JPH11267625A - Purification treatment product of harmful gas containing black smoke, malodor, heavy metal and fly ash and bottom ash deposited on bottom of incinerator or the like and purification treatment of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable easy attainment of clearance of the dioxin regulatory standard value that is considered as most difficult to clear, even at the time of discontinuously operating a medium- or small-size furnace, and reduction in equipment cost, revamping/modification cost of existing equipment and burden on inhabitants. SOLUTION: This purification treatment comprises: bringing an aqueous film forming inorganic compound material consisting of siloxane and a silanol salt(s) into contact with a combustion gas of harmful waste, that contains black smoke, malodor, heavy metals and fly ash, to form a filmily-formed foamy material and at the same time, to form a combustion residue having such a structure that black smoke, malodor, harmful gaseous constituents, heavy metals, etc. are incorporated into the filmily-formed foamy material. Thus, such harmful materials or pollutants, i.e., the black smoke, malodor, harmful gaseous constituents, heavy metals, etc. are concurrently sealed in the combustion residue.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying black smoke, malodor, heavy metals, harmful gases including fly ash, and bottom ash deposited on the bottom of an incinerator, and a method of purifying the same.

[0002]

2. Description of the Related Art From the living environment, black smoke and foul odors generated during the combustion of waste, as well as leaching and pollution of harmful heavy metals contained in incinerated ash and discharged fly ash, and strictly regulated emission in Europe. Strict regulations are also being imposed on dioxin emissions. At present, administrative guidance is given to convert from discontinuous operation of small and medium-sized incinerators for treating waste to continuous operation of large-scale incinerators. However, under the above-mentioned regulations, local governments and intermediate waste disposal companies that operate small and medium-sized reactors are forced to renovate expensive facilities or go out of business. However, practical proposals to solve this are made. Not.

[0003]

SUMMARY OF THE INVENTION Metal or CL
It is a common wisdom that if there is a component, organic matter will be burned to produce a harmful gas dioxin precursor. In addition, dioxin is generated even if cooling or scrubbing is performed on the way to the bag filter that does not have high heat resistance used in the final process of exhaust gas treatment, and adsorption treatment with inorganic substances and minerals is performed. It was necessary to reprocess the residue and the adsorbent. Complete processing required complex processing techniques and expensive equipment.

[0004] In addition, polluted heavy metals remain in the bottom ash of the incineration residue, which had been conventionally treated with a chelating agent and dumped in a managed landfill. It is said that there is a problem. In particular, dioxin and heavy metals are concentrated and remain in fly ash, and it is considered difficult to treat them with a chelating agent.

[0005] In the small incinerator, black smoke and bad smell are generated, which affects nearby residents, and the incinerator with the countermeasure has become expensive. Therefore, a simple and inexpensive method is desired.

[0006] In order to achieve the regulation values of dioxins and other gases and heavy metals by the Environment Agency, the cost of remodeling existing incinerators would be expensive, and the operation would be stopped. There is a concern that the burden on residents for environmental protection will increase.

[0007] The exhaust gas from the incinerator has a high temperature of 200 to 800 degrees Celsius, has no organic filter capable of filtering out black smoke and odor, and is cooled or scrubbed. It was treated with an adsorbent, cooled, and sent to a bag filter. Therefore, since the apparatus is expensive, an inorganic filter and an adsorbent that can withstand high temperatures and do not require post-treatment have been desired. The present invention seeks to solve this.

Conventionally, there has been recognized a method of treating bottom ash and fly ash containing a heavy metal, which includes a method of mixing a chelating agent with an organic substance such as carbamic acid, which has been widely used. Stable is difficult to evaluate chemically, and requires a method to convert heavy metals into chemically stable ionic bonds.

In Europe, dioxin countermeasures have been taken from an early stage, but exhaust gas cooling has been the mainstream until recently, but recent studies have shown that dioxin precursors
Dioxin is generated at low temperature in the presence of HCL. To solve this problem, an adsorption method using activated carbon or slaked lime usable at 450 ° C. or higher has been utilized. However,
Problems remain in the post-treatment of this adsorbent. Nevertheless, a bag filter was still required, and the heavy metal-containing fly ash remaining there had to be scraped and treated. That is,
Naturally, exhaust gas treatment requires fly ash treatment containing a dioxin precursor and iron chloride and heavy metals, and a filter that adsorbs dioxin-decomposing catalysts and pollutants. , And had to be disposed of again.

The present invention has been made in view of such circumstances, and the use of the present invention makes it possible to easily set the dioxin regulation value, which is considered to be most difficult to clear even in a small-to-medium-sized furnace operated discontinuously. It is possible to reduce the cost of equipment and the cost of modifying existing furnaces, reduce the burden on residents, and have a wide range of other industrial uses.

The present inventors have proposed a method for producing an aqueous film-forming inorganic compound (Japanese Patent No. 2028203, Japanese Patent Publication No. 7-1480).
No. 1) "Disaster prevention / fire prevention / fire resistant composite material (Patent No. 201569)
No. 4), etc.-hereinafter referred to collectively as the prior invention silanol salt solution-. This prior invention silanol salt solution is produced from a solid and a concentrated alkali solution reaction using metasilicon and borax, sodium fluoride, a mineral acid or a salt thereof, and an alkali metal (Na, K, Li). Unlike the above, it is composed of a siloxane and a silanol salt. Figs. 1 to 4 show that the aqueous film-forming inorganic compound (LC) used in the present invention is a heat-resistant inorganic substance at 20C / 250C / 550C / 96.
It is a figure which shows the water film | membrane peak reduced by heating at 0 degreeC FTIR analysis, and film formation. The horizontal axis in FIGS. 1 to 4 is
WAVE NUMBERS (wave number), the vertical axis shows ABSORVANCE (absorbance). The analysis report of this Toray Research Center,
According to the FTIR analysis of 4), 780 cm ^-1 of siloxane and 9
00,1000,2400-3800 cm ^-1 indicates the presence of silanol. The silanol salt solution of the present invention has a
It is a heat resistant material that has heat resistance in any high temperature range of 000 ° C. and does not decompose.

The silanol salt solution of the prior invention has an intumescent (intume)
scence). In the above Toray analysis report, 65
It is stated that opal (foam stone) is generated at 0 ° C. The high crystallization rate is due to the 500 ° C XRD shown in FIG.
(This is a special device that analyzes only Si compounds with an X ray diffraction X-ray analyzer.) It can be determined by comparing the peak difference with water glass. In FIG. 5, the vertical axis is the X-ray absorption spectrum cm ² / g, the horizontal axis is the wavelength, and Cu is the target material. The crystal peak of the silanol salt solution of the prior invention is clear, indicating that the film becomes a solid phase precursor at a low temperature to form a film, and may explain the reason why the vaporization phenomenon occurs when the retained water evaporates. In fact, a liquid having a solid content of 50% of the silanol liquid of the prior invention is applied to an iron plate, and the foaming phenomenon is exhibited even when the liquid is heated from below or by a burner from above. This phenomenon continues until the temperature reaches 650 ° C, and thereafter, as the heating temperature rises, the bubbling bubbles disappear and the paste is formed to form a coating film. This phenomenon could be observed with a high temperature microscope manufactured by Japan High Tech Co., Ltd. This phenomenon is shown in the conceptual diagram of FIG. In FIG. 6, the upper diagram is a conceptual diagram showing a state in which the aqueous film-forming inorganic compound (LC) is bubbled and formed into a film by the exhaust gas to form a colloid filter and discharges a purification processing gas such as water vapor and carbon dioxide gas. FIG. 3 is a conceptual diagram showing a state in which foaming is calmed down due to a decrease in the temperature of the residue, and a lower diagram is a conceptual diagram showing a state in which the exhaust gas residue is included in a coating film after returning to normal temperature.
Thus, the aqueous film-forming inorganic compound (LC) colloid acts as a heat-resistant filter. The waste incineration exhaust gas contains high-temperature gas and heavy metal-containing fly ash, and the silanol salt solution of the present invention must be bubbling enough to fill the exhaust gas pipe to include the exhaust gas. Must. Since the silanol salt solution of the present invention becomes a film-forming foam by high-temperature exhaust gas, the silanol salt solution has the effect of achieving the object effect.

It is a conventional theory that the silanol is heated and H and OH are dehydrated to form a siloxane. At that time, it is considered that if a heavy metal is present, it is bonded to -Si-0-R (R is a metal). Analysis of the incinerated product of the mixture of the silanol salt solution of the prior invention and the heavy metal-containing material shows that this is the fact that no heavy metal was eluted. If only the coating is concealed like a paint, it can be eluted by pulverization, but the method of pulverizing and testing the sample shows that heavy metals from solidified and pulverized at a high temperature of 800 ° C or higher Since no elution was observed, it is considered that ionic bonds were formed. In other words, it indicates that there is a heavy metal trapping action.

The silanol salt solution of the present invention is a colloid of 0.5 to 1 micron. As seen from the FTIR of FIGS. 1 to 4 above, even at 900 ° C., the hydroxyl groups have not disappeared.
FIG. 7 is a photomicrograph of a silanol salt solution of the present invention powdered with a spray dryer when the nozzle temperature is 180 ° C. with a heated gas of 450 ° C., in a state of a foamed balloon of 50 to 80 μm in size. Is shown. FIG.
As shown in the conceptual diagram, if heated with high-temperature exhaust gas in the presence of excess water, the colloid that formed the film was fused with the surface gel and the gel-containing water evaporated.
It is thought that the solid content of the waste is encapsulated by the filter action and the residue is deposited. There is a theory that dioxin reaction in harmful exhaust gas does not occur above 450 ° C.
If the precursor and the hydrochloric acid component are captured, the generation of dioxin can be controlled even when the temperature is cooled to 400 ° C. or less, where dioxin is easily generated.

The silanol salt solution of the invention is an alkali metal salt. The excess water is blown away with a spray dryer at an outlet temperature of 200 degrees to form powder, and then added to PVC at a weight ratio of 4%.
0% was kneaded in a roll and analyzed by burning at 750 ° C. with a Doman elemental analyzer. From the results, it was found that volatile hydrochloric acid was underestimated, non-volatile HCL was increased 6000 times, and soot was about 25% by filter collection analysis. %, Volatile hydrochloric acid and soot are significantly reduced, and the odor is also reduced. FIG. 8 is a table of the report of the Zeon Analysis Center showing the report of the gas analysis of the Zeon Analysis Center of Japan, in which the solidified particulate matter shown in FIG. 7 is mixed with PVC and fired. From these results, it was possible to predict that the silanol salt solution of the prior invention had an effect of reducing black smoke and trapping a gas causing an offensive odor. In particular, it is considered that the Li salt of hydrochloric acid is hardly decomposed at a low temperature even if it captures chlorine, and it is considered that the silanol Li salt solution of the present invention effectively acts as a measure against dioxin in PVC.

Since the Pb component is the largest among the heavy metals in the waste, this was used as a model. The bottom ash contained 500 to 2000 ppm of the Pb component and the bottom ash contained 15,000 ppm of fly ash. According to the Pb-containing weight, the ash is mixed with the silanol salt solution of the prior invention from 10% to 140%.
% And heated above 900 ° C. In any case, the results of the Pb dissolution test indicate that the stable analysis value of 0.
A result of 01 ppm / liter was obtained. It is considered that the siloxane bond described above was generated.

The CCA used in wood preservatives contains copper, chrome and arsenic. The 5% solution to which 10% of the silanol salt solution of the previous invention was added and heated and solidified at 900 ° C. was green, but even in the dissolution test, Cr, Cu, A
The amount of s was less than 0.01 ppm. It is considered that these heavy metals were also ionically bonded.

If the silanol salt solution of the prior invention is sprayed into a high-temperature exhaust gas of 200 ° C. or more, it is thought that it instantaneously forms a gel-forming film to form bubbles and contains black smoke and odorous gas. As a result, the gel colloid is considered to exhibit a filter action, and spraying on exhaust gas is an effective means. Since the spraying means needs an instant spread,
When sprayed with an ejector that generates high pressure, a negative pressure is generated that is sufficient for suction, and the action of including exhaust gas in the film-forming foam of the silanol salt solution occurs, and a gelled residue including fly ash is generated. , Is pumped and deposited with a specific gravity difference, and only water vapor evaporates. A similar effect is produced by spraying the exhaust gas blown by the blower under pressure or by dripping the exhaust gas. The pumping, spraying, and dropping of the silanol solution of the prior invention is a necessary means. In the method for contacting the silanol salt solution with the exhaust gas according to the previous invention, the high temperature exhaust gas is blown into the silanol salt solution regardless of whether the silanol salt solution is sprayed or dropped on the exhaust gas sucked or blown. Even when they were brought into contact with each other, the same action and effects were produced due to film formation foaming. Since sedimentation occurs due to the difference in specific gravity, it is effective to mix mineral powders such as kaolin and charcoal.

The silanol solution of the invention can be easily mixed with waste containing organic substances, heavy metals, soil, moisture and the like.
As described above, if the organic matter is burned, the mixed silanol salt solution becomes a film-forming foam and contains the combustion gas, captures carbonized and gasified soot and CL gas, and passes only water vapor. It acts as a filter and is simultaneously mixed with the bottom ash. At the same time, if the silanol salt solution is sprayed on the exhaust gas as described above, the bottom ash and the exhaust gas can simultaneously exhibit the purifying effect of the present invention.

Including the above-mentioned silanol salt solution of the invention,
Exhaust gas residue deposits and bottom ash can be burned at 800 ° C or higher, for example, in a rotary furnace, even if they contain harmful heavy metals.
The ratio of stable valuables that did not elute was reduced to the specified ratio.

[0021]

[Means for Solving the Problems] The present invention makes an aqueous film-forming inorganic compound composed of siloxane and silanol salt into contact with the combustion gas of harmful wastes including black smoke, odor, heavy metals, and fly ash to form film-forming foams. Purification treatment characterized by forming a combustion residue containing black smoke, odor, harmful gas and heavy metal, and simultaneously sealing harmful and polluting substances of black smoke, odor, harmful gas and heavy metal. Things. 2. The present invention also forms a mixture of a bottom ash and an aqueous film-forming inorganic compound by mixing an aqueous film-forming inorganic compound comprising a siloxane and a silanol salt with bottom ash deposited on the bottom of an incinerator for incinerating waste, This is a purification treatment characterized by obtaining a combustion residue whose surface is coated with the film of the aqueous film-forming inorganic compound, and simultaneously sealing harmful substances and pollutants. 3. Further, the present invention is characterized in that the combustion residue or the mixture of both, the surface of which is coated with the film of the aqueous film-forming inorganic compound according to claim 1 or 2, is fired at a temperature of 800 ° C. or more. Item 1 or 2 or both. 4. The present invention also provides an aqueous film-forming inorganic compound comprising a siloxane and a silanol salt, which is brought into contact with the combustion gas or fly ash of waste to form a film-forming foam, in which black smoke, odor and harmful gases and harmful gases are contained. It is a combustion residue containing heavy metals, and is the black smoke, odor and harmful gas, and heavy metals.
Purification of wastes by simultaneously sealing and purifying harmful substances and pollutants such as black smoke, foul odor, harmful gas and heavy metal-containing substances, which are generated by burning wastes that are simultaneously sealed with harmful substances and pollutants. Is the way. 5. The present invention is the method for purifying waste according to claim 4, wherein the contact is performed by spraying an aqueous film-forming inorganic compound composed of a siloxane and a silanol salt onto the combustion gas of the waste. . 6. Also, the present invention provides a method for spraying the aqueous film-forming inorganic compound by attaching a pressurized spraying device to a flue or a suction side passage when the aqueous film-forming inorganic compound is brought into contact with waste combustion gas. 6. The method for purifying waste according to claim 5, wherein the black smoke, the bad smell, the harmful gas and the heavy metal are sucked by the generated negative pressure. 7. Also, the present invention provides that when the aqueous film-forming inorganic compound is brought into contact with waste combustion gas, the waste combustion gas at 200 ° C. or higher is blown into the aqueous film-forming inorganic compound, and the black smoke or The waste purification method according to claim 4, wherein the residue is a residue containing an odor, a harmful gas, and a substance containing heavy metals. 8. In addition, the present invention provides an aqueous film-forming inorganic compound composed of a siloxane and a silanol salt, which is brought into contact with the bottom ash produced by burning the waste to form a film-forming boiler, and a waste for sealing and purifying harmful substances and pollutants. Is a purification treatment method. 9. Further, the present invention also provides a treatment product obtained by simultaneously sealing the harmful substances and pollutants, or a bottom ash or fly ash obtained by burning waste and mixing the aqueous film-forming inorganic compound with the mixture and heating the mixture to 800 ° C. or more. The waste purification method according to any one of claims 4 to 8, wherein the waste material is ceramicized to prevent elution of harmful substances and pollutants. In the above-described three purification treatment products and the five waste treatment methods, in the aqueous film-forming inorganic compound composed of the siloxane and silanol salt, metallic aluminum or metallic silicon is hydrated to borax, boric acid, or fluoride. In reacting soda or hydrofluoric acid and a zinc acid compound with an alkali metal of caustic potash, caustic soda or caustic lithium, a concentrated solution reaction of the metal solid and the alkali metal occurs in water or a solution of the mineral acid compound. In addition, it is preferable to use an aqueous film-forming inorganic compound having a specific gravity of 1.1 or more, while controlling the reaction heat to 50 ° C. or more and 100 ° C. or less. In addition, it is preferable to add a metal compound to the aqueous film-forming inorganic compound generated above to make the metal component excessive. Further, it is preferable to form a precipitate having a specific gravity of 1.3 or more, which is formed by mixing an aqueous film-forming inorganic compound with or without adding a mineral acid. It is preferable to add a natural or synthetic mineral powder, a mineral fiber, or a mineral layer to the aqueous film-forming inorganic compound to increase the viscosity. It is preferable to add a hydroxide metal compound or a hydraulic composition to the aqueous film-forming inorganic compound.

[0022]

From the results of various tests, it has been proved that black smoke and odor of waste incineration gas, hydrochloric acid of dioxin precursor, fly ash and heavy metal which becomes a hotbed are trapped without a bag filter. Also, unlike ordinary liquids, it shows film-forming bubbling phenomena, and as a result of gelation of solidified coating film, water evaporates and the contained residue deposits in a gel-like form. It became a stable valuable material that did not elute heavy metals. A similar effect can be obtained even if the silanol salt solution is blown into the high-temperature exhaust gas or vice versa.

Although dioxin is the most harmful gas in the exhaust gas, it is said that chlorine as a precursor is not synthesized at 450 ° C. or higher. There is no filter available for its high temperature. The silanol salt solution of the previous invention is
As shown in FIGS. 1 to 4, it is heat-resistant, and as shown in FIG. 6, the colloid bubbles and turns into a balloon, has a filter action as shown in the conceptual diagram of FIG. Therefore, it captures HCL, converts it to non-volatile components, and controls the generation and scattering of soot. FIGS. 9 and 10 show general waste (MSW) and shredder dust (S) used in the combustion test.
It is a table | surface which shows the industrial analysis and elemental analysis result of D). Before injecting into the exhaust gas, use the silanol salt solution diluted with a large excess of water, but the specific heat of the silanol salt solution does not change so much at high temperatures, and it coexists with a large excess of water. This causes the exhaust gas to cool down and the small and medium-sized furnaces to operate discontinuously.
Although it is considered dangerous to easily form an environmental temperature of 0 ° C., if the silanol salt solution of the present invention is blown, it is possible to eliminate pollution without discontinuous operation or high-temperature firing. . 200-80 to the above silanol salt solution of the present invention.
When the high-temperature exhaust gas of 0 ° C. is blown in, the silanol salt solution forms a film while evaporating water, and shows a bubbling phenomenon.
It contains black smoke and foul odor generated by organic matter combustion, and is made harmless by heat-resistant inorganic filter.

The following embodiments will show the results of the operation that solved the problem.

EXAMPLE 1 The silanol salt liquid LC of the previous invention is not decomposed even when heated, and is gradually dehydrated to 1000 ° C. to form a siloxane.
FTIR diagrams at 50 ° C, 550 ° C, and 950 ° C (analysis results of Toray Research Center) are shown. As the temperature increased, the water molecule peak became lower, indicating that the film was formed.

[0025]

Example 2 Table 1 shows the analytical values of LC used in the previous example.
Shown in LC includes the raw material elements used, but the analyzed elemental composition ratio is not limited to this.

[0026]

[Table 1] Since this component composition ratio was close to the analysis value of the enamel under the glaze, it was similarly heated and cured to form a ceramic coating.

[0027]

Example 3 Table 2 shows the amount of water loss of the LC-150 having a specific gravity of 50% solids, a specific gravity of 1.5, and a pH of 12.2 in the silanol salt solution of the prior invention, which is shown in Table 2, and 20 to 1200.
The specific heat, the diffusion coefficient and the adiabatic coefficient between ° C are shown in Table 3 (Agne Technology Center analysis values). Dehydration continues to high temperatures, but the specific heat and adiabatic coefficient do not change much from normal temperature to 1000 ° C. The reason that LC-150 hardly rises in temperature even at high temperatures and acts as an endothermic agent for exhaust gas temperature Is shown. Excessive water indicates a synergistic effect of endothermic quenching.

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

Example 4 The silanol salt solution LC-150 of the invention was used
Spraying and drying were carried out at a temperature of 450 ° C at the LPG gas temperature and at an outlet temperature of 180 ° C using the Okawara Kakoki equipment. Since LC is a colloid and foamy, it has a balloon of 50 to 80 microns. The ballooned micrograph is shown in FIG. This was kneaded into a sheet by adding 20 to 50 parts by weight of PVC and a conventional stabilizer and the like.
FIG. 8 shows the results of the 750 ° C. combustion analysis at the Zeon Analysis Center. The analysis was performed by a Doman elemental analyzer and ion chromatography analysis / filter collection method. As a result, PV
Even if C was burned at 750 ° C., the amount of volatile hydrochloric acid was reduced, the amount of nonvolatile hydrochloric acid was increased by 6000 times, and soot was reduced to 25%. In other words, it was shown that even when PVC or CL-containing substances were burned, volatile CL forming dioxin was trapped and dioxin formation was inhibited. At the same time, the generation of soot and odor was inhibited.

[0031]

Embodiment 5 The characteristics of the LC-150 were changed to Si-MAS.
FIG. 5 shows the results of analysis by NMR (a unique analyzer developed by Michigan State University) (test results requested by Iwate University to Michigan State University). According to the analysis results, the LC is composed of dimers and trimers. FIG. 5 shows that the silanol salt solution of the present invention shows a remarkable crystal peak at an average exhaust gas temperature of 500 ° C., and the water glass is crystallized with amorphous. No peak was shown. This indicated that the silanol salt solution had an effect of forming a film at an exhaust gas of 400 to 800 ° C. That is, the LC of the colloid showed that if excess water disappeared, the colloid was aggregated and had a heat- and endothermic film-forming ability.

[0032]

Embodiment 6 The above-mentioned LC-150 was applied to a stainless steel plate, and was photographed and observed with a video while being heated from normal temperature to 900 ° C. with a high-temperature observation microscope of Japan High Tech Co., Ltd. Bubbling from 100 ° C to 300 ° C closed the eyepiece, cleaned the lens and observed again.
The bubbling phenomenon continued until around 50, and it was observed that it solidified into an opal (foamstone) state, plasticized at 800 ° C. or more, and turned into a paste like a syrup. The behavior as shown in the conceptual diagram of FIG. 6 was shown. That is, it was understood that when the LC was sprayed on the flue gas of the flue gas, the bubbles instantaneously bubbled. The flue gas is LC
If the diameter is such that the bubble is filled with bubbles, it works efficiently. Even when high-temperature exhaust gas was introduced into the pre-silanol salt solution, the same deposition effect was produced.

[0033]

Embodiment 7 FIG. 6 is a conceptual diagram showing the operation of the present invention.
In FIG. 6, the silanol salt solution of the present invention is bubbled by the exhaust gas, its colloid is formed into a film to form a filter, purified water vapor, carbon dioxide gas and the like are released, and the bubbles are calmed down to form a gel film. All the test results were in the same state as the conceptual diagram.

[0034]

Example 8 The analysis value of fly ash containing 2220 mg / l of PbO and the LC of 20 parts per 100 parts by weight thereof were analyzed.
Table 4 shows a mixture of １００100 parts by weight. After firing at 900 ° C., the results of the dissolution test at Kanagawa Prefectural Institute of Industrial Science are shown in Table 5. In each case, the regulation value of stable valuables was 0.01 or less, indicating that it has a heavy metal purification effect. The analytical values of the incinerated ash were as follows, but the Pb elution amount was 222 mg / liter.

[Table 4]

[0035]

[Table 5]

[0036]

[Example 9] The following is municipal waste incineration fly ash provided by Kobe Steel.
And heavy metal analysis values of sewage sludge incineration ash. To this
Add 10 to 20 parts by weight of LC-140 (solid content 40%).
And fired at 950 ° C before Kobe Steel
Table 6 shows the results of the test. Of Pb ・ As ・ Ce
The elution of heavy metals was below the stable type regulation value.Heavy metal analysis value  Heavy metal Urban waste Sewer sludge  Pb mg / K 503 200 AS mg / K 1.2 40Ce mg / K 0.4 <0.1

[0037]

[Table 6]

[0038]

[Embodiment 10] Fig. 11 is a side view of a flue of an ordinary incinerator (a), with a side passage (b), and an aqueous solution tank (LC) of the present invention mixed with 20 parts by volume / m3 (50 times). From c), the LC diluted liquid is blown into the side passage (b) through the jet spray (e) by the high pressure pump (d), and the LC liquid bubbles exhaust gas and fly ash sucked by the negative pressure of the high pressure pump. It is introduced into the sedimentation tank (f) and formed as sludge, and is deposited and discharged from the outlet (g). The treated water vapor and carbon dioxide gas, which are free from black smoke and offensive odor, are discharged. (F) The sludge taken out from the bottom is put into a rotary kiln (h), fired at 900 ° C., and discharged (i)
Is an experimental device that can be used as a stable valuable resource.

[0039]

Embodiment 11 FIG. 9 shows the results of industrial analysis and elemental analysis of general waste (MSW) and shredder dust (SD).
The SD has a large CL component of 2.2%. FIG. 10 describes the analysis results of heavy metals and trace rare metals in the incinerated ash. 42. Dioxin precursor Fe ₂ O ₃
72%, 25.700 mg of Cu, 38,000 of Zn
mg / Kg. The aforementioned RDF was burned by the incineration test apparatus of the previous example. When LC was not introduced, black smoke and odor were produced. However, when the above-mentioned LC solution was started to be blown at a pressure of 200 kg / cm ² , both black smoke and odor disappeared from the discharged steam (i). This process was analyzed according to JIS Hazardous Gas Analysis by Kokan Keisoku Co., Ltd. Although the exhaust gas temperature was 260 to 350 ° C., where dioxin was most likely to be generated, HCL, which is a factor of the generation, had a concentration of 250 to 1100 ppm, which was 2.4.
To 2.9 ppm, and the dioxin at the steam outlet was 200 ng TEQ, but the average value was 1.9.
ngTEQ / Nm ³ . In this embodiment, no bag filter was used, no lime and no adsorbent was used, and the silanol salt solution of the present invention acted as a heat-resistant filter to purify hydrochloric acid and dioxin. (H)
The results of the sintering using a rotary kiln were tested for dissolution.
Hazardous heavy metals were less than 0.01 ppm. Even if a towel was placed on the steam outlet (g), no carbon was attached and no odor was felt. Due to the endothermic effect of the LC, the temperature of the precipitation tank (h) did not reach the environmental temperature at which dioxin was formed at 50 to 70 ° C., which was 100 ° C. or less.

[0040]

Embodiment 12 SD of FIGS. 9 and 10 indicates that Pb of heavy metal is 1
313 ppm, Cd 29 ppm, Zn 38,000 ppm
. It contained a large amount of 831 ppm of Cr and 29 ppm of As. This is defined as SD: LC = 10: 10 (solid content ratio).
And calcined at 950 ° C for 2 hours in an electric furnace.
A JIS dissolution test was performed. As a result, the target below the soil environmental standard value was achieved.

[0041]

Embodiment 13 The SD of FIG. 9 is pulverized, and 10% by weight of the above-mentioned silanol salt liquid LC of the present invention is added and mixed to form a waste combustion product.
% (Solid content: 2.5%) and a pressure of 50%.
K and burned as in Example-11. Since the LC was mixed with both waste and exhaust gas, 0.01 mg of Pb, 0.01 mg of Cd,
The target values of 0.05 mg of Cr and 0.01 mg of As were achieved. There was no odor or black smoke generated.

[0042]

Embodiment 13 One of Pb components was added to fly ash generated in a melting furnace.
It contained 7,000 ppm (provided by New Nichinan). To this fly ash, 240% of the above-mentioned LC-150 having a solid content of 60% was added and mixed, followed by firing at 900 ° C. for 1 hour in an electric furnace. According to the dissolution test result of Environment Agency Notification No. 13, it was 0.01 ppm or less.

[0043]

Embodiment 14 FIG. 11 is a conceptual diagram of an incinerator used in the present invention. The chimney of the general incinerator (a) and the chimney sideway (b)
And the LC dilution liquid (c) is blown into the chimney side path (b) from the jet nozzle (e) by the high pressure pump (d),
The steam (g) is put into the sedimentation tank (f), and the vapor (g) becomes harmless, odorless, and colorless, and the sediment is burned in the rotary kiln (h), and the discharge (i) becomes a stable valuable. FIG.
With the device described above, black smoke and foul-smelling cable rubber, PVC sheet, and styrofoam were mixed and burned. It burned as it was, but it stopped producing because of unbearable black smoke and odor around it. The solution in the tank (c) of the apparatus was adjusted to a liquid of 2% (solid content: 1%) of the LC, and 1 liter (solid content: 20 g) per 1 m ^{3 of} combustion gas was discharged into the exhaust gas at an ejector pressure of 100 kg / cm ^2. When I started to burn it, I couldn't feel black smoke and bad smell around. In the settling tank, there was a deposit of black sludge containing carbon. When 400 ° C. of the exhaust gas was drawn into a separately prepared tank by a pipe and blown into the tank (C), the foam instantaneously boiled, the bad odor disappeared, and the black smoke disappeared from the discharged steam. Even when the polyester paint was burned, the black smoke and odor disappeared as described above, and only steam was generated. It could be used several times without discarding the tank liquid.

[0044]

[Operation and effect of the present invention] The present invention is disclosed in Japanese Patent No. 202820.
No. 3 (Japanese Patent Publication No. 7-14801) succeeded by using a solution of an aqueous film-forming inorganic compound. Since the silanol salt solution used in the present invention forms a film even at room temperature, the film formation bubbling phenomenon occurs without being affected by the temperature of the exhaust gas at 200 to 800 ° C., and the exhaust gas flue is filled to cause harmful gases and heavy metals. And a function of cooling the exhaust gas temperature and a function of a heat-resistant colloid filter, purifying the inclusions at the same time, and discharging only harmless water vapor. The silanol salt solution of the present invention is an alkali metal salt,
It has the effect of trapping L and becomes siloxane at a high temperature, has an oxygen binding force with heavy metals, and has the effect of preventing the elution of the trapped heavy metals when fired. Therefore, the chlorinated metal and hydrochloric acid of the dioxin precursor are trapped, so that it has the effect and effect of preventing the generation of dioxin. The silanol salt solution of the present invention has to be selected from 1 to 300% in the amount of solution to be mixed depending on the amount of CL or heavy metal. However, from the reaction equivalent, it contains the solid content of 1 to 5 times the molecular weight of heavy metal. Requires silanol salt solution. In addition, it is difficult to calculate the mixing ratio in practice, because the air is blown to the exhaust gas by the device to increase the air volume. However, the extent to which the reaction gas is kept above neutral is considered to be the solution dilution limit and the blowing amount limit.
Since it is a mixture of various elements, it must be confirmed by experiments. The present invention enables simultaneous treatment of carbon and organic and inorganic odors generated by combustion and heavy metal-containing ash. Prevents the generation of dioxins that require particularly strict regulations. Processing was enabled at the same time as processing.

[Brief description of the drawings]

FIG. 1 shows an aqueous film-forming inorganic compound (L) used in the present invention.
It is a figure which shows the film formation that a water molecule peak falls by heating at 20 degreeC FTIR analysis which shows that it is heat-resistant inorganic substance of C).

FIG. 2 shows an aqueous film-forming inorganic compound (L) used in the present invention.
250 ° C. FTIR indicating that it is a heat-resistant inorganic substance of C)
It is a figure which shows the film formation that a water molecule peak falls by heating by analysis.

FIG. 3 shows an aqueous film-forming inorganic compound (L) used in the present invention.
550 ° C. FTIR indicating that it is a heat-resistant inorganic substance of C)
It is a figure which shows the film formation that a water molecule peak falls by heating by analysis.

FIG. 4 shows an aqueous film-forming inorganic compound (L) used in the present invention.
960 ° C FTIR indicating that it is a heat-resistant inorganic substance of C)
It is a figure which shows the film formation that a water molecule peak falls by heating by analysis.

[Fig. 5] Iwate University requested Michigan University to use Si
FIG. 4 is a diagram showing a film-forming property in which a peak was observed only in LC in a comparison of a product at 500 ° C. between a silanol salt solution of the present invention and water glass by MAS-NMR LC analysis.

[Fig. 6] A silanol salt solution of the present invention containing excess water is blown into high-temperature exhaust gas to form a film-forming foam, which becomes a heat-resistant filter.
It is a conceptual diagram which turns into a coating film by temperature fall.

FIG. 7 shows a gas outlet temperature of 180 ° C. at a gas temperature of 450 ° C.
It is a micrograph of the particles which were actually produced by a spray dryer at ℃ and formed into a film-forming bubble and ballooned.

FIG. 8 is a table showing a report of the results of a gas analysis performed by mixing the solidified granular material shown in FIG.

FIG. 9 is a table showing analysis results of heavy metals in ash of general garbage (MSW) and shredder dust (SD) used in a combustion test.

FIG. 10 is a table showing the results of industrial analysis and elemental analysis of general waste (MSW) and shredder dust (SD) used in the combustion test.

FIG. 11 is a conceptual diagram of an incinerator used in the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B01D 53/70 B09B 3/00

Claims (9)

[Claims] An aqueous film-forming inorganic compound comprising a siloxane and a silanol salt is brought into contact with a combustion gas of harmful waste containing black smoke, odor, heavy metal and fly ash to form a film-forming foam. It is a combustion residue containing black smoke, odor, harmful gas and heavy metal in it, and the black smoke, odor, harmful gas and heavy metal, harmful substances and pollutants are simultaneously sealed. Purified material. 2. An aqueous film-forming inorganic compound comprising a siloxane and a silanol salt is mixed with a bottom ash deposited on the bottom of an incinerator for incinerating waste to form a mixture of the bottom ash and the aqueous film-forming inorganic compound. A purified product characterized by obtaining a combustion residue whose surface is coated with the film of the aqueous film-forming inorganic compound, thereby simultaneously sealing harmful substances and pollutants. 3. A combustion residue or a mixture of both, the surface of which is coated with the aqueous film-forming inorganic compound film according to claim 1 or 2, is fired at a temperature of 800 ° C. or more. A processed product according to claim 1 or 2 or both. 4. An aqueous film-forming inorganic compound comprising a siloxane and a silanol salt is brought into contact with a combustion gas or fly ash from waste to form a film-forming foam, and black smoke, odor and harmful gas are contained therein. And no combustion residue containing heavy metals,
Harmful substances and pollution such as black smoke, foul odors and harmful gases, and heavy metals. A waste purification treatment method in which materials are simultaneously sealed and purified. 5. The method for purifying waste according to claim 4, wherein the contacting is performed by spraying an aqueous film-forming inorganic compound composed of a siloxane and a silanol salt onto the combustion gas of the waste. 6. When the aqueous film-forming inorganic compound is brought into contact with a waste combustion gas, a pressure spray device is attached to a flue or a suction side passage to spray the aqueous film-forming inorganic compound,
6. A method according to claim 5, wherein said black smoke, odor, harmful gas and heavy metal are sucked by a negative pressure generated at that time.
The waste disposal method described in the above. 7. When the aqueous film-forming inorganic compound is brought into contact with a waste combustion gas, the waste combustion gas at a temperature of 200 ° C. or more is blown into the aqueous film-forming inorganic compound, and the black smoke is contained therein. 5. The method for purifying waste according to claim 4, wherein the residue is a residue containing odor, odorous gas, and heavy metal-containing substances. 8. An aqueous film-forming inorganic compound comprising a siloxane and a silanol salt is brought into contact with bottom ash deposited on the bottom of an incinerator that burns waste to form a film-forming foam, thereby forming harmful substances and pollutants. A method for purifying waste by sealing and purifying. 9. The aqueous film-forming inorganic compound is mixed with a treated product obtained by simultaneously sealing the harmful or pollutant, or a bottom ash or fly ash obtained by burning waste, and heated to 800 ° C. or more. 9. The method for purifying waste according to claim 4, wherein ceramics are formed to prevent elution of harmful substances and pollutants.