KR100562512B1 - A material for purifying smog, odor, heavy metals, noxious gas with flying ash, a bottom ash accumulated in the bottom of a trash burner and so on and purifying method to use the material - Google Patents

Abstract

Aqueous film-forming inorganic compounds (abbreviated as LC) are sprayed with the exhaust gas flue to effect the poby action, containing and depositing harmful gases, graphite, chlorides and harmful heavy metals, and decomposing exhaust fumes. . When the deposit mixed with the LC or the incineration ash is heated, it can be treated simultaneously with a stable valuable material by ceramics which do not elute harmful heavy metals.

When the LC is pressurized by incineration flue gas flue, the inclusion of harmful gas or harmful heavy metals is caused by the enveloping action, and the LC produces a heat-filtering effect, in particular, volatile hydrochloric acid as a non-volatile component, thereby generating graphite. The ash containing heavy metals is reduced to encapsulate and the graphite, malodor, dioxins and heavy metal-containing materials are encapsulated simultaneously, and the purified steam is discharged. The residual deposits are heated to form stable valuables.

No identifier above

Description

Purification materials such as harmful gases containing graphite, odors, heavy metals, fertilizers, and flooring material deposited on the bottom of the incinerator, and methods for their purification. BOTTOM ASH ACCUMULATED IN THE BOTTOM OF A TRASH BURNER AND SO ON AND PURIFYING METHOD TO USE THE MATERIAL}

1 to 4 are water molecular peaks by FTIR analysis at 20 ° C., 250 ° C., 550 ° C., and 960 ° C., showing that they are heat-resistant inorganic compounds of the aqueous inorganic membrane (LC) used in the present invention. It is a figure which shows the lowering film | membrane as a peak adds heat.

Figure 5 is a Si MAS-NMR LC analysis commissioned by the University of Michigan at the University of Iwate, comparing the 500 ° C product of the silanol salt solution and water glass of the previous invention, confirming the film formation of the peak recognized only in LC It is also.

FIG. 6 is a conceptual diagram of blowing the film of the previous invention silanol salt containing excess water into the hot exhaust gas to form a film, and to form a heat-resistant filter to lower the temperature to form a film.

FIG. 7 is a micrograph of the particles produced by a spray dryer having a gas temperature of 450 ° C. and a spray dryer having a spray outlet temperature of 180 ° C., respectively.

FIG. 8 is a table showing the results of the Japan Xeon Analysis Center of the gas analysis obtained by mixing the solidified granules shown in FIG. 7 with PVC.

9 and 10 are tables showing the results of industrial and elemental analysis of general waste (MSW) and ground dust (SD) used in the combustion test.

11 is a conceptual diagram of an incineration apparatus used in the present invention.

나 악취와 중금속, 비재

를 함유하는 유해가스와 소각 장치의 바닥에 퇴적된 바닥재 등 정화처리하는 물질과 이의 정화처리방법에 관한 것이다.Black smoke

I smell, heavy metal, ash

It relates to a material for purifying, such as a harmful gas containing and a flooring material deposited on the bottom of the incineration apparatus and its purification treatment method.

Strictly regulate the emission of toxic heavy metals contained in the incineration and discharged ashes, and the emission of dioxins already severely regulated in Europe. Is being

As a result, the government is also planning to switch from the small and medium sized incinerators which dispose of waste to the continuous furnace type incineration method. However, with the above regulations, local governments and intermediate waste disposal companies operating small and medium-sized incinerators face the question of whether to renovate or shut down a large amount of money, but there is no realistic proposal to solve this problem.

If a waste contains a metal or Cl component, it is orthodox that organic substance is burned and a dioxin precursor which is a harmful gas is produced. In addition, even if the cooling or scrubber treatment is performed while reaching the bug filter without high heat resistance used in the final step of the exhaust gas treatment, adsorption treatment of inorganic or mineral is caused by the occurrence of dioxin. Needed to be reprocessed. Complete treatment required complex treatment techniques and expensive equipment.

In addition, heavy metals, which are pollutants, remain in the bottom ash, which is a residue after incineration, and was conventionally treated with a chelating agent to be dumped into a managed landfill, but there is a problem in stability due to the lack of long-term stability. In particular, dioxins and heavy metals remain concentrated in the ash, making it difficult to treat chelating agents.

In addition, since small incinerators generate graphite or odor and affect neighboring residents, and incinerators that solve countermeasures are expensive, a simple and inexpensive method is desired.

In order to realize the dioxin and other gas and heavy metal regulations of the Environment Agency, the cost of remodeling existing incinerators is high, and the operation is inevitable. Is concerned.

The exhaust gas of the incinerator has a high temperature of 200-800 ° C., and is cooled or scrubber-treated without any filter of organic matter that can filter out any accidents or odors, or is cooled by treating with a ceramic catalyst or adsorbent having various proposals, It is being transferred to a bug filter. Therefore, since the apparatus becomes a solid solution, an inorganic filter or an adsorbent that withstands high temperature that does not require post-treatment is required. The present invention intends to solve this.

Conventionally known methods of treating flooring materials or heavy ashes containing heavy metals include a method of mixing chelating agents with organic substances, for example, carbamic acid. It was difficult to evaluate and required a method of chemically stable ionic bonds of heavy metals.

In Europe, the countermeasure against dioxin is early, but until recently, the method of cooling exhaust gas is mainstream. However, in a recent study, dioxin precursors exist in the presence of HCL, and dioxin is generated at low temperatures. For this purpose, adsorption by activated carbon or calcined lime that can be used at 450 ° C or more is utilized. However, a problem remains in the post-treatment of this adsorbent. Still, a bug filter was needed, and the heavy metal-bearing material left behind had to be scraped off.

In other words, the exhaust gas treatment requires a dioxin precursor, a non-reprocessing containing iron chloride or heavy metals, or a filter adsorbing a catalyst or pollutant having a dioxin decomposition action, and the post-treatment needed to be reused.

The present invention has been made in view of such circumstances, and using the present invention, it is possible to easily achieve the dioxin regulation value, which is difficult to dispose of even small and medium in discontinuous operation. It can alleviate the burden of residents and be used for a wide range of other industries.

이나 그 염및 알칼리 금속 (Na, K, Li) 을 사용하여 고체와 농후한 알칼리용액 반응으로부터제조되며, 물유리와는 다른 실록산과 실라놀(silanol)염으로부터 구성되고 있다.MEANS TO SOLVE THE PROBLEM The present inventors described "the manufacturing method of an aqueous film-forming inorganic compound" (Japanese Patent No. 2028203 Special Publication No. 7-14801), "disaster prevention, fire prevention, fireproof composite material" (Japanese Patent 2015694), etc. It is proposed to collectively refer to "noluate". These previous invention silanol salts are metasilicon, borax or sodium fluoride, sublime

Or salts thereof and alkali metals (Na, K, Li) are used to produce solid and rich alkaline solution reactions, and are composed of siloxanes and silanol salts different from water glass.

1 to 4 show that the water molecule peak heating is performed by FTIR analysis at 20 ° C., 250 ° C., 550 ° C., and 960 ° C. showing that the aqueous inorganic inorganic compound (LC) is a heat-resistant inorganic material used in the present invention. It is to show the formation. In Figs. 1 to 4, the horizontal axis represents wave numbers, and the vertical axis represents absorbance (ABSORVANCE). Analysis of the Toray Research Center and the FTIR analysis of FIGS. 1 to 4 shows the presence of silanol at 780 cm ⁻¹ and siloxane at 900, 1000 and 2400 to 3800 cm ⁻¹ . The silanol salt of the present invention is a heat resistant material that is heat resistant and does not decompose in any high temperature range of 200 to 1000 ° C. of the exhaust gas.

의 생성이 있는 것으로 하고있다. 그 결정화속도가 빠른 것은 제 5도에 나타난 500℃의 XRD (X ray diffraction, X선 해 석장치로 Si화합물만을 분석하는 특수장치임)의, 물유리와의 피크차를 비교하여 판단할 수 있다. The silanol salt of the previous invention has intumescence. In the analysis report of Toray mentioned above, it is an opal at 650 degreeC

It is assumed that there is the generation of. The rapid crystallization rate can be judged by comparing the peak difference with water glass of XRD (X ray diffraction, X-ray analyzer).

In Fig. 5, the vertical axis represents absorption spectrum cm ² / g of X-ray, and the horizontal axis represents wavelength, and Cu is a target. The crystal peak of the silanol salt solution of the previous invention is clear and shows a film formation as a solid precursor at a low temperature, and the reason why the holding water evaporates is a poby phenomenon.

In fact, even when 50% of the solid content of the silanol solution of the previous invention is applied to the iron plate, it is foamed even when heated at the bottom or burner at the top. This phenomenon continues until it reaches 650 degreeC, and since foaming ratio disappears as heating temperature rises, it becomes a paste and coats. This phenomenon could be observed with a high temperature microscope of Japan Hi-Tech.

This phenomenon is illustrated in the conceptual diagram of FIG. In FIG. 6, the upper figure shows the state in which the aqueous membrane-forming inorganic compound (LC) is bubbled and coated to form a colloidal filter by the exhaust gas and discharges purified gas such as water vapor and carbon dioxide gas. The conceptual diagram shows the conceptual diagram showing the state in which foaming calms down due to the temperature dropping of the residue. The lower figure is a conceptual diagram showing the state of the film containing the residue of the exhaust gas after returning to normal temperature. In this way, the aqueous colloidal inorganic compound (LC) colloid acts as a heat resistant filter.

The incineration exhaust gas of the waste contains hot gas and heavy metal-containing fertilizer, and the silanol salt solution of the previous invention must be filled to the extent that the exhaust gas pipe is filled to contain the exhaust gas described above. Since the silanol salt solution of the previous invention becomes a film-forming pore with a high-temperature exhaust gas, it has an effect of achieving the object of the present invention.

It is assumed that silanol is heated, H and OH dehydrate to form siloxane, and at this time, it is thought that Si-O-R (R is a metal) bond if there is a heavy metal. The incineration of the mixture of the silanol salt solution and the heavy metal content of the previous invention shows this fact without the elution of heavy metals. If it is only covered and covered like paint, it may be eluted when it is pulverized.However, the results of the method of pulverizing the sample showed no elution of heavy metals from the finely pulverized material by solidification at a temperature higher than 800 ° C. Therefore, it is thought that they are ionically bonded. That is, it shows that there is a capture action of heavy metals.

The prior invention silanol salts are 0.5-1 micron colloids. As can be seen from the FTIR of FIGS. 1 to 4 described above, the hydroxyl group is not lost even at 900 ° C. FIG. 7 shows a 50-80 micron-sized foamed ballooned state by observing the previous invention silanol salt solution in a gas heated at 450 ° C. with a micrograph powdered with a spray dryer at a nozzle temperature of 180 ° C. have. As can be seen from the estimated conceptual diagram of FIG. 6, when heated with a high temperature exhaust gas in the presence of excess water, the film-coated colloid is deposited as a gel-like substance on the surface. The retained water evaporates, but it is thought to contain waste solids by filtration to deposit the residue. Since the dioxin reaction of harmful exhaust gas does not occur above 450 ° C., the formation of dioxin can be controlled even when cooled to 400 ° C. or less, which is easy for dioxin to generate, to capture this precursor and hydrochloric acid component.

The silanol salt of the previous invention is an alkali metal salt. After pulverizing the excess water with a spray dryer with an outlet temperature of 200 ° C, the powder was kneaded with PVC in a roll of 40% by weight, and burned at 750 ° C with a Doman Elemental Analysis System. HCL was increased by 6000 times and soot was reduced to about 25% by filter collection analysis, which significantly reduced volatile hydrochloric acid and soot and reduced odor.

FIG. 8 is a table of a Xeon analysis center report showing a report of a Japanese Xeon analysis center of gas analysis obtained by mixing the solidified particulate material shown in FIG. 7 with PVC. From this result, the silanol salt solution of the previous invention could be expected to reduce the graphite and capture the odor causing gas.

In particular, the Li salt of hydrochloric acid is considered to be difficult to decompose at low temperatures even when chlorine is trapped. Therefore, the silanol Li salt solution of the previous invention is considered to act effectively as a countermeasure against dioxins of PVC.

Since the heavy metals in the waste contain the most Pb components, this model was used as a model, and according to the previous invention according to the Pb content weight in the ash containing 500 ppm to 2000 ppm of Pb component in ash and 15,000 ppm of ash. The glow salt solution was mixed from 10% to 140% and heated to 900 ° C. or higher. In either case, the dissolution test results of Pb yielded 0.1 ppm / l of stable assay value. It is thought to have produced the bond of siloxane described above.

CCA used in wood preservatives contains copper, chromium and arsenic. 10% of the silanol salt solution of the present invention was added to the 5% solution, and the solidified at 900 ° C. was green. However, the content of Cr, Cu, and As was less than 0.1 ppm even in the dissolution test. It is thought that these heavy metals also ion-bonded.

The silanol salt solution of the previous invention is considered to contain graphite and odor gas by foaming in a poby because it gels instantly when sprayed into a high-temperature exhaust gas of 200 ° C or more. As a result, gel colloids are considered to exhibit a filter action, and spraying from the exhaust gas is an effective means. Since the spraying means requires diffusion in a short time, spraying with an ejector that produces a high pressure generates a sufficient negative pressure to be sucked, causing the action of including the exhaust gas in the above-mentioned film-forming wastewater of silanol salt solution. It also contains gelled residue, which is compressed and deposited due to specific gravity difference to evaporate only water vapor. The same action is produced even if it is pressurized by the exhaust gas blown by the blower or sprayed by dropping in the blower exhaust gas. It is a necessary means of conveying, spraying and dropping the silanol salt solution of the previous invention. According to the method of contacting the silanol salt solution with the above-described exhaust gas, the silanol salt solution may be sprayed or dripped onto the exhaust gas which has been sucked and blown, or on the contrary, even if the hot exhaust gas is blown into the silanol salt solution to make contact with the film. To produce the same effect. Sedimentation is a difference in specific gravity, which is effective even if mineral powders such as kaolin and calcium carbonate are mixed.

Previously invented silanol salts can be easily mixed with wastes containing organic matter, heavy metals, soil, water and the like. As described above, the above-described silanol salt mixture mixed with the organic matter is burned to form a crude film, and carbonized and gasified to capture soot or Cl gas to filter through only water vapor and to be mixed at the same time with the bottom ash. . In parallel, if the above-described silanol salt solution is sprayed on the exhaust gas as described above, the purifying treatment effect of the present invention is exerted simultaneously with the flooring material and the exhaust gas.

의 지정비율까지 떨어뜨리는 것이 가능하였다.Stable valuables containing the above-mentioned silanol salt solution of the previous invention, and the residual gas deposits and the bottom ash of the exhaust gas are ceramics and do not elute even if they contain harmful heavy metals when fired in a rotary furnace at 800 ° C or higher, for example.

It was possible to drop the ratio to.

1. In the present invention, an aqueous film-forming inorganic compound composed of siloxane and silanol salt is brought into contact with combustion gases of graphite, odors, harmful metals containing heavy metals and non-materials to form a film-encapsulated material, among which graphite, odors and harmful gases are formed. And a combustion residue containing heavy metals, and simultaneously encapsulating the graphite, odors, harmful gases, and harmful metals or pollutants as heavy metals.

2. The present invention also mixes an aqueous film-forming inorganic compound composed of siloxane and silanol salt with a flooring material deposited on the bottom of an incinerator for incineration of waste to form a mixture of the flooring material and the aqueous film-forming inorganic compound. It is a purification process characterized by obtaining the combustion residue which the surface was coat | covered with the film | membrane of an aqueous film-forming inorganic compound, and sealing harmful substance and pollutant simultaneously.

3. The present invention further provides a firing residue or a mixture of both of which is coated with a film of the aqueous film-forming inorganic compound according to claim 1 or 2, wherein the firing is carried out at a temperature of 800 ° C. or higher. Or the treatment described in both.

4. The present invention also provides an aqueous film-forming inorganic compound composed of siloxane and silanol salts in contact with the combustion gas or the ash of the waste to form a film-encapsulation material, and combustion residues containing graphite, odors, harmful gases and heavy metals therein. Encapsulating and treating simultaneously the harmful substances or pollutants such as the graphite, the malodors, the harmful gases and the heavy metals, etc. It is a method of purification of waste.

5. The present invention is the waste purification method according to claim 4, wherein the contacting is performed by spraying an aqueous film-forming inorganic compound composed of siloxane and silanol salt on the combustion gas of the waste.

6. In addition, in the present invention, when the aqueous film-forming inorganic compound is brought into contact with the waste combustion gas, a pressure spray device is installed on the flue or suction side to spray the aqueous film-forming inorganic compound, and The method for purifying waste according to claim 5, wherein the graphite, the malodor, the noxious gas and the heavy metal are sucked.

7. In the present invention, when the aqueous film forming inorganic compound is brought into contact with the waste combustion gas, the waste combustion gas having a temperature of 200 ° C. or higher is blown into the aqueous film forming inorganic compound, and the graphite, odor, harmful gases and heavy metals are contained therein. A waste treatment method as set forth in claim 4, comprising a residue containing the substance.

8. The present invention is also a method for purifying waste, in which an aqueous film-forming inorganic compound composed of siloxane and silanol salt is brought into contact with the bottom ash combusted to form a film-encapsulated encapsulation, and encapsulated and treated with harmful or pollutants.

9. In the present invention, the aqueous film-forming inorganic compound is mixed with a treated material obtained by simultaneously encapsulating the harmful substances or pollutants, or the flooring material or the non-fired material which is combusted, heated to 800 ° C or higher, and ceramicized. It is the wastewater purification method of Claims 4-8 which prevent the elution of a pollutant.

In the third purification process and the fifth waste treatment method, an aqueous crude inorganic compound consisting of the siloxane and silanol salt solution is metal aluminum or metal silicon, hydrated borax, boric acid, sodium fluoride or When reacting a fluorinated acid and a zinc acid compound with an alkali metal of caustic, caustic soda, or caustic lithium, a concentrated solution reaction between the metal solid and the alkali metal is generated in water or in a solution of the inorganic acid compound, and the heat of reaction. It is good to use the aqueous film-forming inorganic compound which controls to within 50 to 100 degreeC, and makes specific gravity of a product 1.1 or more. In addition, it is preferable to add a metal compound to the aqueous aqueous film-forming inorganic compound to make the metal component excessive. In addition, a precipitate having a specific gravity of 1.3 or more produced by adding an inorganic acid to the aqueous film-forming inorganic compound or by mixing alcohols without addition is important.

The viscosity may be increased by adding natural or synthetic mineral powders, mineral fibers, and mineral layer materials to the aqueous membrane-forming inorganic compound. Alternatively, a hydroxide metal compound or a hydraulic composition may be added to the aqueous film-forming inorganic compound.

Various test results have demonstrated that graphite, odor of waste incineration gas, hydrochloric acid of dioxin precursor, and fertilizers or heavy metals that become hotbeds are captured without bug filter. Unlike ordinary liquids, the film solidified and exhibited a gel solidified film. As a result, water vaporized and the contained residues were deposited in a gel, and when reheated to 900 ° C. or higher, a stable valuable substance that did not elute heavy metals.

Even if the silanol salt solution is blown into the high-temperature exhaust gas, the same effect can be achieved by blowing the exhaust gas into the silanol salt solution.

Dioxin is the most harmful gas in the exhaust gas, but since it is established that chlorine of this precursor is not synthesized above 450 ° C, it is possible to prevent dioxin generation when removed at this stage, but there is no filter available at such a high temperature. As shown in FIGS. 1 to 4, the silanol salt solution of the previous invention has heat resistance, and colloids such as the sixth degree are bubbled to foam and have a filter action as shown in the conceptual diagram of the sixth degree. Since it is an alkali metal salt, HCL is trapped and becomes a nonvolatile component or controls the scattering of soot.

9 and 10 are tables showing the results of industrial and elemental analysis of the general municipal waste (MSW) and pulverized dust (SD) used in the combustion test. Although the diluted silanol salt solution is used at a high temperature, the specific heat does not change very much, and it coexists with a lot of excess water to produce an endothermic cooling effect, thereby cooling the exhaust gas and discontinuous operation of the species and small furnaces. -450 ° C It is dangerous to easily set the environmental temperature, but by injecting the silanol salt solution of the present invention as described above, it becomes possible to become pollution-free even without discontinuous operation at high temperature.

When the high temperature exhaust gas of 200-800 ° C. is blown into the silanol salt solution of the present invention, the silanol salt solution forms a film while evaporating water, and exhibits a poby phenomenon and includes graphite and odor generated by organic combustion. In addition, it became a heat-resistant inorganic filter and became harmless.

The result of the action which solved the subject of this invention by the following Example is shown.

Example 1

Prior invention silanol salt LCs do not decompose on heating. The process of slowly dehydrating to 10 ° C. to form a siloxane is shown in the FTIR diagram (analysis result of Gurere) at 20 ° C., 250 ° C., 550 ° C., and 950 ° C. of FIGS. 1 to 4. As the temperature rises, the water molecule peak is lowered, indicating that a film is formed.

Example 2

Table 1 shows the analysis of the LC used in the Example. LC contains raw material elements, but the analyzed elemental composition ratio is not limited thereto.

TABLE 1

※ Analysis result of Agne technical center (Japan)

This component ratio is close to the analysis of sewage of enamel, so it is heated and cured in the same shape to form a ceramic coating.

Example 3

Table 2 shows the temperature-dependent decrease in water content of the LC-150 with a pH of 12.2 with a specific gravity of 1.5% of the solid content of the silanol salt solution of 1.5, and the specific heat, diffusion coefficient, and thermal insulation coefficient between 20 and 1200 ° C Marked. (Agne technical center analysis results) Dehydration continues until high temperature, the specific heat insulation coefficient is not changed much even from room temperature to 1000 ℃ LC-150 is difficult to increase the temperature at high temperature, the endothermic agent of exhaust gas temperature To act as. If excess water is present, a synergistic effect indicates an endothermic quenching effect.

TABLE 2

TABLE 3

Example 4

The prior invention silanol salt LC-150 was sprayed and dried under the conditions of the LPG gas temperature of 450 degreeC and the outlet temperature of 180 degreeC with the apparatus of Okawa Genka Kooki.

Because LC is a colloid, and because of its porosity, it became a bubble of 50-80 microns. This bubbled photomicrograph is shown in FIG. It was added to 20-50% by weight of PVC and the stabilizing agent and the other to form a mixed sheet. The combustion analysis at 750 ° C. in the Xeon analysis center is shown in FIG. 8. Doman element analysis, ion chromatographic analysis, and filter collection were performed. As a result, even when PVC was burned at 750 ° C, the amount of volatile hydrochloric acid was reduced, the amount of nonvolatile hydrochloric acid was 6000 times, and soot was reduced to 25%. In other words, the combustion of vinyl chloride or Cl-containing material also showed the action of capturing spontaneous Cl that forms dioxin and inhibiting dioxin formation. At the same time, it prevented the generation of soot or odor.

Example 5

The characteristics of the LC-150 are analyzed by Si-MAS-NMR (unique analysis device developed by Michigan State University) (the test results commissioned by Iwate University to Michigan State University) are shown in FIG. In the analysis results, LC consists of a dimer and a trimmer, and FIG. 5 shows that the previous invention silanol salt solution did not show a significant crystal peak at 500 ° C., which is an average exhaust gas temperature. This indicated that the silanol salt solution had a film forming action with an exhaust gas of 400 to 800 ° C. That is, the colloid showed that the LC had a film forming ability with heat hygroscopicity when the colloid was collected when the excess moisture was lost.

Example 6

The LC-150 was applied to a stainless plate, and was heated and heated up to 900 ° C. under a high-temperature observation microscope manufactured by Japan Hi-Tech Co., Ltd., and photographed and observed by video. Foamed at 100 ℃ to 300 ℃, the eyepiece was blocked and the poby phenomenon continued to solidify to opal until the observed 650 degrees. Could. The conceptual diagram of FIG. 6 shows the behavior of the street. In other words, it was understood that when the LC was sprayed on the exhaust year of the combustion exhaust gas, it foamed in a moment and was prepared. The emission year works well with the LC being the full diameter of the foam. The same sedimentation effect was produced by introducing hot exhaust gas into the silanol salt solution of the previous invention.

Example 7

6 is a conceptual diagram showing the operation of the present invention. In FIG. 6, the silanol salt of the present invention is foamed into exhaust gas, the colloid is formed into a filter, and purified water vapor, carbon dioxide, and the like are released, and bubbles are precipitated to form a gel film. . All the test results obtained the same state as the conceptual diagram.

Example 8

산업종합연구소에서 용출시험한 결과를 표5에 나타내었다. 어느 경우도 안정형 유가물의 규제치 0.01 이하로 중금속의 정화작용이 있는 것으로 나타내었다. 소각재의 분석치는 다음과 같았지만 Pb 용출량은 222mg/ℓ였다.Table 4 shows a table in which 20-100 wt% of LC is mixed with respect to the analysis value of the base material containing 2220 mg / l PbO and 100 wt%. After baking this at 900 degreeC, Kanagawa

Table 5 shows the results of the dissolution test at the Industrial Research Institute. In all cases, it was shown that there was a purification effect of heavy metals below the regulation value of stable valuables. The incineration ash analysis was as follows, but the Pb elution was 222 mg / l.

TABLE 4

TABLE 5

NKK provided, analysis was conducted by Kanagawa Institute of Industrial Research

Example 9

제강소 제공의 도시먼지 소각 비재와 하수도 진흙 소각재의 중금속 분석치이다. 이에 상기 LC-140 (고형분40%)를 10-20 중량%를 첨가혼합하여, 950℃로 소성한 후에, 고오베 제강소가 용출시험을 한 결과를 표6에 나타낸다. Pb, As, Ce의 중금속의 용출은 안정형 규제치 이하였다.Koobe below

An analysis of heavy metals from urban dust incineration ash from sewage and sewage sludge incineration. Table 6 shows the results of the dissolution test conducted by Kobe Steel Mill after adding and mixing 10-20% by weight of LC-140 (40% solids) to 950 ° C. The leaching of heavy metals of Pb, As and Ce was below the stable regulation value.

TABLE 6

Example 10

From the 11th to turn attach the measure (b) in the year of the ordinary incinerator (a) and the LC-140 according to the present invention 20 capacity% / 1m ³ (50-fold) the aqueous solution tank (c) mixing the high-pressure pump ( d) is blown through the jet nozzle (e) and the LC diluent is blown into the measurement (b), and the LC liquid contains the discharge gas and the non-foam material sucked under the negative pressure of the high pressure pump, and foamed into the settling tank f. After being discharged from the bottom of the sedimentation tank (f), the methane taken out from the bottom of the settling tank (f) is put into a rotary kiln (h) and fired at 90 ° C. Exhaust (i) is an experimental device with stable valuables.

Example 11

계측(주)이 JIS 유해가스분석법에 따라서 분석하었다. 다이옥신이 가장 발생하기 쉬운 260 - 350。C의 배출가스온도 이었지만, 생성요인인 HCL은 250 - 110O ppm이고, 2.4 - 2.9 ppm 까지 격감하고, 증기배출구에 있어서 다이옥신은 20O mg TEQ 이였지만, 평균치로 1.9ng TEQ/Nm³ 이였다. 본 실시에는 버그필터의 사용하지 않고, 석회도 흡착재의 사용도 없이 본 발명 실라놀염액이 내열필터의 작용을 하여 염산과 다이옥신을 정화한 것이다. 이 진흙탕을 (h)인 로터리킬른에서 소성한 결과를 용출시험하였지만, 유해중금속은 O.O1 ppm이하였다. 상기 증기배출구(g)에 타올을 대어도 카본의 부착은 전무하여 악취를 느끼지 못했다. 침전조(f)의 온도는 상기 LC의 흡열작용에 의해 100。C 이하의 50-70 ℃로 다이옥신 생성하는 환경온도에서는 좋지않았다.9 shows the results of industrial analysis and elemental analysis of general waste (MSW) and ground dust (SD). In the above-mentioned SD, Cl component is large at 2.2%. Fig. 10 shows the analysis results of heavy metals and trace rare metals of the incineration ash. Fe ₂ O _{3, which} is a dioxin precursor, was 42.72%, Cu was 25.700 mg, and Zn had 38,000 mg / kg. The RDF described above was burned by the incineration test apparatus of the above embodiment. When LC was not added, graphite and odor were present. However, when the LC liquid described above began to be blown at ²⁰⁰ kg / cm ² pressure, neither graphite nor odor were lost in the exhaust steam (i). Gokan this process

Measurement Co., Ltd. analyzed in accordance with JIS noxious gas analysis method. Dioxin was the most likely 260-350 ° C off-gas temperature, but the resulting HCL was 250-110Oppm, decreased by 2.4-2.9ppm, and dioxin was 200 mg TEQ at the steam outlet, but on average 1.9ng TEQ / Nm ³ . In this embodiment, the silanol salt of the present invention acts as a heat-resistant filter to purify hydrochloric acid and dioxins without using a bug filter and without using lime or an adsorbent. The result of calcining the mud in a rotary kiln (h) was tested for elution, but the harmful heavy metals were less than 0.1 ppm. Even if the towel was applied to the steam outlet g, there was no adhesion of carbon and no odor was felt. The temperature of the precipitation tank (f) was not good at the environmental temperature of dioxin formation at 50-70 ° C. below 100 ° C. by the endothermic action of the LC.

Example 12

SD of FIGS. 9 and 10 contained a large amount of Pb of 1313 ppm, Cd of 29 ppm, Zn of 38,00 ppm, Cr of 831 ppm, and As of 29 ppm of heavy metals. The mixture was mixed at SD: LC = 10:10 (solid content ratio) and calcined at 950 ° C for 2 hours in an electric furnace, followed by a dissolution test of JIS. This result was able to achieve the target below the soil environmental standard value.

Example 13

SD of FIG. 9 is pulverized, the silanol salt liquid LC of the present invention described above is mixed with 10 wt%, and the jet spray liquid is 5% (solid content 2.5%) of the above-mentioned LC with waste as a combusted product. The pressure was 50 k and burned in the same manner as in Example 11. Since both the waste and the exhaust gas were mixed with the LC, the target values of Pb 0.0l mg, Cd 0.0l mg, and Cr 0.05 mg As 0.0l mg per liter of the soil waste threshold were achieved. Odor could not be felt or seen by the body.

Example 14

The ash from the smelting furnace contained 17,000 ppm of Pb (provided by Nippon Nippon Corp.). LC-150 having a solid content of 60% as described above was added to the base material, mixed and calcined at 900 ° C. for 1 hour in an electric furnace. The dissolution test results of No. 13 at the time of environmental cleanup were less than 0.1 ppm.

Example 15

11 is a conceptual diagram of an incinerator for use in the present invention. Connect the stack side (b) to the stack of the general incinerator (a), and inject the LC diluent (c) from the jet nozzle (e) into the settling tank (f) in the stack side (b). The steam (g) becomes harmless, odorless and colorless, and the sediment deposit is calcined in the rotary kiln (h) so that the discharge (i) becomes a stable valuables. In the apparatus of Fig. 11, a mixture of graphite, odorous cable rubber, PVC sheet, and foamed styrene residue was mixed and burned. It burned as it was, but it stopped burning because it made graphite and odor that was hard to endure. The solution of the tank (c) of the apparatus was adjusted to 2% (solid content 1%) of the liquid LC, and 1 liter (solid content 20 g) per 1 m ^{3 of} combustion gas was blown into the exhaust gas at an ejector pressure of 10 kg / cm 2. When combustion started, the graphite and odor could not be felt around. The sedimentation tank had carbon black mud deposits. When the exhaust gas 400 ℃ was piped into a separately prepared tank and blown into the tank (c), it was immediately bubbled to eliminate odors and graphite from exhaust steam. Even when the polyester paint was burned, graphite and odor disappeared as described above, and only steam was generated. It could be used many times without discarding the tank liquid.

The present invention succeeded in using a solution of the aqueous membrane-forming inorganic compound of Patent No. 2028203 Patent No. 7-14801. Since the silanol salt solution used in this invention is deposited at room temperature, the exhaust gas temperature does not affect the elevation of 200-800 ℃, causing the film formation and causing the exhaust gas year to fill the exhaust gas, which contains harmful gases or heavy metals. It contains the gas and cools the exhaust gas temperature and the heat-resistant colloid filter, and simultaneously purifies the contents to discharge only harmless water vapor.

The silanol salt solution of the present invention is an alkali metal salt, has an action of capturing HCL, becomes a siloxane at high temperature, has an oxygen bonding bond force with heavy metals, and exhibits an effect of preventing elution of the trapped heavy metals when fired. Therefore, since it captures the combustion metal and hydrochloric acid of a dioxin precursor, it has the effect and effect which prevent generation | occurrence | production of dioxin in advance. The silanol salt solution of the present invention should be selected from 1-300% by the amount of the solution mixed by Cl or the heavy metal amount, but from the reaction equivalent, the silanol salt solution containing 1-5 times the solid content of the heavy metal molecular weight is required. do. In addition, it is difficult to calculate the compounding ratio because it blows the exhaust gas by the apparatus and increases the air volume. However, it is considered that the degree of maintaining the reaction gas in the neutral phase is the dilution limit of the solution or the limit of the blowing amount. Because it is mixed, it must be confirmed by experiment.

The present invention enables the simultaneous treatment of carbon, organic and inorganic odors caused by combustion and ashes containing heavy metals. In particular, the treatment of exhaust gas prevents the generation of dioxin, which requires strict regulations, by treating odors and graphite. And simultaneous treatment with heavy metal pollutants.

Claims (9)

Aqueous film-forming inorganic compounds composed of siloxanes and silanol salts are contacted with combustion gases of graphite, odors, harmful metals containing heavy metals and fertilizers to form a crude film, containing graphite, odors, harmful gases and heavy metals. A purification treatment comprising the combustion residues to simultaneously encapsulate the graphite, odors, harmful gases and harmful metals or heavy metals at the same time. An aqueous film-forming inorganic compound composed of siloxane and silanol salt is mixed with a flooring material deposited on the bottom of an incinerator for incineration of waste to form a mixture of the flooring material and the aqueous film-forming inorganic compound, thereby forming the aqueous film-forming inorganic compound. A purification treatment characterized by obtaining a combustion residue covered with a surface of a compound film and simultaneously encapsulating harmful or pollutants. The purified material according to claim 1 or 2, wherein the combustion residue or a mixture of both of which is coated with a film of the aqueous film-forming inorganic compound is calcined at a temperature of 800 ° C or higher. An aqueous film-forming inorganic compound composed of siloxane and silanol salt is brought into contact with the combustion gas or the ash of the waste to form a film-encapsulated matter, and a combustion residue containing graphite, odor, harmful gas and heavy metals is formed therein. A method of purifying wastes by simultaneously encapsulating and treating harmful substances or pollutants such as graphite, malodors, harmful gases and heavy metals, etc., produced by burning wastes that simultaneously contain odors, harmful gases, and heavy metals. 5. The method of claim 4, wherein the contacting is performed by spraying an aqueous film-forming inorganic compound consisting of siloxane and silanol salts on the combustion gas of the waste. 6. The method according to claim 5, wherein when the aqueous film forming inorganic compound is brought into contact with the waste combustion gas, a pressure spray device is provided on the flue or suction side to spray the aqueous film forming inorganic compound, and the negative pressure generated in this case is generated. By the suction of the graphite, odor, harmful gases and heavy metals. 5. The method according to claim 4, wherein when the aqueous film forming inorganic compound is brought into contact with the waste combustion gas, the waste combustion gas having a temperature of 200 DEG C or more is blown into the aqueous film forming inorganic compound, and the graphite, odor, harmful gas or heavy metal are contained therein. A purification treatment method comprising the residue containing the contents. An aqueous film forming inorganic compound consisting of a siloxane and a silanol salt is brought into contact with a flooring material deposited on the bottom of a burned incinerator to form a film-forming waste material, and a waste material and pollutant are encapsulated and purified. The aqueous film forming inorganic compound according to any one of claims 4 to 8, wherein the aqueous film-forming inorganic compound is mixed with the treated material formed by simultaneously encapsulating the harmful substances or the pollutants, or the flooring material or the non-fired material that has combusted the waste material, and the temperature is 800 ° C. A method for the purification of wastes by heating and ceramics to prevent the release of harmful or pollutants.

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