8, reference numeral 51 is a third catalyst, which removes the thiophene-based odorant, and is the first catalyst 3 for the mercaptan-based odorant.
3 and the second catalyst 34 for the sulfide-based odorant are disposed further downstream. Incidentally, this third catalyst 51
Since the first catalyst and the second catalyst 34 can remove both the first odorant and the second odorant, these arrangements can be interchanged before and after.

With this structure, almost all of the odorant is used even if a gas fuel containing a mixture of three types of odorant such as a mercaptan type, a sulfide type, and a thiophene type is used. Can be reliably removed before being supplied to the gas engine 1.

In FIG. 9, reference numeral 52 is a catalyst capable of removing both the thiophene odorant and the sulfide odorant. This catalyst 52 is used as a first mercaptan odorant
By arranging it on the downstream side of the catalyst 33, the above three types of odorants can be removed.

As described above, before introducing the gas fuel containing at least three kinds of odorous components to the gas engine, the catalyst capable of removing at least one kind of odorous components from the odorous components is used as a catalyst. The deodorizing method / apparatus may be configured to remove all of the three types of odorous components by using a plurality of types according to the above. The device shown in FIG. 9 has a structure in which only the catalyst 52 on the downstream side of the gas fuel passage and closer to the gas engine 1 is cooled by the cooling device 53. The cooling device 53 has the same structure as that shown in FIG. 5, and has a structure in which engine cooling water cooled by the radiator 35 is circulated by flowing it to the catalyst 52 by the cooling water pump 36. Although not shown, the cooling water passage of the gas engine 1 also has the cooling device 53.
Supplies engine cooling water.

FIG. 10 is a block diagram showing another embodiment of a gas engine type air conditioner adopting the deodorizing device according to the present invention. Unlike the above-described embodiment, in this embodiment, the gas fuel from which the odorant has been removed by the catalysts 33 and 34 is controlled by the injection nozzle opening / closing control valve 107 and the injection nozzle 10
It is directly injected into the cylinder 4 from 6. On the other hand, air is
The flow rate is adjusted by the throttle valve 105 and flows into the cylinder 4 from the intake port 104. The gas fuel and air are mixed in the cylinder 4 and burned.

As in this embodiment, air and fuel gas are independently guided to the cylinder, and a catalyst capable of removing odorous components is arranged in the fuel passage for supplying the fuel gas to the cylinder. The odorant can be removed more efficiently than when the catalyst is arranged in the passage of the air-fuel gas mixture.

[0057]

The present invention will be described in more detail below with reference to examples, but these examples do not limit the scope of the present invention.

(Example 1) A first Mn oxide-ceramic catalyst (SAP-1 manufactured by Sakai Chemical Industry) having a honeycomb structure and a specific surface area of 80 M ² / g, and a specific surface area of 150 M. ² / g, which has a honeycomb structure
Mn oxide-ceramic-based catalyst (manufactured by Sakai Chemical Industry, SA
P-10), a deodorizing device having a structure as shown by the deodorizing device 24 in FIG. 1 was produced so that the first Mn oxide-ceramic based catalyst was on the upstream side in the flow direction of the gas fuel. T-Butyl mercaptan as fuel gas
LPG containing 1.0 ppm and dimethyl sulfide of 0.5 ppm was passed through the deodorizing apparatus. At that time, the temperature of the catalyst was 30 ° C., and the SV value was 5 × 10 ³ H ⁻¹ . The concentrations of t-butyl mercaptan and dimethyl sulfide in the fuel gas after passing through the deodorizer were measured by gas chromatography. The results are shown in Table 1.

(Example 2) C having a honeycomb structure
u-H ion-exchanged zeolite-based catalyst (made by Nippon Steel, H
CYZ) and a Mn oxide-ceramic catalyst having a honeycomb structure and a specific surface area of 150 M ² / g (SAP-10 manufactured by Sakai Chemical Industry Co., Ltd.), a Cu-H ion exchange zeolite catalyst is used. A deodorizing device having a structure as shown in the deodorizing device 24 in FIG. 1 was prepared so as to be on the upstream side in the flow direction of the gas fuel. As the fuel gas, city gas 13A containing 1.0 ppm of t-butyl mercaptan and 0.5 ppm of dimethyl sulfide was used and passed through the deodorizing device. At that time, the temperature of the catalyst is 30 ° C., and the SV value is 1 ×
It was 10 ⁴ H ^-1 . T- in the fuel gas after passing through the deodorizing device
The concentrations of butyl mercaptan and dimethyl sulfide were measured by gas chromatography. The results are shown in Table 1.

(Comparative Example 1) Similar to Example 1 using only Mn oxide-ceramic catalyst (SAP-10 manufactured by Sakai Chemical Industry) having a honeycomb structure and a specific surface area of 150 M ² / g. Then, LPG was passed through. Table 1 shows the results of measuring the concentrations of t-butyl mercaptan and dimethyl sulfide in the fuel gas after passing through the deodorizing device.

[0061]

[Table 1]

As is clear from Table 1, the odorant in the fuel gas can be completely removed by using a plurality of types of catalysts.

[0063]

EFFECTS OF THE INVENTION According to the present invention, since the odorous components in the gas fuel can be removed, it is possible to prevent the generation of oxides in the gas engine, and therefore the combustion chamber, the exhaust path, and the lubrication section. Corrosion can be suppressed and engine durability can be improved.

[Brief description of drawings]

FIG. 1 is a flowchart showing a deodorizing method according to a first embodiment of the present invention.

FIG. 2 is a flowchart showing a deodorizing method according to a second embodiment of the present invention.

FIG. 3 is a flowchart showing a deodorizing method according to a third embodiment of the present invention.

FIG. 4 is a flowchart showing a deodorizing method according to a fourth embodiment of the present invention.

FIG. 5 is a configuration diagram showing an embodiment of a gas engine type air conditioner adopting the deodorizing device according to the present invention.

FIG. 6 is a graph showing how an odorant is removed.

FIG. 7 is a configuration diagram showing another example of a gas fuel passage.

FIG. 8 is a configuration diagram showing another embodiment in which three kinds of catalysts are arranged in series.

FIG. 9 is a configuration diagram showing another embodiment in which only the catalyst on the gas engine side can be cooled.

FIG. 10 is a configuration diagram showing another embodiment of a gas engine type air conditioner adopting the deodorizing device according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Gas engine 3 ... Gas fuel supply pipe 24 ... Deodorizing device 33 ... First catalyst 34 ... Second catalyst 51 ... Third catalyst 52 ... Thiophene-based / sulfide-based odorant catalyst

Claims (14)

[Claims] 1. A catalyst capable of removing at least one odor component of the odor components before introducing a gas fuel containing at least two odor components to a gas engine, according to the type of the odor components. A deodorizing method in a gas engine, characterized in that the odorous components are removed by using a plurality of them. 2. A catalyst capable of removing at least one odor component of the odor components before introducing the gas fuel containing at least two odor components to the gas engine, depending on the type of the odor components. A deodorizing method in a gas engine, characterized in that the odorous component is removed by using a plurality of them, and the exhaust gas is purified by using a three-way catalyst, an oxidation catalyst or a reduction catalyst. 3. A catalyst capable of removing at least one odor component of the odor components before introducing a gas fuel containing at least two odor components to a gas engine, according to the type of the odor components. By using a plurality of odor components, the exhaust gas is purified using an oxidation catalyst, and a stimulating odor is removed by using a solid and / or an alkaline aqueous solution that is alkaline when dissolved in water. The deodorizing method in a gas engine. 4. The deodorizing method for a gas engine according to claim 1, wherein the gas fuel is represented by the following chemical formula (1): A first odorant comprising a compound having a structure represented by the following chemical formula (2) A second odorant comprising a compound having a structure represented by
As a catalyst of Cu-H ion-exchanged zeolite-based catalyst,
At least one selected from the group consisting of Mn oxide-ceramic catalyst, Cu-Mn catalyst, hopcalite catalyst, and Mn-Fe catalyst is used, and Mn oxidation is used as the second catalyst for the second odorant. Material-Ceramic type catalyst, C
A method comprising arranging the first catalyst and the second catalyst in series, using at least one selected from the group consisting of u-Mn catalyst, hopcalite catalyst, and Mn-Fe-based catalyst. 5. The method for deodorizing a gas engine according to claim 4, wherein the specific surface area of the Mn oxide-ceramic catalyst as the first catalyst is 10 to 150 M ² / g, and the specific catalyst has a specific surface area of 10 to 150 M ² / g. A method characterized in that the Mn oxide-ceramic based catalyst has a specific surface area of 50 to ²⁰⁰ M ² / g. 6. The deodorizing method for a gas engine according to claim 4 or 5, wherein the first catalyst is arranged upstream in the flow direction of the gas fuel. 7. The deodorizing method for a gas engine according to claim 1, wherein the catalyst is cooled. 8. The deodorizing method for a gas engine according to claim 3, wherein the solid exhibiting alkalinity when dissolved in water is selected from the group consisting of potassium hydroxide, sodium hydroxide, calcium hydroxide, calcium carbonate and sodium carbonate. At least one compound selected from the group consisting of potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, calcium hydroxide aqueous solution, calcium carbonate aqueous solution, and sodium carbonate aqueous solution. A method characterized by being. 9. A catalyst capable of removing at least one odor component among the odor components is provided in a fuel supply path for introducing a gas fuel containing at least two odor components to a gas engine, depending on the type of the odor component. A deodorizing device for a gas engine, wherein a plurality of deodorizing devices are provided. 10. The deodorizing device for a gas engine according to claim 9, wherein an odor component as a gas fuel is represented by the following chemical formula (1): A first odorant composed of a compound having a structure represented by the following formula and an odor component having the following chemical formula (2): A first catalyst for a compound having a structure represented by the chemical formula (1) is mainly used in a fuel gas as a catalyst, and a second odorant containing a compound having a structure represented by An apparatus characterized in that a second catalyst mainly for a compound having the structure of the chemical formula (2) is used in a fuel gas, and these two catalysts are arranged in series. 11. The deodorizing device for a gas engine according to claim 10, wherein the first catalyst is arranged on the upstream side in the flow direction of the gas fuel. 12. The deodorizing device for a gas engine according to claim 9, wherein the catalyst is cooled. 13. A gas engine having a mixer capable of mixing a gas fuel containing an odorous component and air, wherein the air-fuel mixture mixed by the mixer is introduced from an intake port into a cylinder. By arranging a catalyst that can remove odorous components in the fuel passage on the upstream side,
A deodorizing method in a gas engine, comprising removing the odorous component. 14. A gas engine is configured so that air is introduced into a cylinder and gas fuel containing an odor component is introduced into the cylinder independently of the air, and an odor is introduced into a fuel passage for supplying the gas fuel to the cylinder. A deodorizing method in a gas engine, comprising removing the odorous component by disposing a catalyst capable of removing the component. [0000]