KR101279548B1 - Method of improving performance and device of sulfide removal device - Google Patents

Abstract

The present invention activates the oxidation catalyst action of the sulfur compound contained in the pre-reactor and then converts the sulfur compound into harmless and odorless sulfur by the oxidation catalyst in the main reactor to reduce sulfur compounds. A desulfurization catalyst used in the preliminary or main reactor is recovered by a catalyst regeneration device, reacted with an oxidant for continuous regeneration, and then recycled to the prereactor and the main reactor for recycling. The desulfurization catalyst used in the main reactor is regenerated by contacting with an oxidizing agent such as air, oxygen, ozone or hydrogen peroxide using a venturi device to maximize the desulfurization efficiency of the desulfurization device and method, and injected into the catalyst regeneration device. By supplying the catalyst to the powder by air flow And significantly reduce the power ratio, to provide an improved performance apparatus and a method of sulfur compound removal device of the processing target gas by installing a methane separation concentrator to increase the added value of the methane fuel.

Description

Method and improving performance and device of sulfide removal device

The present invention is a sulfur compound removal device for desulfurizing by contacting anaerobic digester gas and landfill gas with a reaction liquid containing a desulfurization catalyst, catalyst regeneration device using a venturi device, pre-reactor, oxygen supply device, methane separation and concentration device, etc. It is to provide a performance improving apparatus and method comprising a.

When sulfur compounds present as gaseous contaminants in anaerobic digester and landfill gas, and wastes containing sulfur components in the gasification melting method of waste are incinerated in a high-temperature melting furnace, hydrogen sulfide (H) ₂ S), mercaptans (a reducing sulfur compound, such as also known as RSH, thiol) is left punggigo odors to be removed because it is harmful to the human body.

Currently, commercially available sulfur compounds are removed in two types: dry adsorption and wet absorption.

In the adsorption and removal method of sulfur compounds, the gas to be treated is removed by contacting with a solid adsorbent such as iron oxide (Fe ₂ O ₃ ) and activated carbon.The adsorption performance is excellent at low temperatures and low humidity, but heat is generated when treating a high concentration of material. There is this badly occurring problem. In addition, the adsorption performance is significantly reduced when the temperature of the gas is high, and when the gas is treated with high humidity, the adsorption efficiency is drastically deteriorated due to adsorption obstruction or channeling phenomenon due to moisture.

Absorption is a technique for removing sulfur compounds by contacting gas and liquid (absorbent) in countercurrent or cocurrent flow through a cleaning device. The caustic soda method and the liquid phase oxidation method are commercially available. Caustic soda method is the oldest technology, one of the most common in the past because of its easy operation and high performance. However, the disposal cost of waste caustic soda after use is expensive, and it is classified as uneco-friendly technology because excessive caustic soda is consumed due to reaction with carbon dioxide in anaerobic digester and excessive operating cost and excess alkali caustic soda are generated. Therefore, the diffusion of technology is suspended in developed countries. On the other hand, liquid phase oxidation is a method of radically reducing sulfur compounds in an anaerobic digestion tank by converting sulfur compounds (hydrogen sulfide, mercaptan, etc.) into harmless and odorless sulfur by using environmentally friendly solid or liquid catalysts.

In order to solve this problem, two domestic patents, such as Korean Patent Publication Nos. 10-762715 and 10-780904, have been filed and registered by the inventors and applicants of the present invention.

Korean Patent Publication No. 10-762715 relates to a digestion gas desulfurization and catalyst regeneration apparatus and a method thereof, wherein a sulfur oxide compound in an anaerobic digester is removed by a liquid oxidation catalyst, but the oxidation catalyst action of the sulfur compound contained in the primary reactor is activated. The present invention relates to a digestion gas desulfurization method and apparatus for reducing sulfur compounds by converting sulfur compounds into harmless and odorless sulfur by an oxidation catalyst in a second reactor, and the desulfurization catalyst used in the first or second reactor is It was to provide a catalyst regeneration method and apparatus that was recovered to the regeneration process unit to perform a continuous regeneration to react with the oxidant and then recycled to the first and second reactors to be recycled.

Patent No. 10-780904 discloses a main reactor for oxidizing a sulfur compound in a gas to be treated by contacting a gas to be treated with a reaction liquid containing a slurry of a solid desulfurization catalyst, and contacting the solid desulfurization catalyst used with an oxidant. And a catalyst supply device for supplying a slurry of the solid desulfurization catalyst to the main reactor, and a catalyst regeneration device for regenerating the waste material and partially discharging it to the spent catalyst.

However, the two registered patents also had a poor removal efficiency of sulfur compounds. In order to improve the inventors, the inventors of the two registered patents continued to conduct an in-depth study to derive the present invention.

The present invention provides an apparatus and a method for improving the performance of a sulfur compound removing apparatus for removing an sulfur compound while oxidizing sulfur dioxide by contacting an anaerobic digester gas containing a sulfur compound and a landfill gas with a reaction liquid containing a desulfurization catalyst. The sulfur compound removal device includes a main reactor for oxidizing sulfur compounds while contacting a treatment gas containing sulfur compound with a reaction liquid containing a catalyst, a catalyst regeneration device for regenerating a desulfurization catalyst used in the main reactor, and disposed in front of the main reactor. Although pre-reactors that increase the efficiency of sulfur compound treatment in kitchen reactors by primarily treating sulfur compounds by using catalysts, and catalyst supply devices that supply a mixture of catalyst and water to a catalyst regeneration device, are mainly used according to the type and supply method of oxidant. The catalyst regeneration efficiency in the regeneration device and the desulfurization performance in the main reactor are different, and the mixing ratio of the catalyst and water is supplied by the catalyst feeder to adjust the mixing ratio. Problems have been pointed out. There is a problem in that renewable fuel such as methane is wasted in the generated exhaust gas.

In order to solve the above problems, the venturi device is installed on the discharge pipe of the pump which sends the catalyst used in the main reactor to the catalyst regeneration device, and automatically sucks air by the transport force of the fluid and mixes it with the catalyst slurry. The catalyst can be regenerated with high efficiency, and the catalyst regeneration device transfers the desulfurization catalyst to the catalyst regeneration device in the form of powder by air flow to solve the problems caused by the pre-mixing of the catalyst and water. Provided are an apparatus and a method for improving the performance of a sulfur compound removing device treated with a methane separation thickener.

By using the apparatus and method for improving the performance of the sulfur compound removing device of the present invention, sulfur compounds such as hydrogen sulfide and mercaptan present in the gas to be treated can be efficiently removed and the catalyst regeneration process can be used to extend the life of the desulfurization catalyst. You can dramatically reduce your usage. A venturi device is installed on the discharge pipe of the pump that sends the catalyst used in the main reactor to the catalyst regeneration device, and the air is automatically sucked by the conveying force of the fluid and mixed with the catalyst slurry so that the catalyst can be recycled with high efficiency. And since it does not require an acid generator, power cost can be drastically reduced, and problems such as water temperature rise and clogged acid pipes can be maintained, so that the desulfurization performance in the main reactor can be kept constant. Dissolved oxygen concentration can be maintained to reduce the regeneration time of the catalyst to less than half, and therefore, when desulfurizing the same capacity of gas, the regeneration apparatus can be miniaturized to 1/2. In addition, the basic wastewater / waste catalyst can be used to remove the acid in the gas to be treated, which is an environmentally friendly device and method that can suppress or minimize the use of basic compounds. When the sulfur compound removal apparatus and method of the present invention is applied to a high temperature melting furnace incineration apparatus, it is possible to improve the overall economics of the high temperature melting equipment. In addition, the present invention can significantly reduce the capacity of the reactor by improving the desulfurization of the reactor by additionally supplying air or oxygen in the air, it is possible to significantly reduce the power consumption by adding a catalyst air flow transfer device By installing a methane separation and concentration device, it is possible to increase the added value of renewable fuel.

end. Brief description of the drawing (correction)
1 is an embodiment of the present invention having a venturi device
2 is an embodiment of the present invention with a pre-reactor
Figure 3 is an embodiment of the present invention with an oxygen supply device
4 is a diagram showing an entire embodiment of the present invention.
5 is one embodiment of the methane separation concentration device
Figure 6 is one embodiment methane separation concentrated system with a dehumidifier
7 is a graph comparing the dissolved oxygen concentration according to Example 1
8 is a graph showing desulfurization performance of a catalyst according to oxygen concentration change according to Example 2

The present invention relates to a main reactor for oxidizing sulfur compounds while contacting an anaerobic digester gas containing a sulfur compound and a landfill gas with a reaction solution containing a desulfurization catalyst, and the desulfurization catalyst used in the main reactor using air, oxygen, and ozone. Or a catalyst regeneration device for contacting with an oxidizing agent containing at least one or more of hydrogen peroxide, the catalyst regenerating device for supplying a desulfurization catalyst, and a catalyst regeneration device for recharging the spent catalyst to a waste catalyst. It is about.

The present invention will be described in detail with reference to the illustration of FIG. 1. The catalyst used in the main reactor 1 is sent to the catalyst regeneration device 20 for regeneration of the catalyst. In the catalyst regeneration device, an oxidant such as air, oxygen, ozone or hydrogen peroxide is contacted with the used catalyst for regeneration. At this time, the catalyst regeneration efficiency in the regeneration apparatus and the desulfurization performance in the main reactor 10 vary according to the type and supply method of the oxidizing agent. Maintaining a high concentration of the oxidizing agent in the catalyst regeneration apparatus 20 improves the contact efficiency with the catalyst, thereby smoothly regenerating the catalyst, thereby maintaining high desulfurization performance in the main reactor 10.

However, in the case of regeneration using chemicals, a lot of chemical costs are required to improve the efficiency, and when using oxygen or ozone, there is a problem of using a separate generating device. It is common to regenerate a catalyst by dissolving oxygen in air in a catalyst slurry by aeration.

However, when the air is aerated using the blower and the air diffuser, the water temperature of the catalyst regeneration device 20 increases due to the heat of compression of the blower, so that the oxygen solubility gradually decreases, and the air diffuser efficiency is blocked by the fine catalyst powder. There is a problem that this is lowered and the efficiency of the catalyst regeneration device 20 is reduced.

Therefore, the venturi device 30 is installed on the discharge pipe of the pump which sends the catalyst used in the main reactor 10 to the catalyst regeneration device 20, and automatically sucks air by the fluid transfer force and mixes the catalyst with the slurry. Can be recycled with high efficiency. In this case, since the concentration of sulfur compound in the gas treated in the main reactor 10 is high, a large amount of oxidant is required, and when the amount of air sucked by the catalyst liquid transferred to the catalyst regeneration device 20 is insufficient to regenerate the catalyst, the catalyst It is possible to install a separate catalyst liquid circulation pump and a venturi device 30 in the regeneration device 20 to regenerate the catalyst with high efficiency. In addition, since there is no need for a separate blower and an air diffuser, the power cost can be drastically reduced, and problems such as water temperature rise and clogging of an acid pipe can be maintained, so that the desulfurization performance in the main reactor can be kept constant, and a catalyst regeneration device ( At 30), the dissolved oxygen concentration can be maintained about twice as high as that of the acid generator, and the regeneration time of the catalyst can be reduced to less than half. Therefore, when desulfurizing the same capacity of gas, the regeneration apparatus can be reduced to 1/2. Do.

In the present invention, the catalyst regeneration device 20 includes a catalyst supply device 40 for supplying the desulfurization catalyst in powder form by air flow transfer. The catalyst supply device 40 also passes through the venturi device while blowing air into the blower, and installs the venturi device to automatically inhale the catalyst by the conveying force of the air to move the catalyst regeneration device 20 and separate the water into the catalyst. By injecting into the regeneration apparatus 20, it is possible to solve a problem in the process such as adjusting the mixing ratio according to the pre-mixing of the catalyst and water in the prior art to the catalyst transfer apparatus.

In addition, when the catalyst is directly supplied to the catalyst regeneration device 20 as an air flow transfer device using a venturi device, it is possible to drastically improve the operation power ratio of the device. Conventionally, the catalyst supply device of the desulfurization process was a catalyst suspension supply device for supplying water and powder catalyst after a constant concentration was made using a stirring tank, but the catalyst supply device was used to directly supply a catalyst in a powder state to a desulfurization system using a venturi device. Compared to the conventional suspension feeder, the airflow feeder has less power drive than the conventional suspension feeder, and the power consumption is reduced by 1/3, and the larger the desulfurization system, the greater the operating cost. to be.

Another embodiment of the present invention will be described with reference to FIG. The sulfur compound further comprises a pre-reactor 50 for oxidizing the sulfur compound by contacting the waste catalyst discharged from the catalyst regeneration device 20 with the gas to be treated and moving the oxidized gas to the main reactor 10. Provide a removal device.

The liquid phase oxidation catalyst used in the pre-reactor 50 and the main reactor 10 is a solid alkaline earth metal oxide such as magnesium oxide (MgO), calcium oxide (CaO), tin oxide (SrO), and barium oxide (BaO). In which at least one component selected from the group consisting of transition metals iron, zinc, molybdenum, manganese, copper and oxides thereof is supported on the support, in the group consisting of alkali metal hydroxides and iron chelates At least one shall be included. And the supported amount of the transition metal or its oxide is used in the range of 0.1 to 50% by weight based on the total solid catalyst. The desulfurization catalyst according to the present invention is referred to as C, and the reaction between the desulfurization catalyst in water and the sulfur compound in the digester gas is as follows.

As in the reaction, a desulfurization catalyst is used to convert sulfur compounds such as hydrogen sulfide and mercaptan into harmless elemental sulfur. In the above reaction, since oxygen is used for regeneration of the catalyst, it is applied to the catalyst regeneration device 20 for supplying an oxidizing agent such as oxygen, air, ozone, or hydrogen peroxide to the desulfurization catalyst slurry, thereby improving the performance and lifetime of the catalyst by the sulfur compound. In the case of supplying the oxidant to the catalyst regeneration device, the venturi device 30 was used to improve the use of a separate feeder to supply the oxidant. In addition to the sulfur component, the anaerobic digester gas contains siloxane (Siloxane) and various volatile organic compounds (Volatile Organic Compounds) to accelerate the catalyst deactivation by the phenomenon that they cover the catalytic active surface. Electron microscopy observed that a polymeric material, such as siloxane, covered the surface of the catalyst. Therefore, by regenerating the catalyst in the main reactor after the regeneration of the catalyst discharged to the spent catalyst to the pre-treatment process of the pre-reactor 50 to react to delay the catalyst deactivation by polymer foreign substances such as siloxane and the pre-reactor (50) By removing a certain amount (about 30 to 50%) of the sulfur compound in the main reactor (50) to increase the reaction efficiency and maximize the utilization of the catalyst can significantly reduce the amount of catalyst used.

In the present invention, the pre-reactor 50 and the main reactor 10 are selected from among scrubbers, slurry reactors, packed columns, or sieve plate type reactors. In the desulfurization apparatus configured as described above, the desulfurization reaction may be performed by using a catalyst used in the preliminary reactor 50 to maximize the removal of sulfur compounds by the oxidation catalyst in the main reactor 10. do. When desulfurization is carried out using only the main reactor 10 when the same amount of catalyst is used, desulfurization up to a level of 88% is possible, whereas when the main and prereactors 10 and 50 are used, 50% is used in the preliminary reactor 50. Since the desulfurization can proceed to the level, the main reactor 10 has the advantage of being able to desulfurize up to a final level of about 98%.

Another embodiment of the present invention will be described with reference to FIG. It is characterized in that it further comprises an oxygen supply device 60 for supplying the treatment target gas mixed with oxygen to the treatment target gas to the main reactor (10). The oxygen supply device 60 may be installed at the preliminary stage of the pre-reactor 50, supply pure oxygen, separate oxygen using an air separator, and supply oxygen, or supply air.

Specifically, referring to FIG. 3, the oxygen supply through the oxygen supply device 60 is additionally supplied to the digester gas and the landfill gas into the pre-reactor 50, and the oxygen supply amount through the oxygen supply device 60 is It is possible to supply in a range that does not reach the combustion limit of the gas. For example, a gas with a methane content of 50 parts by volume can be mixed up to 50 parts by volume of oxygen with respect to 100 parts of gas. However, when the mixing ratio of oxygen is increased, the performance in the desulfurization apparatus is improved, but the capacity of the air separation apparatus is increased, and the amount of processing gas is increased, which makes economic treatment difficult. Therefore, the mixing ratio of oxygen is preferably mixed at a fraction of 5 to 20 volumes of oxygen with respect to 100 volumes of gas. Given that the oxygen concentration of the digester gas and landfill gas is generally 2v / v% or less, it is possible to maintain 3 times higher desulfurization performance when maintaining the oxygen concentration at 10v / v%, thus desulfurizing the same capacity of gas. In this case, the size of the reactor and the regeneration process can be reduced to 1/3.

Another embodiment of the present invention will be described with reference to FIG. The present invention includes a pre-reactor 50 and the oxygen supply device 60 transfers the gas to be treated to the pre-reactor 50 mixed with oxygen, the pre-reactor 50 in the catalyst regeneration device 20 The waste catalyst discharged is contacted with the gas to be treated to oxidize the sulfur compound, and the oxidized gas to be treated is transferred to the main reactor 10.

Hereinafter, referring to FIG. 4, the material balance of the gas to be treated may be summarized as shown in Table 1 below in each step ① to ⑤ step of the performance improving apparatus and method of the sulfur compound removing device of the present invention. ① step is a step of injecting the gas to be treated into the pre-reactor 50, ② step is to remove the oxygen in the air using the oxygen supply device 60 to remove the oxygen in the pre-reactor 50 to inject Mixing step 3, step 3 is injecting the mixed gas into the pre-reactor 50, the step ④ is the step of transferring the reaction gas of the pre-reactor 50 to the main reactor 10, step ⑤ Is composed of the step of discharging the reaction gas of the main reactor (10).

Step by step ① ② ③ ④ ⑤ CH ₄ 50-70% 44.7 ~ 63% 45.2 ~ 63% 45.5-63.7% CO ₂ 27-50% 25-44.7% 25-45.2% 25.3-45.5% H ₂ S 0.02-0.3% 0.02-0.3% <0.1% <0.005% O ₂ <0.2% 90-99% 8.4-9.2% 7.6-8.4% 6.8-7.5% N ₂ <0.9% 1 to 10% 0.9-1.7% 0.9-1.6% 0.9-1.6% Gas volume 100 Nm ³ / hr 10 Nm ³ / hr 110 Nm ³ / hr 109 Nm ³ / hr 108Nm ³ / hr

Step ① shows the general gas composition of the digester gas and landfill gas, the oxygen supply in step ② can be supplied in a range that does not reach the combustion limit of the gas. For example, a gas with a methane content of 50% by volume can be mixed up to 50% by volume of oxygen with respect to 100% of gas. However, when the mixing ratio of oxygen is increased, the performance of the desulfurization apparatus is improved, but the capacity of the air separation apparatus is increased, and the amount of processing gas is increased, which makes economic treatment difficult. Therefore, the mixing ratio of oxygen is preferably mixed at 5 to 20% by volume of oxygen with respect to 100% by volume of gas.

Another embodiment of the present invention will be described with reference to FIG. In the sulfur compound removal apparatus of the present invention, the gas to be treated is brought into contact with a reaction solution including a desulfurization catalyst to transfer the gas to which the sulfur compound is removed to a methane separation concentration system, and methane of high purity is separated and concentrated in the methane separation concentration system. The methane separation and concentration system is composed of an adsorption tower, a gas compressor, and a methane separation and concentration device as shown in FIG. 5, and a dehumidification device is installed between the desulfurization and regeneration device and the adsorption tower as shown in FIG. Characterized in that the transfer to the separation thickening device.

In a methane separation enrichment system, the off-gas is separated into methane and CO ₂ gas and methane can be reused as a high value added fuel. The added value of fuel can be increased by adding a system to separate and concentrate methane from gas after desulfurization of the digester gas and landfill gas.In this case, the methane separation and concentration system operates at a high pressure of 5 to 7 atm, so that the digester can be safely operated. It is preferable not to mix oxygen and process gas and landfill gas. The methane separation concentrator may use a two-stage or three-stage membrane device, or a PSA (Presure Swing Absorbtion) device that separates by adsorption and desorption at high pressure on a molecular sieve. Methane separation concentrator by removing trace impurities such as hydrogen sulfide, water, siloxane, etc. by installing gas cooling device and adsorption column before introducing desulfurization gas into methane separation concentrator such as membrane device or PSA. Can increase the operational efficiency.

In addition, the present invention comprises the steps of (1) the anaerobic digester gas containing sulfur compounds and the gas to be treated such as landfill gas mixed with oxygen supplied from the oxygen supply device to the pre-reactor, (2) the pre-reactor is discharged from the catalyst regeneration device Contacting the waste catalyst with the gas to be treated to oxidize the sulfur compound, and transferring the oxidized gas to the main reactor, (3) in the main reactor, by contacting the gas to be treated with the reaction solution containing the desulfurization catalyst, Oxidizing, (4) regenerating the desulfurization catalyst used in the main reactor by contacting with an oxidizing agent containing at least one of air, oxygen, ozone or hydrogen peroxide using a venturi device, and partially discharging it to the spent catalyst. (B) feeding the desulfurization catalyst to the catalyst regeneration apparatus in the form of powder by air flow, (6) removing sulfur compounds The present invention relates to a method for improving the performance of a sulfur compound removing device comprising a step of transferring the treated gas from which sulfur compounds are removed from the fuel to a methane separation concentration system consisting of a dehumidifier, an adsorption tower, a gas compressor, and a methane separation concentrate.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are intended to illustrate the present invention more specifically, but the present invention is not limited by the following examples.

When the desulfurization catalyst used in the main reactor was regenerated in the catalyst regeneration device, the dissolved oxygen concentration in the regeneration device was measured to determine the regeneration efficiency according to the regeneration method. At this time, the amount of air supplied was 6 L / min for the air diffuser and 3.6 L / min for the venturi device. In the case of the diffuser, the dissolved oxygen concentration of the regenerator was 1.4 mg / L at 1 hour after the regenerator was operated. In the case of the venturi device, the dissolved oxygen concentration of the regenerator was 2.9 mg / L even though lower air was supplied. As L, the result was more than twice as high as the diffuser, and it was confirmed that such performance difference persists. Therefore, in the case of desulfurization of the same capacity of gas, the regeneration process using the venturi device can be miniaturized to less than 1/2 compared to the process using the conventional air dispersing device. The result is shown in FIG.

In order to confirm the change of desulfurization performance according to the oxygen mixing ratio in the digester gas and the landfill gas, the removal performance of hydrogen sulfide according to the oxygen concentration was compared using a 6% iron / magnesium oxide (Fe / MgO) catalyst. At this time, the catalyst was suspended in a 250 ml washing bottle, and desulfurization performance was measured while flowing a gas having a different mixing ratio of nitrogen and oxygen into the washing bottle. The total gas was 5 L / min, the hydrogen sulfide concentration was 1000 ppm, and the concentration of oxygen in nitrogen gas was changed from 0 to 20.8 v / v%.

Desulfurization efficiency lasted more than 85% for gas without oxygen, but 35 minutes for 5v / v% oxygen and 60 minutes for 10v / v% oxygen. When 20.8v / v% of oxygen was mixed, the desulfurization efficiency of 95% or more was maintained for 2 hours or more. Considering that the oxygen concentration of digester gas and landfill gas is generally 2v / v% or less, it was confirmed that 3 times higher desulfurization performance can be maintained when oxygen concentration is 10v / v%. Therefore, when desulfurizing the same capacity of gas, it is possible to reduce the size of the reactor and the regeneration process to 1/3. The result is shown in FIG. 8.

Digester gas and landfill gas are commonly used as fuel for boilers or power plants. Therefore, in Example 3, when the composition of the combustion gas, the amount of combustion gas, and the amount of combustion air generated when the gas is used as the boiler fuel after desulfurization treatment using the general composition of the digester gas and the landfill gas are not adjusted to the oxygen concentration in the digester gas and the landfill gas And the case of adjusting the oxygen concentration were compared. At this time, the composition of fuel gas was based on wet gas with CH ₄ 60.9%, CO ₂ 32.5%, N ₂ 0.9%, O ₂ 0.2%, H ₂ O 5.6%, and oxygen was supplied to this gas to supply oxygen of the mixed gas. When the concentration was adjusted to 10.3% and 20%, the excess air ratio was set to 1.2.

Oxygen 10% mixed gas has a 17.8% reduction in the amount of gas released after combustion and a 19.4% reduction in the amount of air required for combustion. The 20% oxygen mixed gas reduces the amount of gas emitted after combustion by 35% compared to before mixing, and reduces the amount of air required for combustion by 38.7%. When the amount of gas emitted after combustion decreases, it is economical because the exhaust gas aftertreatment process for treating pollutants present in combustion flue gas such as nitrogen oxides (NOx) is small.

Comparative Table of Combustion Air Content and Chlorine Gas Content according to Oxygen Content in Desulfurization Mixture Gas Gas before oxygen mixing Oxygen 10% Mixed Gas Oxygen 20% Mixed Gas Combustion
gas
Furtherance N ₂ 75.7% 74.1% 71.9% O ₂ 3.9% 3.8% 3.7% CO ₂ 20.4% 22.1% 24.5% Combustion air volume 0.31Nm ³ / Nm ³ 0.25 Nm ³ / Nm ³ 0.19Nm ³ / Nm ³ Combustion gas volume 6.62Nm ³ / Nm ³ 5.44Nm ³ / Nm ³ 4.30Nm ³ / Nm ³

Example 3 relates to a system for separating and concentrating methane in gas after desulfurization of digester gas and landfill gas. As shown in FIG. 5, the methane separation and concentration system includes the septic tank gas and the landfill gas through the desulfurization and regeneration device, the gas cooling device, the adsorption tower, the gas compressor, and the methane separation concentration device. Collected and separated by gas, the material balance of each step was obtained as shown in Table 3 below. In Example 3, as the source gas, a digester gas was used, a gas cooling device and an adsorption tower were installed to remove trace impurities such as hydrogen sulfide, water, and siloxane remaining in the digester gas, followed by methane separation concentration using a membrane device. .

  Material Balance Table in Methane Separation Concentration System ㉮ ㉯ ㉰ ㉱ ㉲ ㉳ ㉴ CH ₄ 50-70% 50-70% 50-70% 50-70% 50-70% 95-98% 2-5% CO ₂ 20-50% 20-50% 20-50% 20-50% 20-50% 0.3-5% 95-98% H ₂ S 0.02-0.4% <0.01% <0.01% <0.0001% <0.0001% N.D. - O ₂ <0.2% <0.2% <0.2% <0.2% <0.2% <0.1% - N ₂ <0.9% <0.9% <0.9% <0.9% <0.9% <0.9% - moisture 5.5-7.3% 5.5-7.3% <0.8% <0.1% <0.05% - N.D. gas
pressure 250 ~ 350mmH ₂ O 250 ~ 350mmH ₂ O 250 ~ 350mmH ₂ O 150 ~ 250mmH ₂ O 5 ~ 7kg / cm ² 5 ~ 7kg / cm ² -

The added value of fuel can be increased by adding a system that separates and digests the digester gas and landfill gas in the gas after desulfurization treatment.In this case, the separated concentration system operates at a high pressure of 5 to 7 atm, so that the digester gas and landfill can be safely operated. It is preferable not to mix and process in gas.

10 Main reactor 20 Catalytic regeneration unit 30 Venturi unit 40 Catalyst supply unit 50 Pre-reactor 60 Oxygen supply unit

Claims (9)

Oxygen supply device for supplying oxygen to anaerobic digester gas or landfill gas containing sulfur compound to transfer mixed gas to main reactor, contacting the transported gas with reaction liquid containing desulfurization catalyst to oxidize sulfur compound Catalytic regeneration apparatus and desulfurization in which the desulfurization catalyst used in the main reactor and the main reactor is contacted with an oxidizing agent containing at least one or more of air, oxygen, ozone or hydrogen peroxide by using a venturi device, and some are discharged to the spent catalyst. An apparatus for improving the performance of a sulfur compound removing device comprising a catalyst supply device for supplying a catalyst.

The apparatus of claim 1, further comprising a catalyst supply device for supplying the desulfurization catalyst to the catalyst regeneration device in the form of powder by airflow.
The method of claim 1, further comprising a pre-reactor for contacting the waste catalyst discharged from the catalyst regeneration device with the gas to be treated to oxidize the sulfur compound, and transfer the oxidized gas to the main reactor. Performance improvement device for sulfur compound removal device.
delete The apparatus of claim 1, further comprising a pre-reactor, wherein the oxygen supplying device transfers oxygen-treated gas to the preliminary reactor, and the pre-reactor carries the waste catalyst discharged from the catalyst regeneration device. And a sulfur compound to oxidize and transfer the oxidized treatment gas to the main reactor. The apparatus of claim 1, further comprising a methane separation and concentration system in the sulfur compound removal apparatus.
The apparatus of claim 6, wherein the methane separation and concentration system comprises an adsorption tower, a gas compressor, and a methane separation and concentration device.
8. The apparatus of claim 7, wherein the methane separation and concentration system further comprises a dehumidifier.
(1) transporting the gas to be treated, such as anaerobic digester gas and landfill gas, containing sulfur compounds, to the pre-reactor by mixing oxygen supplied from the oxygen supply device; (2) the pre-reactor treats waste catalyst discharged from the catalyst regeneration device. Contacting the target gas to oxidize the sulfur compound and transferring the oxidized treated gas to the main reactor, (3) oxidizing the sulfur compound while contacting the treated gas with a reaction solution containing a desulfurization catalyst in the main reactor; (4) a catalytic regeneration device in which the desulfurization catalyst used in the main reactor is regenerated by contacting with an oxidizing agent containing at least one of air, oxygen, ozone or hydrogen peroxide using a venturi device, and partly discharged to the spent catalyst, ( 5) feeding the desulfurization catalyst in powder form by air flow to the catalyst regeneration device, (6) sulfur sulfide in the sulfur compound removal device. Performance improved method of processing the gas to the dehumidifier, the adsorption tower, a gas compressor, the methane separation apparatus and concentrated to remove sulfur compounds consisting of the step of conveying the concentrated methane separation system consisting of removing the device.

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