JP4850141B2 - Decomposition method for waste materials containing asbestos - Google Patents

Description

  The present invention relates to a method for decomposing waste materials containing asbestos.

  Asbestos is used in a wide range of applications as a construction material because it is excellent in durability, heat resistance, chemical resistance, electrical insulation, and other properties and is inexpensive.

  However, if the fiber that is frequently used as construction material is scattered and sucked into the human body, there is a risk of health, so measures to prohibit its use are taken, and waste materials that have already been used as construction material. Processing is taken (for example, refer to Patent Document 1).

JP 2005-279589 A

  However, the conventional method for treating waste materials containing asbestos requires large-scale equipment and is expensive, and asbestos is scattered during the treatment, which may cause harm to workers and the environment. was there.

Therefore, in the present invention according to claim 1, in the decomposition method of the waste material containing asbestos, the waste material containing asbestos, the crushing medium, lithium (Li), sodium (Na), potassium in the closed container (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra) Lithium sulfide (Li ₂ S _X ), sodium sulfide (Na ₂ S _X ), potassium sulfide (K ₂ S _X ), rubidium sulfide (Rb ₂ S _X ), or one or a mixture of these and ion-bonded sulfur cesium sulfide (Cs ₂ S _X), francium sulfide (Fr ₂ S _X), beryllium sulfide (BeS _X), magnesium sulfide (MgS _X), calcium sulfide (CaS _X), sulfide strike Nchiumu (SrS _X), barium sulfide (BaS _X), and mixed with stirring with an aqueous solution of polysulfide of x = 6 to 12 of radium sulfide (RaS _X), as well as crushed by crushing medium waste materials containing asbestos It was decided to break down the asbestos that had been crushed.

  Further, in the present invention according to claim 2, in the present invention according to claim 1, the temperature inside the sealed container is increased during the stirring and mixing.

  Moreover, in this invention which concerns on Claim 3, in the said invention which concerns on the said Claim 1 or Claim 2, it decided to raise the pressure inside an airtight container during the said stirring and mixing.

  Moreover, in this invention which concerns on Claim 4, in this invention which concerns on the said Claim 1-3, it decided to add the raw material which produces | generates a metal hydroxide or a hydroxide to the said airtight container.

  Moreover, in this invention which concerns on Claim 5, in this invention which concerns on the said Claim 1-4, it decided to add water or a hot water to the said airtight container.

  And in this invention, there exists an effect described below.

  That is, in the present invention, asbestos-containing waste material is prepared by stirring and mixing a waste material containing asbestos, a crushing medium, and a polysulfide aqueous solution in which an alkali metal body and sulfur are ion-bonded in an airtight container. Can be crushed with a crushing medium, and the crushed asbestos can be decomposed and reformed from a fibrous form to a massive form.

  Below, the decomposition | disassembly processing method of the waste material containing asbestos based on this invention is demonstrated concretely.

  In the present invention, the asbestos-containing waste material is decomposed by stirring and mixing the waste material containing asbestos, the crushing medium, and the polysulfide aqueous solution in which the alkali metal body and sulfur are ion-bonded inside the sealed container. Like to do.

  The polysulfide aqueous solution in which an alkali metal body and sulfur are ion-bonded is mainly a sulfurized aqueous solution in which either one or two kinds of metal bodies or other alkali metal bodies or a mixture thereof and sulfur are ion-bonded. Is an ingredient

Here, the class 1 metal body refers to any one of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). Indicates beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), and other alkali metal bodies include slaked lime, quick lime, and these This refers to a substance such as a mixture or a substance that becomes alkali metalized by addition of water or heat. The aqueous sulfide solution is lithium sulfide (Li ₂ S), sodium sulfide (Na ₂ S), potassium sulfide (K ₂ S), rubidium sulfide ( rb ₂ S), cesium sulfide (Cs ₂ S), francium sulfide (Fr ₂ S), beryllium sulfide (BeS), magnesium sulfide (MgS), calcium sulfide (CaS), sulfide stolons Um (SrS), refers to an aqueous solution of barium sulphide (BaS), radium sulfide (RaS), and the aqueous solution of polysulfide, lithium sulfide (Li ₂ S _X), sodium sulfide (Na ₂ S _X), potassium sulfide ( K ₂ S _X ), rubidium sulfide (Rb ₂ S _X ), cesium sulfide (Cs ₂ S _X ), francium sulfide (Fr ₂ S _X ), beryllium sulfide (BeS _X ), magnesium sulfide (MgS _X ), calcium sulfide ( CaS _X ), strontium sulfide (SrS _X ), barium sulfide (BaS _X ), radium sulfide (RaS _X ) refers to an aqueous solution of x = 12 to 12, and the metal hydroxide is lithium hydroxide (Li ₂ OH), Sodium hydroxide (Na ₂ OH), potassium hydroxide (K ₂ OH), rubidium hydroxide (Rb ₂ OH), cesium hydroxide (Cs ₂ OH), francium hydroxide (Fr ₂ OH), beryllium hydroxide (BeOH) ), Magnesium hydroxide (MgOH), calcium hydroxide (CaOH), hydroxide It refers to trontium (SrOH), barium hydroxide (BaOH), and radium hydroxide (RaOH).

  A sulfurized aqueous solution in which sulfur is ion-bonded with any one or a mixture of one or two kinds of metal bodies or other alkali metal bodies and sulfur can be generated using a known chemical reaction.

  In particular, as a method for stably and safely producing polysulfides (however, Sx (x = 6 to 12)), any one of potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide or a mixture thereof is used. There is a method in which sulfur and sulfur are reacted in an airtight container while stirring and mixing under high pressure of 98 ° C to 345 ° C without discharging steam.

For example, when calcium hydroxide and sulfur are used, they can be produced by mixing slaked lime, sulfur and water,
^{_{Ca (OH) 2 → Ca ++}} + 2OH -
Ca ⁺⁺ + S → CaS
Reaction occurs.
This CaS is
_{^{2CaS + 4OH - → H 2 S}} + Ca (OH) 2 + S + Ca + O 2
It becomes.

  Here, in the conventional manufacturing method, a part of hydrogen sulfide and oxygen was released to the atmosphere as steam, but in the present invention, this reaction is performed in a sealed container so that the steam is not discharged. .

Therefore, the above reaction proceeds accurately,
H ₂ S + Ca (OH) ₂ + S + Ca → Ca (HS) ₂ + Ca (OH) ₂
It becomes.

CaS is
2CaS + 2H ₂ O → Ca (HS) ₂ + Ca (OH) ₂
It becomes.

In addition, CaS
CaS + (x-1) S → CaSx
Thus, CaSx (x = 6) is stably generated.

  This is not limited to the case where calcium hydroxide is used, and even when potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide or a mixture thereof is used, Sx (x = 6) is contained. Can be stably produced.

  In particular, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide, or a mixture thereof and sulfur and potassium, magnesium, calcium, or sodium adhering to the surface of the sulfur particles are crushed and peeled off. By reacting while stirring and mixing, a treatment agent containing polysulfide (however, Sx (x = 6)) as a main component can be generated more stably.

  In addition, when the reaction is performed at a temperature equal to or higher than the melting temperature of sulfur, a treatment agent containing polysulfide (however, Sx (x = 8)) as a main component can be stably generated.

  In addition, when a predetermined amount of potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide or a mixture thereof is continuously mixed in a mixed solution of sulfur and hot water, polysulfide However, it is possible to stably produce a treatment agent mainly composed of Sx (x = 8 to 10).

  Moreover, slaked lime is mixed in a mixed solution of potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide or a mixture thereof and sulfur and hot water in a low temperature environment (−20 ° C. to 0 ° C.). In this case, it is possible to stably produce a milk-like treatment agent that is mainly composed of polysulfide (however, Sx (x = 6 to 12)) and can solidify the object to be treated.

  In addition, calcium is mixed in a mixed solution of potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide or a mixture thereof and sulfur and hot water in a low temperature environment (-30 ° C to -25 ° C). In this case, it is possible to stably produce a treatment agent containing polysulfide (however, Sx (x = 8)) as a main component.

  In addition, when sulfur pulverized to 100 μm or less (preferably 50 μm or less), potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydroxide or a mixture thereof is used in a powder or silt state Can stably produce a treating agent mainly composed of polysulfide (however, Sx (x = 10 to 12)).

  In addition, the decomposition treatment agent can be generated using alkaline ash, which is waste, as a raw material. For example, fly ash (coal species; generated by co-firing 50% Musselburg and 50% Drayton, alkalinity PH13.5) as alkali ash, 20 parts by weight fly ash, 20 parts by weight sulfur, 100 parts by weight water First, 20 parts by weight of fly ash and 100 parts by weight of water are placed in a reaction can, the top lid is closed, and the mixer is operated to mix for about 10 minutes.

Next, a safety valve is set, the exhaust pressure is set to about 10 kg / cm ² as the upper limit reaction pressure, the furnace body cooling drain valve and the cooling valve are opened, and the cooling water inlet valve is opened to allow water to flow.

Next, in order to suppress evaporation during the reaction, a preload of about 2.5 kg / cm ² is applied by pressurization with an air compressor.

Next, the burner is ignited, the pressure gauge and the thermometer are confirmed, and the temperature is raised while mixing. At this time, the pressure is set to 10 kg / cm ² or less, and after the thermometer display reaches 110 ° C., the mixture is reacted for about 30 minutes.

  Next, the burner is stopped and left until the pressure gauge is lowered. When the pressure gauge is stabilized, the final residual pressure is completely discharged by the exhaust valve and assimilated with the atmospheric pressure.

  Next, the mixer is stopped, the discharge valve is opened, the precipitate and liquid are discharged, and these are collected.

  Next, the recovered product is cooled and separated by precipitation to obtain a chemical solution and a precipitate. Here, 130 parts by weight of the chemical solution and 20 parts by weight of the precipitate could be obtained.

  The recovered chemical solution contained calcium polysulfide and was a yellow-green pH 10 liquid with a liquid specific gravity of 1.2 g / cc.

  Further, when incineration fly ash pH 13.5 was used as a raw material, a brown pH 11 liquid containing calcium polysulfide and having a liquid specific gravity of 1.15 g / cc was obtained.

  The liquid thus produced, and further the aqueous precipitate solution can be used as an asbestos decomposition treatment agent.

  Further, as the sealed container, a ball mill type hermetic crusher can be used, and the crushing medium in this case is a ball.

  For example, the crushing device 1 shown in FIGS. 1 and 2 can be used. In this crushing device 1, a cylindrical rotating container 3 is rotatably supported by a pair of left and right bearings 4 and 5 on an upper portion of a base 2.

  In the rotating container 3, a supply pipe 8 is coaxially connected to the right side of a hollow cylindrical container body 6, while a discharge pipe 9 is coaxially connected to the left side of the container body 6.

  The rotating container 3 forms a crushing space 10 in the hollow portion of the container body 6 and accommodates a plurality of balls 11 as crushing media in the crushing space 10.

  In addition, the rotating container 3 has a rotating gear 12 formed at the outer peripheral right end of the container body 6, and a driving source 13 is linked to the rotating gear 12.

  The drive source 13 has a transmission 15 linked to a drive motor 14 attached to the base 2, a drive gear 17 is attached to the output shaft 16 of the transmission 15, and the drive gear 17 is engaged with the rotary gear 12. Yes. In the figure, 19 is a bearing.

  As a result, the crushing device 1 rotates the rotating container 3 using the drive source 13, so that the object to be crushed and the ball 11 rolled into the crushing space 10 roll together. The object to be crushed can be crushed.

  In addition, the rotating container 3 is connected to a supply device 20 for supplying an object to be processed to the crushing space 10 at the right end of the supply pipe 8.

  The supply device 20 has a supply pipe 8 connected in a sealed manner to a rectangular box-shaped supply container 21 attached to the base 2, and a head portion 23 of a hydraulic cylinder 22 attached to the supply container 21 is connected to the supply pipe 8. A supply port 25 for supplying an object to be processed is formed at the upper part of the supply container 21, and the supply port 25 is connected to the head portion 23 of the hydraulic cylinder 22 via a flexible pipe 26. Communication connection. In the figure, 28 is a supply source and 30 is an open / close valve.

  The supply device 20 advances the head portion 23 of the hydraulic cylinder 22 to close the right opening end of the supply pipe 8, opens the open / close valve 30, and supplies the workpiece from the supply source 28 to the head portion 23. Is injected into the crushing space 10 from the head portion 23 via the supply pipe 8.

  Further, the rotary container 3 has a pressurizing device 31 for pressurizing the inside of the crushing space 10 connected to the left end of the discharge pipe 9 in communication.

  The pressurizing device 31 has a discharge pipe 9 connected in a sealed manner to a pressurization container 32 attached to the base 2, accommodates a filter 33 inside the pressurization container 32, and is disposed above the pressurization container 32. The pump 34 is communicatively connected via an opening / closing valve 35, and the discharge pipe 36 is communicatively connected to the lower portion of the pressurized container 32 via an opening / closing valve 37.

  The pressurizing device 31 can pressurize the interior of the crushing space 10 to a high pressure state by opening the open / close valve 35 and driving the pump 34 with the open / close valve 37 closed.

  Furthermore, the crushing device 1 has a heating device 7 for heating the rotating container 3 attached to the base 2.

  In the heating device 7, a heater 24 is disposed below the rotating container 3, the outside of the rotating container 3 is covered with a heat insulating booth 27, and an exhaust port 29 is formed at the upper end of the heat insulating booth 27.

  Thereby, the crushing device 1 can heat the inside of the crushing space 10 of the rotating container 3 to a high temperature state by the heating device 7.

  In the present invention, the polysulfide aqueous solution in which the alkali metal body and sulfur described above are ion-bonded as an object to be processed and the waste material containing asbestos are intermittently or continuously charged into the crushing space 10 of the crushing apparatus 1. The rotating vessel 3 is rotated using the drive source 13 and the waste material containing asbestos, the crushing medium, and the polysulfide aqueous solution in which the alkali metal body and sulfur are ion-bonded are stirred and mixed in the crushing space 10. I am doing so.

  Thereby, in this invention, while the waste material containing asbestos can be crushed with a crushing medium, the crushed asbestos can be decomposed | disassembled and can be reformed from fibrous form to lump form.

  In the present invention, the heating device 7 can be used to increase the temperature inside the crushing space 10 during stirring and mixing to improve the decomposition rate. The means for raising the temperature inside the crushing space 10 is not limited to the case where the heating device 7 is used. Various means such as heating by electromagnetic waves, heating using reaction heat at the time of crushing, heating by blowing in steam, etc. Various means can also be used.

  Further, in the present invention, the pressure inside the crushing space 10 can be increased during the stirring and mixing using the pressurizing device 31 to improve the decomposition rate. The means for increasing the pressure inside the crushing space 10 is not limited to the case where the pressurizing device 31 is used, and means such as pressurization due to temperature rise can also be used.

  In the present invention, a decomposition rate can be improved by adding a raw material for generating metal hydroxide or hydroxide (for example, quick lime for generating hydroxide by hydration) in the crushing space 10.

  Furthermore, in the present invention, water or hot water can be added to the crushing space 10 to improve the decomposition rate.

The front view which shows the crushing apparatus. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Crushing device 2 Base 3 Rotating container 4,5 Bearing 6 Container body 7 Heating device 8 Supply pipe 9 Discharge pipe
10 Crushing space 11 balls
12 Rotating gear 13 Drive source
14 Drive motor 15 Transmission
16 Output shaft 17 Drive gear
19 Bearing 20 Feeder
21 Supply container 22 Hydraulic cylinder
23 Head 24 Heater
25 Supply port 26 Flexible pipe
27 Insulation booth 28 Supply source
29 Exhaust port 30 Open / close valve
31 Pressurizer 32 Pressurized container
33 Filter 34 Pump
35 Open / close valve 36 Discharge pipe
37 Open / close valve

Claims (5)

Inside the sealed container, waste material containing asbestos, crushing medium, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (Be ), Magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), or a mixture of these and lithium sulfide (Li ₂ S _X ) , Sodium sulfide (Na ₂ S _X ), potassium sulfide (K ₂ S _X ), rubidium sulfide (Rb ₂ S _X ), cesium sulfide (Cs ₂ S _X ), francium sulfide (Fr ₂ S _X ), beryllium sulfide (BeS _X ), magnesium sulfide (MgS _X ), calcium sulfide (CaS _X ), strontium sulfide (SrS _X ), barium sulfide (BaS _X ), radium sulfide (RaS _X ) x = 6 to 12 polysulfides A waste material containing asbestos, wherein the waste material containing asbestos is crushed with a crushing medium and the crushed asbestos is decomposed.   The method for decomposing a waste material containing asbestos according to claim 1, wherein the temperature inside the sealed container is raised during the stirring and mixing.   The method for decomposing a waste material containing asbestos according to claim 1 or 2, wherein the pressure inside the sealed container is increased during the stirring and mixing.   The raw material which produces | generates a metal hydroxide or a hydroxide is added to the said airtight container, The decomposition processing method of the waste material containing the asbestos in any one of Claims 1-3 characterized by the above-mentioned. The method for decomposing a waste material containing asbestos according to any one of claims 1 to 4, wherein water or hot water is added to the sealed container.

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