KR101451910B1 - Agent for removing hydrogen sulfide and recycling method of the same - Google Patents

Abstract

The present invention provides a method of recycling a hydrogen sulfide remover, which is characterized by including the steps of: mixing yellow soil powder including iron oxide (Fe_2O_3), aluminum oxide (Al_2O_3) and silicon oxide (SiO_2), limonite including protein, carbohydrate and fat, and water and extruding the resultant mixture to prepare a hydrogen sulfide remover in a pellet shape; mixing the hydrogen sulfide remover with an object from which hydrogen sulfide is to be removed, to absorb hydrogen sulfide; collecting the hydrogen sulfide remover on which hydrogen sulfide be absorbed, to pulverize the hydrogen sulfide remover; neutralizing and recycling the hydrogen sulfide remover pulverized in a powder state; and drying the recycled hydrogen sulfide remover and supplementing yellow soil powder to prepare a hydrogen sulfide remover, wherein the iron oxide (Fe_2O_3) is included in 40 to 65% by weight. Accordingly, hydrogen sulfide that is a main cause of odor among domestic pollution can be effectively absorbed to be removed. A hydrogen sulfide remover includes yellow soil powder as a main ingredient, thereby removing, and also ammonia, oil, and phosphorus can be removed due to porosity, thereby effectively treating livestock excretion. In addition, a hydrogen sulfide remover can be prepared simply at low cost, and hydrogen sulfide remover on which hydrogen sulfide is adsorbed, can be recycled to be used.

Description

A hydrogen sulfide removing agent and a hydrogen sulfide removing agent regeneration method,

The present invention relates to a method for regenerating a hydrogen sulfide removing agent and a hydrogen sulfide removing agent capable of removing hydrogen sulfide which is a main component of an offensive odor during livestock pollution, and more particularly, to a method for regenerating hydrogen sulfide To a regeneration method of a hydrogen sulfide removing agent capable of neutralizing an adsorbed hydrogen sulfide removing agent and regenerating it again as a hydrogen sulfide removing agent.

The livestock industry has serious problems such as odor, dust, and housing drainage, which are called livestock pollution. The harmful gases generated in the breeding environment of livestock include ammonia, carbon dioxide (CO ₂ ), carbon monoxide (CO), sulfur dioxide (SO ₂ ), methane (CH ₄ ) and hydrogen sulfide (H ₂ S). The effect of sulfur dioxide and methane on the odor is insufficient, but hydrogen sulfide is a colorless gas with a serious odor and is normally produced by the decay of sulfur-containing proteins, which is a major obstacle to the livestock industry.

Due to the development of the livestock industry, the scale of the livestock facilities has been enlarged and the problems caused by the odor of the livestock facilities have been continuously increasing due to the expansion of people's residence. In addition, it is necessary to develop a remover that effectively adsorbs and removes hydrogen sulphide because it is a hydrogen sulphide as a main cause of the odor generated in the composting process of the food and livestock manure as well as the livestock facility.

On the other hand, loess is also called Loess, which means that the rocks deposited in the desert or glacier were carried by the wind and deposited. It is light yellow, yellowish brown or brownish, and its color varies depending on its composition. The loess has a particle diameter of 0.004 to 0.06 mm usually, and is formed of a porous material. The mineralogical characteristics of the loess have a tendency to vary depending on the kind of the origin rock and the degree of weathering, and thus have a different composition depending on the calculated location.

In Korea, diatomaceous earth and soil containing iron oxide are produced in large quantities. In particular, yellow loess in Jeollanamdo province tends to have strong red color because it contains a lot of iron oxide. The constituents of the loess include minerals, amorphous materials and organic matter, and clay minerals, quartz and other minerals in the minerals.

The porosity of the loess is known to be effective for adsorbing various substances, and in Korean Patent No. 10-0357765, a deodorizing filter composed of one or more of nonwoven fabric, activated carbon, zeolite, .

However, the produced deodorization filter has a disadvantage that the deodorization effect on hydrogen sulfide is not large and the deodorization filter can not be used again. Therefore, there is a need for a method capable of regenerating and using the hydrogen sulfide removing agent because the malodor removing performance is increased, the manufacturing efficiency is good, and the like.

The present invention provides a hydrogen sulfide removing agent capable of removing odor which is a big problem of livestock pollution by using yellow loess having a large amount of iron ion content and is also capable of regenerating a hydrogen sulfide removing agent adsorbing hydrogen sulfide through a simple process, A method is provided.

The present invention, iron oxide (Fe ₂ O _3), aluminum oxide (Al ₂ O ₃₎ and silicon oxide ocher powder comprising a (SiO _2), a pellet by mixing galcheolseok and water containing protein, carbohydrate and fat, and extruding Lt; RTI ID = 0.0 > hydrogen sulfide < / RTI > Mixing the hydrogen sulfide removing agent with a hydrogen sulfide removing object to adsorb hydrogen sulfide; Recovering and pulverizing the hydrogen sulfide-removing agent adsorbed by hydrogen sulfide; Neutralizing and recovering powdered hydrogen sulfide scavenger; And a step of drying the regenerated hydrogen sulfide removing agent and replenishing the loess powder to prepare a hydrogen sulfide removing agent, wherein the iron sulfide (Fe ₂ O ₃ ) is contained in an amount of 40 to 65 wt% .

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The step of preparing the hydrogen sulfide removing agent may further include the step of collecting the loess powder and drying it for 3 years in the exposure.

In addition, in the step of neutralizing and regenerating the hydrogen sulfide removing agent, an alkali solution may be added, and air may be blown in to adsorb sulfur to change the water solubility of the hydrogen sulfide removing agent that has been insolubilized.

Also, the alkali solution can be characterized by at least one selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH ₄ OH) and lithium hydroxide (LiOH).

The hydrogen sulfide removing agent according to the present invention can adsorb and remove hydrogen sulfide, which is a main cause of odor during livestock pollution, very efficiently. It is possible to remove odor by using loess powder as a main component, and it is possible to remove ammonia, oil and phosphorus because of porosity, and is very effective in the treatment of animal manure. In addition, it can be produced at low cost with simple production, and the hydrogen sulfide-removing agent capable of adsorbing hydrogen sulfide can be regenerated again through the neutralization process.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing yellow soil powder as a raw material of a hydrogen sulfide removing agent according to an embodiment of the present invention. FIG.
FIG. 2 is an SEM image of a yellow soil powder as a raw material of a hydrogen sulfide removing agent according to an embodiment of the present invention after being mined.
3 is a schematic diagram of an apparatus for measuring hydrogen sulfide removal efficiency.
FIG. 4 is a graph showing a breakthrough curve of hydrogen sulfide as a raw material of a hydrogen sulfide removing agent according to an embodiment of the present invention. FIG.
FIG. 5 is a graph showing breakthrough curves for hydrogen sulfide with different kinds of loess powder, which is a raw material of the hydrogen sulfide scavenger, according to an embodiment of the present invention.
FIG. 6 is a graph showing breakthrough curves of hydrogen sulfide in comparison with the same volume of activated carbon, which is the raw material of the hydrogen sulfide scavenger according to an embodiment of the present invention. FIG.
7 is a graph showing breakthrough curves of methyl mercaptan of loess powder and activated carbon, which are raw materials of a hydrogen sulfide scavenger, according to an embodiment of the present invention.
8 is a graph showing breakthrough curves of trimethylamine in yellow clay powder and activated carbon, which are raw materials of the hydrogen sulfide scavenger according to an embodiment of the present invention.
9 is a photograph showing a hydrogen sulfide removing agent according to an embodiment of the present invention.
10 is a flowchart illustrating a method of regenerating a hydrogen sulfide remover according to another embodiment of the present invention.

The inventor of the present invention confirmed that iron oxide (Fe ₂ O ₃ ) component was adsorbed by bonding with hydrogen sulfide while trying to remove hydrogen sulfide (H ₂ S) which is a main cause of bad odor in harmful gas generated in a living environment of livestock, The hydrogen sulfide scavenging agent with improved adsorption capacity was prepared by preparing the iron oxide component contained in the loess powder with the optimum composition. In addition, a method of regenerating a hydrogen sulfide removing agent to recover the hydrogen sulfide removing ability and the oil adsorption property through the neutralization treatment of the hydrogen sulfide absorbing remover was completed.

Hereinafter, the present invention will be described in detail with reference to examples.

The present invention relates to a method of mixing and extruding calcite and water containing ocher powder, proteins, carbohydrates and fats comprising iron oxide (Fe ₂ O ₃ ), aluminum oxide (Al ₂ O ₃ ) and silicon oxide (SiO ₂ ) Of a hydrogen sulfide removing agent; Mixing the hydrogen sulfide removing agent with a hydrogen sulfide removing object to adsorb hydrogen sulfide; Recovering and pulverizing the hydrogen sulfide-removing agent adsorbed by hydrogen sulfide; Neutralizing and recovering powdered hydrogen sulfide scavenger; And a step of drying the regenerated hydrogen sulfide removing agent and replenishing the loess powder to prepare a hydrogen sulfide removing agent, wherein the iron sulfide (Fe ₂ O ₃ ) is contained in an amount of 40 to 65 wt% .

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The step of preparing the hydrogen sulfide removing agent may further include a step of collecting the yellow loess powder and drying the exposed yellowish soil for 3 years.

In the drying step in the drying step, the specific surface area can be increased to 80 m 2 / g or more by weathering, erosion or the like due to air and ultraviolet ray, and the adsorption capacity of not only hydrogen sulfide gas but also oil can be increased.

The step of recovering and pulverizing the hydrogen sulfide-adsorbed hydrogen sulfide removing agent may be performed by pulverizing the hydrogen sulfide-removing agent adsorbed with hydrogen sulfide into 30 to 100 mesh and mixing with the hydrogen sulfide removing object in the form of powder.

The pelletized hydrogen sulfide removing agent is advantageous in transportation and storage, but it is preferable to increase the surface area through pulverization after hydrogen sulfide is adsorbed so that it can be easily separated from hydrogen sulfide.

In the step of neutralizing and regenerating the hydrogen sulfide removing agent, an alkali solution may be added, and air may be blown to adsorb sulfur to change the water solubility of the hydrogen sulfide removing agent that has been insolubilized.

Here, the alkali solution may be at least one selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH ₄ OH) and lithium hydroxide (LiOH).

When hydrogen sulfide is adsorbed on the hydrogen sulfide removing agent, sulfur is adsorbed on the iron ion. Since iron (Fe ₂ S ₃ ) is insoluble, it is difficult to precipitate and regenerate. However, when it is treated with an alkali solution, it becomes water-soluble iron hydroxide (Fe (OH) ₃ ) and can be regenerated.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

≪ Example 1 > Removal of hydrogen sulfide and regeneration of hydrogen sulfide removing agent

The hydrogen sulfide removing agent was reacted with hydrogen sulfide, methyl mercaptan, and trimethylamine gas. After the reaction, the deodorizing performance of the sulphated address remover was analyzed.

In order to measure the efficiency of the regeneration process of the hydrogen sulfide scavenger, the hydrogen sulfide scavenger was filled with the hydrogen sulfide scavenger instead of the activated carbon in the adsorption tower filled with the conventional activated carbon, and the hydrogen sulfide discharged from the livestock facility was passed through.

When the concentration of hydrogen sulfide discharged from the adsorption tower is 20 ppm or less, the hydrogen sulfide removing agent is separated from the adsorption tower, pulverized, and neutralized.

The neutralized hydrogen sulfide removing agent was dried, and yellowing powder was added to regenerate the hydrogen sulfide removing agent.

<Experimental Example 1> Analysis of efficacy and regeneration method of hydrogen sulfide scavenger

1. The efficacy of hydrogen sulphide remover

The composition of loess powder used as raw material was analyzed by Xray fluorescence spectrometry (XRF).

The composition of four different types of loess was investigated in order to determine loess with high efficiency of removal of hydrogen sulfide because loess has different composition depending on geological environment, hydrological environment, topography and climate.

Hwangto A was produced in Jeolla province and Hwangto B was produced in Gyeongsang province. Yellow soil C was dried at room temperature to compare the removal efficiency according to the moisture content. Hwangto D is derived from the Kyushu region of Japan.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing yellow soil powder as a raw material of a hydrogen sulfide removing agent according to an embodiment of the present invention. FIG.

Hwangto A Loess B Loess C Loess D Al ₂ O ₃ 27.09% 26.03% 27.58% 3.08% SiO ₂ 58.74% 60.71% 59.17% 12.48% Fe ₂ O ₃ 8.17% 7.42% 7.20% 71.69% Other residues 6% 5.84% 6.05% 12.75%

Table 1 is a table showing the major components of loess through XRF analysis.

As a result of analysis of the samples, the yellow loess A, B, and C contained 27 to 28 wt% of aluminum oxide, 58 to 60 wt% of silicon oxide, and 7 to 8 wt% of iron oxide. On the other hand, the yellow loess D contained much iron oxide as compared with other samples and was selected as the yellow loose powder constituting the inorganic substance of the hydrogen sulfide removing agent according to the present invention.

FIG. 2 is an SEM image of a yellow soil powder as a raw material of a hydrogen sulfide removing agent according to an embodiment of the present invention after being mined.

It was confirmed that porosity was increased when yellow loess powder was mined in the process of producing hydrogen sulfide removing agent and dried in exposure for 3 years.

The removal efficiency of odor components was measured with yellow loess A, B, C, and D.

3 is a schematic diagram of an apparatus for measuring hydrogen sulfide removal efficiency.

One of the two gas cylinders was filled with hydrogen sulphide. A gas cylinder filled with methylmercaptan or trimethylamine in addition to hydrogen sulfide was prepared to compare the degree of adsorption of sulfur.

The hydrogen sulfide, methyl mercaptan, and trimethylamine used herein were nitrogen gas balance gases adjusted to 150 to 300 ppm (Li Gas Co., Ltd.). The components were analyzed using gas chromatography (GC, HP, 5890 Series II). The detector used FPD (Flame Photometric Detector) for hydrogen sulfide and methyl mercaptan, and Flame ionization detector (FID) for trimethylamine. The inlet temperature was 180 ° C and the discharge temperature was 200 ° C.

The sample was pulverized to 30 to 100 mesh and put into a U-tube. In the lower part of the citrullus, a glass filter supported powder particles, while hydrogen sulfide, methyl mercaptan, and trimethylamine gas were passed at a flow rate of 50 ml / min.

The concentration of hydrogen sulfide discharged from the citrullus was measured by GC / FPD with 0.5 g of each sample.

4 is a graph showing breakthrough curves of hydrogen sulfide as a raw material of a hydrogen sulfide removing agent according to an embodiment of the present invention.

The results show that the concentration of hydrogen sulfide discharged from the citrus canal is higher than that of the nitrogen stream when more hydrogen sulfide is removed. This is because metal ions on the surface of the loess soil remove hydrogen sulfide by oxygen in the air.

FIG. 5 is a graph showing breakthrough curves for hydrogen sulfide with different types of loess powder, which is a raw material of the hydrogen sulfide removing agent, according to an embodiment of the present invention.

It was confirmed that most of the hydrogen sulfide was removed by using the yellow soil D. As a result of measuring the change of the weight of the loess, the weight of loess D was increased by about 30%.

6 is a graph showing breakthrough curves of hydrogen sulfide in comparison with the same volume of activated carbon, which is the raw material of the hydrogen sulfide scavenger according to the embodiment of the present invention.

The activated carbon (manufactured by Kurary) was used without being processed and used as it was. When the same volume was used, the same amount of hydrogen sulfide removal rate was exhibited by the activated carbon or the loess for air conditioning.

7 is a graph showing the breakthrough curves of methyl mercaptan of the loess powder and activated carbon, which are raw materials of the hydrogen sulfide scavenger, according to an embodiment of the present invention.

As shown in the drawing, when the same volume was used, the ocher powder showed methylmercaptan removal efficiency almost similar to that of activated carbon even for methylmercaptan.

8 is a graph showing breakthrough curves of trimethylamine in the yellow coal powder and the activated carbon, which are raw materials of the hydrogen sulfide scavenger according to the embodiment of the present invention.

It was confirmed that the same volume of raw material, Hwangto, and the air-conditioning activated carbon showed almost the same adsorption capacity.

Therefore, it was confirmed that the hydrogen sulfide scavenger prepared from the loess powder was also able to adsorb to methyl mercaptan and trimethylamine in addition to hydrogen sulfide.

2. How to regenerate hydrogen sulfide scavenger

9 is a photograph showing a hydrogen sulfide removing agent according to an embodiment of the present invention.

10 is a flowchart illustrating a method of regenerating a hydrogen sulfide remover according to another embodiment of the present invention.

First, a hydrogen sulfide removing agent was prepared in the form of pellets and filled in an absorption tower.

The hydrogen sulfide gas discharged from the waste collection tank was introduced into the absorption tower and reacted.

[Reaction Scheme 1]

SO ₄ ^-2 + 2 (CH ₂ O) (organic matter) + 2H ⁺ → H ₂ S (gas) ↑ + 2H ₂ O + ₂ CO ₂ (gas)

Fe (OH) ₃ (aq) + H ₂ S → Fe ₂ S ₃ (solid) ↓ + 3H ₂ O

2Fe ₂ S ₃ + 6H ₂ O + 3O ₂ → 4Fe (OH) ₃ (aq) + 3S ₂ (solid) ↓

Reaction 1 shows that hydrogen sulfide was generated by anaerobic digestion in the presence of organic compounds in aqueous solution containing sulfate ions. At this time, iron ion (Fe ³⁺ ) of the hydrogen sulfide removing agent exerted an effect as a deodorant. The precipitated iron sulfide was reduced to sulfur and iron hydroxide when the alkali solution was added to the aerobic solution, and the iron hydroxide was regenerated to produce the hydrogen sulfide remover.

FIG. 11 is a graph showing adsorption of hydrogen sulfide over time of the hydrogen sulfide remover according to an embodiment of the present invention, and FIG. 12 is a graph showing adsorption of organic substances with time of the hydrogen sulfide remover according to an embodiment of the present invention.

As shown in the drawing, it was confirmed that the concentration of hydrogen sulfide was greatly reduced as the time was hardened, and the adsorption power was excellent also for ammonia, phosphorus, trimethylamine and methyl mercaptan as well as hydrogen sulfide, It is confirmed that

As described above, the hydrogen sulfide removing agent according to the present invention can easily remove hydrogen sulfide at a low cost. In particular, in the livestock industry which discharges a large amount of hydrogen sulfide, it is possible to eliminate the hydrogen sulfide with high efficiency to solve the odor problem, and since the after-use hydrogen sulfide removing agent can be regenerated by a simple process, the efficiency of hydrogen sulfide removal is greatly increased.

While the invention has been described with reference to a limited number of embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

Claims (9)

delete delete delete delete delete A mixture of calcite and water containing ocher powder, protein, carbohydrate and fat including iron oxide (Fe ₂ O ₃ ), aluminum oxide (Al ₂ O ₃ ) and silicon oxide (SiO ₂ ) is mixed and extruded to form a pellet- ;
Mixing the hydrogen sulfide removing agent with a hydrogen sulfide removing object to adsorb hydrogen sulfide;
Recovering and pulverizing the hydrogen sulfide-removing agent adsorbed by hydrogen sulfide; Neutralizing and recovering powdered hydrogen sulfide scavenger; And a step of drying the regenerated hydrogen sulfide removing agent and replenishing the loess powder to prepare a hydrogen sulfide removing agent, wherein the iron sulfide (Fe ₂ O ₃ ) is contained in an amount of 40 to 65 wt% . The method according to claim 6, wherein the step of preparing the hydrogen sulfide removing agent further comprises the step of collecting the loess powder and drying in the exposure for 3 years. [Claim 6] The method according to claim 6, wherein the step of neutralizing and regenerating the hydrogen sulfide removing agent comprises adding an alkali solution and blowing air to adsorb sulfur to change the water solubility of the insoluble hydrogen sulfide removing agent. The method according to claim 8, wherein the alkali solution is reproduction of hydrogen sulfide removal, characterized in that at least one selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH ₄ OH) and lithium hydroxide (LiOH) Way.

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