KR101287013B1 - Solidifying agent for sludge using industrial by-product - Google Patents

Abstract

PURPOSE: A functional solidifying agent for sludge is provided to improve a problem on price rise of solidifying agents by using industrial byproduct. CONSTITUTION: A functional solidifying agent for sludge comprises: 10-60wt% of non-ferric smelting process byproduct, 10-60wt% of oil refining process byproduct, 10-30wt% of paper manufacturing process byproduct, and 10-30wt% of heat power plant or waste incineration byproduct.

Description

{Solidifying agent for sludge using industrial by-product}

The present invention relates to a sludge-based functional sludge using industrial by-products, and more particularly, to a sludge-based sludge-based sludge which can control odors while maintaining the performance of a sludge, and which is economical, environmentally friendly, And to sludge functional fires.

Domestic sewage sludge has been rapidly increasing from 7,631 tons / day in 2007 to 10,259 tons / day in 2011 due to improvement in people's living standards and conditions. Therefore, the government recognizes the seriousness of this problem and establishes a treatment plan by installing treatment facilities for each city and province in order to treat sewage sludge.

However, in the case of marine discharges (68.5% of total sewage sludge in 2010), which is one of the sewage sludge disposal methods, the total ban is scheduled for 2012 from the London Convention. In case of incineration and landfill, We are reluctant to worry about material outbreaks and to curb greenhouse gas emissions and promote recycling. In the recycling of sewage sludge, the Ministry of Agriculture is opposed to composting because the harmful substances contained in the sludge can harm the human body through crops. Therefore, there is a growing expectation for the recycling of sewage sludge as a cover material, but this also faces various problems.

Constituents of the sewage sludge is mostly _{SiO 2, Al 2 O 3,} Fe 2 O 3 a possible use of boktojae as it consists of inorganic materials such, it generally forms a sponge-like structure dehydrated with water contained by capillary forces It is very difficult to use as a soil material and it is likely to cause public health problems by providing habitat of pathogens, flies and mosquitoes due to moisture and organic substances contained in the sewage sludge, And it generates secondary pollutants such as ground water pollution and odor due to leachate.

In order to solve the above-mentioned problems, it is indispensable to develop a fire which can reduce the water content and sterilize by self-heating.

On the other hand, most of the currently used fires are mainly due to the use of CaO-based alkaline materials or FeSO ₄ -based acidic materials that induce absorption and heat generation, and thus they are vulnerable to the odor reduction part which is most problematic in sewage sludge treatment in recent years.

When analyzing the odor of sewage sludge having a water content of about 80%, about 50 kinds of substances are detected. Among them, the substances having relatively high concentration and low minimum detection value are shown in Table 1. As shown in Table 1, the sulfur compound, the aldehyde compound and the nitrogen compound are generated in a complex manner, and the odor is attributed to their odor.

Table 1 shows the percentage of contribution by the minimum detection value of the odor component to the actual generated substance. This contribution rate is a method of selecting the substance to be removed, and it is the main data for determining the ratio of the deodorant inside the deodorant when the odor is not caused by a single substance. It is a major object to remove acidic and basic systems.

No. Substance density
(ppm) Minimum sense value
(ppm) Theoretical dilution Odor contribution rate
(%) One Hydrogen sulfide 0.26 0.00041 634 0.5 2 Methyl mercaptan 4.81 0.00007 68,714 51.1 3 Dimethyl sulfide 3.09 0.003 1,030 0.8 4 Dimethyl disulfide 0.62 0.0022 282 0.2 5 Acetaldehyde 0.51 0.0015 340 0.3 6 Acrolein 0.32 0.0085 38 0.03 7 Propionaldehyde 0.16 0.001 160 0.1 8 Benzaldehyde 0.02 0.028 One - 9 Trimethylamine 2 0.000032 62,500 46.5 10 ammonia 98 0.15 653 0.5

As shown in Table 1 above, methyl mercaptan and trimethylamine are considered to be the main odor substances. Considering the working environment in the workplace and taking into account the characteristics of the malodorous substance, hydrogen sulfide in the acidic substance and ammonia in the methylmercaptan And trimethylamine in an amount equal to the amount of generation of trimethylamine. Hydrogen sulphide and ammonia are highly volatile and have a large amount of change depending on conditions such as temperature and pH in the presence of water. , 22 odor substances regulated by the Ministry of Environment should also be reduced.

On the other hand, in treating a large amount of sludge, there is a problem that the cost of the fire increases sharply in order to control the odor while maintaining the fire performance.

Therefore, the present inventors have made efforts to solve the problems of the prior art, by using industrial by-products such as non-ferrous smelting process by-products, petroleum refining process by-products, coal-fired power plant by-products or paper processing by-products as a raw material of a solid fire and environmental The present invention has been completed by revealing that a friendly functional solid fire can be produced.

Accordingly, an object of the present invention is to provide an economical and environmentally friendly sludge-based functional sludge which can control the odor while maintaining the performance of the sludge.

In order to achieve the above object, the present invention, in the functional solidified material for sludge using industrial by-products, non-ferrous smelting process by-products 10 to 60% by weight, petroleum refining process by-products 10 to 60% by weight, papermaking process by-products 10 to 30% by weight And it provides a functional solidified fire for sludge using industrial by-products, including 10 to 30% by weight of thermal power plants or waste incineration by-products.

The non-ferrous metal smelting process by-product is a waste gypsum-based by-product obtained by treating waste sulfuric acid generated in the non-ferrous metal smelting process with a neutralizing agent, preferably having an average particle diameter of 2 ~ 100 ㎛, when the average particle diameter exceeds 100 ㎛ During the solidification process, problems may occur in the strength of the solidified material, that is, the pozzolanic reaction and the carbonation reaction.

The by-product of the petroleum refining process is a spent catalyst used in a catalytic catalytic catalytic cracking process, and is preferably a spherical catalyst loaded with zeolite on silica-alumina. Increased moisture content of may cause a problem of hardening.

The papermaking by-product may be a fly ash generated after incineration of paper sludge, and when applied to less than 10% by weight may cause problems in the moisture content of the solids themselves, and when the content exceeds 30% by weight, the pH is increased. This may cause a problem of severe alkaline odor.

The thermal power plant by-product is a fly ash generated after incineration during the thermal power generation process using a raw material selected from coal, charcoal or petroleum, the waste incineration by-product may be a fly ash generated after incineration of industrial waste, out of the content range If included, a lot of odor may be generated due to the increase of the final solidified pH, and may also cause a problem of incompatibility between the sludge and the solidified material during the solidification process.

The sludge may include, but is not limited to, sewage, sewage, wastewater, livestock manure or food sludge.

Hereinafter, the present invention will be described in more detail.

The conventional method has a problem in that the cost of the sludge is rapidly increased in order to control the odor while maintaining the performance of the sludge in the process of treating a large amount of sludge. Therefore, the present inventors have tried to complete the present invention by emphasizing economic aspects, such as non-ferrous metals by-products, waste catalyst of petroleum refining process, paper ash by-product fly ash, fly ash of coal-fired power plant by-products (coal, petroleum, charcoal) By producing solidified fires by-products, economic efficiency was improved.

Therefore, in the present invention, inorganic sludge generated in the non-ferrous metal smelting process, waste catalyst generated in the petroleum refining process, fly ash generated in the papermaking process, and fly ash generated in thermal power generation using coal, petroleum or charcoal, etc. are possible. The present invention was completed by using each sludge as a raw material for solidified fire.

In the following, the present invention will be described in more detail with reference to each process by-product.

1. Byproducts of Nonferrous Smelting Process

Most non-ferrous smelting industries, such as copper smelting, zinc smelting, and smelting, use sulfide ore as a raw material. Thus, waste sulfuric acid containing 2 to 15% of sulfuric acid concentration is generated during the smelting process. When such waste sulfuric acid is treated with neutralizing agents such as calcium carbonate (CaCO ₃ ), calcined lime (Ca (OH) ₂ ), some industrial gypsum is produced, and a large amount of waste gypsum containing impurities is generated.

The following reaction formula shows the process of treating waste sulfuric acid.In the first neutralization process, when calcium carbonate (CaCO ₃ ) is added to the waste sulfuric acid at a pH range of 2 to 6, most of the sulfuric acid is neutralized with gypsum. The gypsum filtrate, which is sold as a product and contains impurities, is sent to the secondary neutralization process.

[Reaction Scheme 1]

_{H 2 SO 4 + CaCO 3 +} H 2 O → CaSO 4 · H 2 O ↓ + CO 2 ↑

In the secondary neutralization step, when calcium hydroxide (Ca (OH) ₂ ) is added to adjust the pH to 9-12, most impurities are precipitated with hydroxides, and at the same time, some unreacted sulfuric acid is neutralized in the primary neutralization step. Waste gypsum containing impurities is generated.

[Reaction Scheme 2]

Me (SO ₄ ) X + xCa (OH) ₂ + xH ₂ O → Me (OH) X ↓ + xH ₂ SO ₄

H ₂ SO ₄ + Ca (OH) ₂ → CaSO ₄ 2H ₂ O

Various technical approaches have been attempted to reduce and recycle the waste gypsum, but since there are no commercialized economic measures, the waste gypsum containing useful components is mostly buried as waste. There is a problem of increasing the burden of phosphorus.

Thus, in the present invention, by utilizing the waste gypsum generated in the current non-ferrous smelting process can be used as a raw material of the solidified material. When the waste gypsum is added to water, the reaction between the constituents and water in the soil is started, that is, a hydration reaction, and a large amount of ettringite is produced by the reaction between aluminate and gypsum upon contact with water. The ettringite absorbs a large amount of water into the binding water and grows finely into a needle to lower the water content of the solids, and at the same time, the effect of consolidation is promoted to promote solidification.

For example, A company generates 150 ~ 200 tons of inorganic sludge per day during the non-ferrous metal smelting process, only part of it is used as cement raw material, the rest depends on landfilling, and other process by-products are partially recycled. Although it depends on the landfill or the like, it can be used as the raw material of the solidified material of the present invention by utilizing the inorganic sludge thus embedded.

In addition, fly ash generated as a non-ferrous smelting process by-product has a pH of 10 or more, and thus has an ability to remove acidic gas.

2. Petroleum Refining Process [Fluid Catalytic Catalytic Cracking (FCC) Process]

Fluidized Catalytic Cracking (FCC) is the most widely used process in petroleum refining plants to produce valuable hydrocarbon materials from crude oil.Fluidized diesel or diesel oil from crude oil distillation is combined with catalysts in fluidized bed reactors. Contact and decompose into gasoline or naphtha oil. The FCC process is the largest among the petrochemical processes due to the increase in automobiles, the demand for gasoline, and the development of the petrochemical industry, and the increase in naphtha demand.

In the FCC process, a spherical catalyst made by mixing silica-alumina with zeolite Y is used.The zeolite particles are contained in the large pores of silica-alumina, so that the large reactants are first decomposed at the silica-alumina acid point, and then diffused into the zeolite pores to form octane number. Is converted to highly branched hydrocarbons.

The spent FCC process catalyst is usually calcined in air to remove deposited carbon and used as cement raw material. Recycling is considered as a brick manufacture or other zeolite synthetic raw material, but it is generated and mixed with limestone because of its high generation and low economic efficiency. The waste catalyst of FCC process has little other components except silica and alumina, so there is no fear of pollution and it is suitable as a raw material for cement production because of its excellent mechanical strength. However, since a considerable amount of zeolite components still remain in the FCC process waste catalyst, the use as an odor removing solidifying material is more effective, and therefore, the FCC process waste catalyst may be used as the odor removing solidifying material.

The waste catalyst of the FCC process has a specific surface area of 200 m ² / g or more, has a zeolite structure, and has a pH of 7 to 10, which may be useful for removing odors of neutral gases and solvents.

3. By-products of thermal power plants (charcoal, oil, coal-fired power generation)

Coal ash, a byproduct of coal-fired power plants, consists of fly ash, bottom ash and cinder ash. In recent years, attempts have been made to directly sort and recycle waste incinerators, except that fly ash is about 60% recycled, and most of it is landfilled and disposed of, especially in the past 20-30 years. The amount of coal ash that is buried in the coal mine is not only significant, but the cost of securing and dumping the ash processing plant is very high. Moreover, the general coal ash plant is located on the coast near the coal-fired power plant, and is treated by the strong wind compared to the inland part. Due to the blowing of fine dust from the surface layer, it is a serious problem for the living environment of nearby residents. Landfill coal ash is a mixture of fly ash and bottom ash.

Previously, fly ash and bottom ash are separated and recycled through separate screening process for landfill coal ash.However, the direct use of coal ash generated from incinerators and the separate screening process for landfill coal ash dumped at thermal power plant ash processing plant Recycling intact, without going through can be an economical way to reduce the time and cost required for primary processing.

To date, fly ash has been recycled more than 60% as a cement substitute, and bottom ash has recently been proposed to improve the compaction characteristics and apply it as road fill material. The proposal has not been proposed yet. Each category also includes charcoal and petroleum fired power for their own generation.

Fly ash generated from coal-fired thermal power plant is pH 10 or more, so it has the ability to remove acid gases.Fly ash generated from petroleum-based (bunker C oil) thermal power plant is pH 5 or less, so it can remove basic gas. It may play a role of increasing the miscibility when mixing between the raw materials and the sludge in the manufacture of the solidified material.

4. Papermaking process or waste fly ash

Fly ash, a ash generated after incineration of paper sludge, which is a secondary by-product generated in paper production, may also be used as a solidifying material in the present invention.

Fly ash, which is ash generated after incineration of household waste or industrial waste, can also be used as a raw material for solidification in the present invention.

The fly ash does not have its own silica (SiO ₂ ) and alumina (Al ₂ O ₃ ) material, but when it is finely pulverized and contains moisture, it reacts with gypsum-based compound at room temperature to form a solid material. Serves to create the

The fly ash generated during the papermaking process or waste incineration is above pH 10 and therefore has the ability to remove acidic gases.

Therefore, the present invention is meaningful to manufacture a new functional solidified material deodorizing function by using the total amount of by-products by using the quicklime, cement, etc. as an important raw material, and by using the total amount of by-products from the existing solidified material by using a small amount of by-products, This can have two advantages: addressing the problem of recycling of by-products from each process and creating new value-added industries.

That is, the solidification phenomenon by Si, Ca, Fe, SO ₄ ^2- component in the solidification composition of the present invention is important for the solidification of the sludge, waste catalyst having a specific surface area of 200 m ² / g or more to remove the smell And fly ash, which is an acidic and alkaline raw material, plays a necessary role. At this time, Si, Ca component is a material that plays a major role in the moisture control and dispersing power, solidification of the solidification during the treatment of the solidified fire, it is contained in a non-ferrous smelting process by-products, thermal power by-products fly ash, fly ash of the papermaking process.

The sludge functional sludge according to the present invention can control the odor while maintaining the performance of the sludge in the treatment of sludge such as sewage, sewage, wastewater and the like. In particular, the functional solid fire can improve the problem of rising the price of solidified fire by using non-ferrous smelting process by-products, petroleum refining process by-products, paper process by-products or thermal power plant by-products, as well as environmentally friendly and each process This can solve the problem of resource recycling from by-products.

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

Example 1 Manufacture of Fire A

Non-ferrous smelting process by-product (Cosmo Chemical) 50.0% by weight, 15.0% by weight of paper ash (Daehan Paper) and 25.0% by weight of fly ash (Hadong Thermal Power Plant), using ultrafast shear omni mixer (CHIYODA OMH-30NA, Japan) Solid Fire A was prepared by mixing 10.0 wt% of facility waste catalyst (SK-energy). Solidified fire temperature was mixed at 350 RPM for 3 minutes at 20 ℃. At this time, the results of analyzing the solidified material A component is shown in Table 2 below.

Chemical composition Constituent SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ CaO MgO K ₂ O Na ₂ O SO ₃ LOI XRF
analysis content(%) 40.62 21.80 8.72 17.31 2.06 0.12 0.78 0.526 7.68

Example 2 Manufacture of Fire F

50.0% by weight of waste catalyst (GS Caltex), 20.0% by weight of paper ash (Daehan Paper), 20.0% by weight of fly ash (Yeongnam Thermal Power Plant), using an ultrafast shear omni mixer (CHIYODA OMH-30NA, Japan). Sintering process by-product (Dongbu Hitech) 10.0% by weight of the raw material was mixed to prepare a solid fire B. Solidified fire temperature was mixed at 350 RPM for 3 minutes at 20 ℃. At this time, the results of analyzing the solidified B component is shown in Table 3 below.

Chemical composition Constituent SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ CaO MgO K ₂ O Na ₂ O SO ₃ LOI XRF
analysis content(%) 46.39 26.75 5.03 10.36 1.36 0.73 0.52 0.025 8.45

Experimental Example 1 Applying Fire A to Sludge

The sludge used in this experiment is a Jeju sewage sludge obtained from the Cheju National High School, where 22 odors are generated including nitrogen compounds and sulfur compounds. As a control group, we used the fire alarm of F company, which was previously applied to the Jeju high school. 20 g of solidified fire A was added to 100 g of Jeju sewage sludge, followed by stirring for 5 minutes, and then the pH and temperature were measured. Odor trends were analyzed by -MSD. The results are shown in Table 4 below.

<Experiment 2> Solidified fire B applied to the sludge

As in Experiment 1, 20 g of solidified fire B was added to 100 g of Jeju sewage sludge, followed by stirring for 5 minutes, and then the pH and temperature were measured. Odor trends were analyzed by PFPD, HPLC and GC-MSD. The results are shown in Table 4 below.

Analysis contents Existing fire fighting
(Control group) Apply Fire A Apply Fire B Odor component
(ppm) ammonia 1200 600 300 Hydrogen sulfide 1.069 0.913 0.412 Methyl mercaptan 0.411 0.321 0.253 DMS 0.201 0.119 0.113 DMDS 0.759 0.551 0.449 Acetaldehyde 0.519 0.045 0.043 Propionaldehyde 0.018 N.D. N.D. Butylaldehyde 0.004 N.D. N.D. Valeraldehyde 0.006 N.D. N.D. I-valeraldehyde 0.001 N.D. N.D. Styrene 0.001 N.D. N.D. Trimethylamine 5 0.5 0.1 toluene 0.002 N.D. N.D. Xylene N.D. N.D. N.D. Methyl ethyl ketone N.D. N.D. N.D. Methyl isobutyl ketone 0.003 N.D. N.D. Butylacetate 0.006 0.002 0.003 Propionic acid 0.009 N.D. N.D. Butyrate 0.010 0.001 N.D. Valeric acid 0.001 N.D. N.D. I-valeric acid 0.003 N.D. N.D. I-butyl alcohol 0.009 0.001 0.002 Properties pH (high load) 10 9 8.7 Moisture content (high cargo,%) 42.5 36.5 34.8

As shown in Table 4, it was confirmed that a variety of VOCs, aldehydes, sulfur compounds, ammonia is generated in the sludge, and apply the solidified fire A and solidified fire B according to the present invention in comparison with the product of the company F applied to the existing Jeju solidification office When it was confirmed that the amount of ammonia is significantly reduced. In addition, the F company through the physical property analysis when applying the solidified material, when the solidified fire occurs when the aggregation phenomenon is inferior in dispersibility, while the application of solidified fire A and solidified B according to the present invention does not occur agglomerated phenomenon It was confirmed that the dispersibility is better than the product.

As mentioned above, although this invention was demonstrated by the limited embodiment, this invention is not limited by this and it will be described below by the person of ordinary skill in the art, and the following. Of course, various modifications and variations are possible within the scope of the claims.

Claims (9)

In the functional solidified material for sludge using industrial by-products,
For sludge using industrial by-products, including 10 to 60% by weight of non-ferrous metallurgical process by-products, 10 to 60% by weight of petroleum refining process by-products, 10 to 30% by weight of papermaking process by-products and 10 to 30% by weight of thermal power plants or waste incineration by-products Functional solid fire. The functional solidified material for sludge using industrial by-products according to claim 1, wherein the non-ferrous smelting process by-product is waste petroleum-based by-product obtained by treating waste sulfuric acid generated in the non-ferrous smelting process with a neutralizing agent. The functional solidified material for sludge using industrial by-products according to claim 2, wherein the waste gypsum-based by-product has an average particle diameter of 2 to 100 µm. The functional solidified material for sludge using industrial by-products according to claim 1, wherein the petroleum refining process by-product is a waste catalyst used in a fluidized bed catalytic catalytic cracking process. The functional solidifying material for sludge using industrial by-products according to claim 4, wherein the waste catalyst is a spherical catalyst in which zeolite is supported on silica-alumina. The functional solidifying material for sludge using industrial by-products according to claim 1, wherein the by-product process is fly ash generated after incineration of paper sludge. The functional solidified material for sludge using industrial by-products according to claim 1, wherein the thermal power plant by-product is a fly ash generated after incineration in a thermal power generation process using a raw material selected from coal, charcoal, or petroleum. The functional solidified material for sludge using industrial by-products according to claim 1, wherein the waste incineration by-product is a fly ash generated after incineration of industrial waste. The sludge as claimed in claim 1, wherein the sludge is sewage, sewage, wastewater, livestock manure or food sludge.