KR101781377B1 - Method of Deodorization and Modification for Livestock Manure or Organic or Inorganic Sludge Using Aluminum By-product and Acid Solution - Google Patents

Abstract

The present invention relates to a method of removing and modifying odor of an animal manure or an organic or inorganic sludge using aluminum by-products and an acidic solidifying agent. The present invention causes an exothermic reaction and induces sterilization and microorganism death using an aluminum dross generated in an aluminum manufacturing process in the animal manure or the organic or inorganic sludge having a high moisture content. The present invention reduces the odor generated in a reaction process by controlling pH using the acidic solidifying agent, and reduces the moisture content of animal manure having high moisture content or organic or inorganic sludge.

Description

METHOD FOR DEODORIZATION AND MODIFICATION FOR LIVESTOCK MANUAL OR ORGANIC OR INORGANIC SUDDLE USING ALUMINUM BY-PRODUCT AND ACID SOLUTION USING LIQUID CRYSTAL EXTRACTION OR ALUMINUM SULFUR

The present invention relates to a method of removing and modifying odor of an animal manure or an organic or inorganic sludge using an aluminum by-product and an acidic liquid solidifying agent, and more particularly, The aluminum dross is used to induce heat generation, sterilization, and microbial death, and the occurrence of odors generated during the reaction is induced by pH change using an acidic liquid solidifying agent, thereby reducing the generation of odor, The present invention relates to a method for removing odor and modifying odor of an organic / inorganic sludge capable of modifying the water content of inorganic sludge.

Sewage and water purification sludge generated in Korea occur more than 4,000 tons a day at sewage treatment plants and industrial complexes in the whole country and each single plant or industrial complex. Most of them are landfilled or dumped into the sea.

However, when landfilling sludge containing 80% moisture is problematic, it is reluctant to bring in the landfill, and since there is also a limitation in throwing it in the sea, development of a technology for completely treating the sludge has already been attempted in various countries .

In addition, since sludge contains organic matter, energy can be recovered if it is properly used. However, when it is disposed of, sludge may cause secondary pollution such as odor generation and may be recycled as resources as much as possible in terms of waste of effective resources desirable.

In particular, organic wastes have a high water content and organic matter content, which causes rapid decay and odor during the summer season. Methods of treating such organic and inorganic sludge include composting, feed conversion, incineration, carbonization, solidification, treatment with some inorganic acids (waste acid), and sewage merger treatment, some of which are currently being implemented. However, some processes such as energy generation by methane gas generation, incineration treatment, sewage merging treatment, and solidifying treatment have been delayed due to problems such as temporal, economic, site location, and throughput problems. Particularly, Because of this, some of the processing methods are difficult to operate due to operational problems.

On the other hand, in order to recycle the organic and inorganic wastes without simply landing them, the water content of the organic wastes having a high water content should be reduced and the wastes should be solidified. For this purpose, conventional dehydration treatment has been carried out, but secondary environmental pollution caused by chemicals may occur. Therefore, research on a physical treatment before dehydration has been required.

Accordingly, a method of maximizing the dewaterability by using ultrasonic waves, which are widely used in the environmental field, is proposed as a method of treating the sludge having a high moisture content. This ultrasonic method uses ultrasonic wave to apply ultrasonic wave to the sludge and to destroy the bond between the inner and the joint water which can not be removed in the sludge by the ultrasonic energy.

On the other hand, the solidification treatment method is to add a solidifying agent to dehydrated sludge having a high water content and then to utilize it in engineering. This is to improve the physical properties and chemical properties of the sludge by adding a solidifying agent to the dewatered sludge, thereby improving the working efficiency, harmlessness and stabilization of harmful substances such as heavy metals, and improving the soil characteristics such as strength.

In addition, when using the alkaline type solidifying agent alone, it induces the generation of a large amount of ammonia gas by stimulating the nitrogen component in the sludge, and excessive deodorizing equipment is required and the environment is not stable.

As the solidifying agent, various kinds of cement such as portland cement, crude steel cement, solidified cement, aluminum-based special cement, asphalt, plastic, quicklime and the like are used. Among them, special cement is used as a solidifying agent in the method of solidifying the sewage sludge cake, and this method is excellent in the effect of solidification, but it is uneconomical because it is the most expensive alumina cement. Inorganic sludge also causes considerable problems in storage and treatment due to its high water content, so if priority is given to secondary recycling, preferential moisture reduction treatment is essential.

As a technique of solidifying such sludge, Korean Patent Registration No. 10-1534830 discloses an adsorbent for removing acidic odor sources of sludge produced by using aluminum-based byproducts. In Korean Patent Registration No. 10-0948658, Sewage sludge solidifying agent recycling incinerator is disclosed.

From these prior arts, the present inventors have attempted to utilize waste resources using organic / inorganic sludge, and have attempted to induce exothermic reaction and microbial death by acid-alkali reaction using aluminum dross generated in the aluminum manufacturing process . The present invention has been completed based on the fact that the odor generated in the reaction process is induced by the acidic liquid solidifying agent to reduce the occurrence of odor and lower the water content of the organic / inorganic sludge of the high water content of the subject, .

Korean Patent Publication No. 10-1534830 Korean Patent Publication No. 10-0948658

SUMMARY OF THE INVENTION The present invention has been made in view of the background art as described above, and it is an object of the present invention to improve the water content of livestock manure or oil-sludge having high water content by the solidification process not the dry / And a method of removing and modifying odor of an animal manure or an organic / inorganic sludge which can be recycled to the environment.

In addition, it is possible to prevent secondary environmental pollution caused by shore dumping and nightfall, and to treat waste at a low cost within a short period of time, thereby achieving a competitive advantage by drastically reducing the production cost of the waste generator. In addition, The object of the present invention is to provide a method of removing odor and modifying odor of animal manure or organic / inorganic sludge which can prevent secondary environmental destruction due to lack of soil and can replace deficient resources.

In order to solve the above problems, the method of removing and modifying odor of an animal manure or an organic / inorganic sludge using an aluminum by-product and an acidic liquid solidifying agent according to the present invention, a primary mixing step of mixing an aluminum dross; A secondary mixing step of additionally mixing an acidic liquid solidifying agent when the exothermic phenomenon of livestock manure or sludge and the generation of steam and gas are started in the primary mixing step; And a reforming step of reforming the mixture obtained through the secondary mixing step.

At this time, the acidic liquid solidifying agent is a sulfuric acid-based substance selected from the group consisting of persulfuric acid, concentrated sulfuric acid, dilute sulfuric acid, and spent sulfuric acid; A phosphoric acid-based material selected from the group consisting of orthophosphoric acid and phosphoric acid; And a ferrous salt-based material selected from ferrous sulfate monohydrate or ferrous sulfate ferrous sulfate, and may be any one of the sulfuric acid-based material, the phosphoric acid-based material, and the iron-based material.

The acidic liquid solidifying agent may be prepared by mixing the livestock manure or the mixture of the organic and inorganic sludge with the aluminum dross at a pH of 11 to 12 and mixing the acidic liquid- 8 < / RTI >

It is preferable to mix 15 to 50 parts by weight of the aluminum dross with respect to the livestock manure or the organic-inorganic sludge, wherein the acidic liquid solidifying agent comprises 5 to 12 parts by weight of a sulfuric acid-based material, 6 to 12 parts by weight, and 20 to 45 parts by weight of the iron salt-based substance.

The primary and secondary mixing steps can be carried out using a mixer, and the livestock manure or sludge subjected to the reforming step has a moisture content of 40% or less after 1 day and a pH of 6 to 7 .

The organic-inorganic sludge may be any one or more of sewage sludge, waste sludge, purified sludge, wastewater sludge, waste sludge, waste rock, livestock wastewater, food sludge, dredged soil, dyeing sludge and slaughter sludge.

The aluminum dross is characterized in that the content of aluminum is 10 to 30% by weight.

According to the manufacturing method of the present invention, the odor removing and modifying method of an animal manure or organic / inorganic sludge can reduce the water content of the livestock manure or the organic / inorganic sludge by using the aluminum dross and the acidic liquid solidifying agent, It is possible to prevent secondary environmental pollution caused by marine dumping and field pollution by making the same type of solid cargo, and it is economical, and when CO _{2 is} discharged, water is discharged together with the amount of organic matter, .

In addition, it is possible to provide a sludge reforming method which can be used as an artificial soil material, compost soil, improved soil of harmful sediments, compost, etc. since the odor is hardly generated in the reaction step and the solidification efficiency is excellent. In addition, due to the simplicity of the process and the shortest treatment period, economical efficiency can be secured in the livestock manure or sludge reforming treatment.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process diagram showing a method for removing and modifying odor of an animal manure or oil-organic sludge using an aluminum by-product and an acidic liquid solidifying agent according to the present invention.
2 is a photograph showing the exothermic state (b) of the slaughtered sludge (a) and the slaughtered sludge after mixing the aluminum by-product and the acidic liquid phase solidifying agent.

Hereinafter, the present invention will be described in more detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

As shown in FIG. 1, the method of removing and modifying the odor of an animal manure or an organic / inorganic sludge using an aluminum by-product and an acidic liquid solidifying agent according to the present invention is characterized in that an animal manure or an aluminum sludge A primary mixing step of mixing an aluminum dross; A secondary mixing step of additionally mixing an acidic liquid solidifying agent when the exothermic phenomenon of livestock manure or sludge and the generation of steam and gas are started in the primary mixing step; And a reforming step of reforming the mixture obtained through the secondary mixing step.

At this time, in the primary mixing step, the aluminum dross has a function of maximizing heat generation in the function of heat generation and solidifying agent and reaction with acid, and a function of oxidizing solid matter in contact with air, And the temperature range is from 60 to 120 DEG C, so that the point at which the acidic liquid phase-setting agent is mixed can be determined by measuring the exothermic temperature.

The aluminum dross is a by-product generated in an aluminum manufacturing process. When aluminum ground or aluminum scrap is melted, a molten metal is formed, and an oxidizing compound is formed on the upper surface of the molten metal, Thereby generating a nitrogen compound, which is generated as a by-product. In the present invention, the aluminum dross containing aluminum in an amount of 10 to 30% by weight is used. However, when aluminum dross is too small or too much as a raw material, It was confirmed that it is preferable to use aluminum dross having the above-mentioned aluminum content.

The aluminum dross generates hydrogen gas and ammonia while reacting with aluminum or aluminum nitride as follows, so that it produces odor and gas, and the reaction proceeds as an exothermic reaction. (The heat amount obtained from 1 kg of aluminum dross is 1,664 kcal.) This exothermic reaction not only evaporates water distributed in the livestock manure or sludge, but also sterilizes and kills microorganisms.

Al + 3H ₂ O? Al (OH) ₂ + 3 / 2H ₂

_{AlN + 3H 2 O → Al (} OH) 3 + NH 3

As shown in the example of the slaughterhouse sludge (a) of FIG. 2, this exothermic reaction can be confirmed by mixing the aluminum by-product and the acidic liquid phase solidifying agent in the slaughtered sludge as shown in FIG. 2 (b) ).

In addition, the acidic liquid solidifying agent used in the second mixing step is added to maximize the exothermic reaction of the aluminum dross and to adjust the pH to reduce odor generation. At this time, when the acidic liquid solidifying agent is added in an excessively large amount, It is important to mix them in a certain amount because the curing speed may be delayed or the curing may not be performed.

Wherein the acidic liquid phase solidifying agent is selected from the group consisting of sulfuric acid-based materials selected from the group consisting of persulfuric acid, concentrated sulfuric acid, dilute sulfuric acid, and waste sulfuric acid; A phosphoric acid-based material selected from the group consisting of orthophosphoric acid and phosphoric acid; And a ferrous salt-based substance selected from ferrous sulfate monohydrate or ferrous sulfate ferrous sulfate. It is preferable to use a mixture of sulfuric acid-based substances, phosphoric acid-based substances, and sulfuric acid based on the kind, moisture content and solids content of the livestock manure or sludge, Any one of iron-based materials may be used.

The acidic liquid stiffening agent is mixed at a pH value of 11 to 12 of the mixture obtained by mixing the livestock manure or the organic and inorganic sludge with the aluminum dross. In the case of the high water content livestock manure or the organic / inorganic sludge, And when the pH value is elevated to about 11 to 12, the generation of ammonia gas and odor rapidly increases, which is a problem. In this process, the pH value is decreased by mixing the acidic liquid solidifying agent, and the pH value is adjusted to the range of 5 to 8, so that the exothermic phenomenon can be maintained while reducing a large amount of odor.

In the primary mixing step, it is preferable to mix 15 to 50 parts by weight of the aluminum dross with respect to the livestock manure or the organic-inorganic sludge. When the content of the acidic liquid stiffening agent is too small, it is difficult to control the pH The time is too much, and if it is too much, the exothermic phenomenon is not maintained and the efficiency of the modification of the animal manure or slurry is decreased. In this case, it is most preferable to use a mixture of 5 to 12 parts by weight of the sulfuric acid-based material, 6 to 12 parts by weight of the phosphoric acid-based material and 20 to 45 parts by weight of the iron-based based material.

The first and second mixing steps are preferably performed using a mixer. However, when it is difficult to use a mixer at a work site, mixing can be carried out step by step using a variety of artificially mixable equipment. The odor removing and reforming method of the present invention can be applied.

In the present invention, the term "modification" refers to a process of changing livestock manure or sludge so as to have physical properties such as water content, pH change, compaction pressure increase, solidification, and granulation capable of air flow in the livestock manure or sludge. · When the inorganic sludge is reformed, the water content is reduced, neutralized, monolithic, and the compaction pressure body is formed. The improvement characteristic of the present invention is that the water content of the livestock manure or sludge that has undergone the above-described reforming step is 40% or less after 1 day, and the pH is 6 to 7, thereby determining whether the manure or sludge is complete.

In the reforming step, the mixture of the second mixing step is dried to remove moisture and dried. In the embodiment of the present invention, the first mixture is immediately mixed with the acidic liquid solidifying agent and then heated at a high temperature The steam starts to be generated, and the solidified material starts to harden, and the solidified material after one day becomes a water content of 40% or less.

In the reforming step, the mixture is allowed to dry naturally for a minimum of 24 hours. This is because the mixture keeps a high temperature exotherm of about 60-120 deg. C for 120 minutes immediately upon mixing, so that the mixture is dried until the exotherm is over.

The drying temperature may vary depending on the object to be mixed, the water content, and the room temperature. Usually, the drying temperature is maintained at 50-80 ° C. for 3 hours or more.

That is, in the present invention, a method for modifying livestock manure or organic / inorganic sludge using aluminum dross and an acidic liquid solidifying agent can be applied to an animal manure sludge containing 60 to 80% moisture or an organic acid sludge The alkaline aluminum dross is reacted with the livestock manure or the organic / inorganic sludge to generate a high temperature. At this time, the acidic liquid stiffening agent with strong acidity is vigorously reacted to generate a high temperature, It is based on the principle that livestock manure or sludge solidifies while the water of sexual sludge evaporates to water vapor. At this time, the iron (Fe) contained in the solidified material reacts with the air to be oxidized to ocher, and the solidified mixture becomes a solid material having the same shape as the soil.

The organic-inorganic sludge used in the present invention may be any one or more of sewage sludge, waste sludge, purified water sludge, wastewater sludge, waste sludge, waste stone, livestock wastewater, food sludge, dredged soil, dyeing sludge and sowing sludge .

In the livestock manure or oil-organic sludge reforming treatment of the present invention, the secondary mixing step may be performed such that the weight ratio of the mixture in the primary mixing step to the acidic liquid solidifying agent is 100: 5-12 .

When 3 to 15 parts by weight of the sulfuric acid-based substance and 6 to 12 parts by weight of the phosphoric acid-based substance are mixed and 20 to 45 parts by weight of the iron salt-based substance are mixed based on the solid content on the mixed sludge, Thus, a strong alkaline mixture with a pH value of 10-12 can be transferred to a slightly acidic (pH 4-8).

In the secondary mixing step, it is preferable to mix the acidic liquid phase solidifying agent to the mixture of the first mixing step little by little, and in the drying step, the first mixture is heated using the high temperature heat generated when mixing with the acidic liquid phase solidifying agent, It is preferable that the cargo is allowed to have a water content of 20 to 40% and air dried.

A major technical feature of the present invention is the use of aluminum dross instead of the alkali material conventionally used in the livestock manure or in the process of modification of the organic-inorganic sludge.

Generally, waste acids contain a large amount of heavy metals, so the soil obtained by reforming with these substances may cause problems when used as an organic fertilizer. In order to prevent this, the present invention uses 5 to 12 parts by weight of an acidic liquid solidifying agent per 100 parts by weight of the mixture of the first mixing step.

In addition, CaO or MgO calcined as an alkali substance is conventionally used, and aluminum dross is used in place of such alkali substance to accelerate drying by promoting heat generation and gas release, and the inorganic specific gravity is low to increase the effective organic matter content, It is possible to obtain effects such as death.

Hereinafter, effects of the present invention will be described with reference to examples.

The water content, pH, and ammonia content after 1000 g of food sludge (W / T 72.3%), 300 g of aluminum dross (Al 15% by weight) and 150 g of acidic liquid solidifying agent were measured and the state after 3 days was measured. In the examples, a mixture of 10 parts by weight of chitosanic acid, 8 parts by weight of polyphosphoric acid, and 30 parts by weight of ferrous sulfate monohydrate was used as the acidic liquid solidifying agent.

The water content, pH, and ammonia content after 1000 g of sewage sludge (W / T 82.7%), 40 g of aluminum dross (Al 15% by weight) and 150 g of acidic liquid solidifying agent were measured and the state after 3 days was measured. The acidic liquid phase solidifying agent was the same as in Example 1.

The water content, pH and ammonia content after 1000 g of dredging sludge (W / T 79.3%), 400 g of aluminum dross (Al 15% by weight) and 20 g of acidic liquid solidifying agent were measured and the state after 3 days was measured. The acidic liquid phase solidifying agent was the same as in Example 1.

The results of Examples 1 to 3 are summarized in Table 1.

division
Moisture content
(%) Aluminum dross 2 minutes mixing Acid liquid solidifying agent added 3 minutes mixing After 3 days pH Heat (℃) NH ₄ (ppm) pH Heat (℃) NH ₄ (ppm) pH Heat (℃) NH ₄ (ppm) moisture Example 1 72.3 11.4 84 180 7.6 124 70 6.6 41 50 30.9 Example 2 82.7 12.1 76 250 8.3 114 65 6.5 36 40 41.3 Example 3 70.3 12.2 91 90 8.6 128 30 6.5 31 40 29.8

As a result of Example 1, the water content of the food sludge having a water content of 72.3% was mixed with the aluminum dross to induce heat generation and mixed with the acidic liquid solidifying agent, and after 3 days, the water content decreased to 30.9% 11.4 to 6.5, and the effect of reducing the generation of odor was confirmed.

In Example 2, the water content of 82.7% was reduced to 41.3% in 3 days when the aluminum dross and the acidic solidifying agent were added, and the pH value decreased from 12.1 to 6.5, It is difficult to recognize.

Further, in Example 3, the dredging and solidifying agent is a fine silt material in which a small amount of organic matter and an inorganic material are mixed. When the sludge having a high water content of 79.3% is modified, the water content falls to 29.8% It can be confirmed that it is stabilized by the conversion to

Therefore, it has been confirmed that the modification method of the present invention is a modification method of sludge capable of effectively converting livestock manure or sludge into a landfill soil remover and regenerated soil.

Claims (10)

A primary mixing step of mixing 15 to 50 parts by weight of aluminum dross, which is an aluminum by-product, with respect to 100 parts by weight of livestock manure or organic sludge or inorganic sludge or organic and inorganic sludge;
In the primary mixing step, the exothermic phenomenon of livestock manure or sludge,
A secondary mixing step of additionally mixing an acidic solidifying agent when the generation of the acidic solidifying agent starts;
A reforming step of reforming the mixture obtained through the secondary mixing step;
/ RTI >
Wherein said acidic liquid phase solidifying agent comprises 5 to 12 parts by weight of a sulfuric acid based material selected from the group consisting of concentrated sulfuric acid, dilute sulfuric acid and sulfuric acid, 6 to 12 parts by weight of a phosphoric acid based material selected from the group consisting of normal phosphoric acid and phosphoric acid, And 20 to 45 parts by weight of an iron-based substance selected from the group consisting of iron-based materials and an acidic liquid-solidifying agent, or an organic sludge or inorganic sludge or a malodor removing and reforming method of organic and inorganic sludge .
delete delete The method according to claim 1,
Wherein the acidic liquid solidifying agent is mixed in the state that the pH of the livestock manure, organic sludge or inorganic sludge or the mixture of aluminum sludge and organic dross is 11 to 12, and mixing of the acidic liquid solidifying agent Wherein the pH is adjusted to a range of from 5 to 8 by using the acidic liquid solidifying agent and the aluminum by-product, or an organic sludge or an inorganic sludge or an organic and inorganic sludge.
delete delete The method according to claim 1,
Wherein the primary and secondary mixing steps are carried out using a mixer, characterized in that the liquor removal is carried out using a mixer, and an odor removing and reforming method of an organic sludge or an inorganic sludge or an organic and inorganic sludge using an acidic liquid solidifying agent .
The method according to claim 1,
Wherein the livestock manure or sludge subjected to the reforming step has a water content of 40% or less after 1 day and has a pH of 6 to 7, and an animal manure using an acidic liquid solidifying agent or an organic sludge or inorganic sludge A method for removing and reforming odor of sludge or organic and inorganic sludge.
The method according to claim 1,
The organic sludge or inorganic sludge or the organic and inorganic sludge may be any one or more of sewage sludge, waste sludge, purified sludge, wastewater sludge, waste sludge, waste stone, livestock wastewater, food sludge, dredged soil, dyeing sludge, Or an organic sludge or an inorganic sludge or an organic and inorganic sludge using an aluminum by-product and an acidic liquid solidifying agent.
The method according to claim 1,
Wherein the aluminum dross has an aluminum content of 10 to 30% by weight. The method according to claim 1, wherein the aluminum sludge is an aluminum sludge.

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