Abstract:
A processing method is presented for treating sludges from municipal and waste materials. The ashes from such sludges, containing SiO 2  as a primary constituent, are treated with additives to tailor the feed material composition. Thermal processing, including melting, rapid cooling and subsequent annealing, produces a crystallized glass microstructure in which needle-shaped shaped crystals of anorthite and β-wollastnite are infiltrated with a vitreous material. Such crystallized glasses having superior mechanical and aesthetic properties are an attractive architectural material which can be utilized for interior finishing, exterior walls, flooring as well as for interior decorations.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a process for converting ashes from the industrial and municipal wastes, such as sludges and the like, to crystallized glass. 
     2. Background Art 
     Heretofore, most waste materials, including industrial and municipal sludges have been buried in landfill or otherwise disposed of. The problems associated with the conventional method of disposal have become obvious lately, because of the difficulties in securing the landfill sites, as well as the destruction of environments, including the emission of offensive odors and the like. Recently, such waste material has been subjected to incineration treatment in order to reduce the quantity of the waste and to stabilize the waste. Lately, subsequently disposal of the incinerated ashes has also become difficult, because such disposal often resulted in a secondary environmental problem such as leaching of heavy metals and the like into the ground. Therefore, attempts have been made to utilize sludges by converting them to slags by melting. 
     Conventional methods for manufacturing a structural aggregate materials comprise the steps of: (1) combusting the waste at high temperatures to perform ashing and melting simultaneously; or combusting the waste to form an ash and then to melt the ash at high temperatures; and (2) cooling the melted ash to form a slag. The cooling methods may be roughly divided into two types: one is a water-granulation method in which the melted slag is rapid-cooled by dropping the slag into water to obtain small glassy globules. Another is an annealing method for manufacturing large crystallized slag by annealing the melted slag held in a metal mold. 
     In addition, a method for manufacturing crystallized slag is proposed, for example in Japanese Patent Application Second Publication No. 1-24739, which comprises the steps of: (1) preparing a mixture of incinerated ash and other materials so as to have a ratio of (CaO+MgO)/SiO 2  of 0.8 to 1.2; (2) melting the mixture at 1350° C. to 1500° C.; (3) crushing the melted mixture by rapid cooling thermal shock; and (4) maintaining the crushed mixture at 1000° C. to 1200° C. for 30 minutes. 
     Furthermore, another method for manufacturing crystallized slag is proposed, for example in Japanese Patent Application Second Publication No. 61-24074, which comprises the steps of: (1) preparing a mixture of incinerated ash and other materials so as to have a ratio of (CaO+MgO)/SiO 2  of 0.8 to 1.2; (2) melting the mixture at 1350° C. to 1500° C.; (3) molding the melted mixture in a mold maintained at 300° C. to 600° C.; and (4) maintaining the molded mixture at 1020° C. to 1180° C. for 30 minutes or more. 
     The water granulation method described above has a disadvantage that the impact strength of the aggregates is low due to its glassy structure. In addition, in the annealing method described above, since the type of crystals to be precipitated is not controlled, the product thus produced has low bending and impact strengths and it cannot be used as produced. For this reason, all the crystallized slag materials have been used as aggregate materials for such applications as crushed road bed materials. 
     Furthermore, the conventional method for processing slags described above needs a large amount of additives such as calcium when the incineration ash is from municipal wastes or from the dehydrated polymer flocculant which constitutes the main ingredient of such sludges. The processing steps were also slanted towards producing aggregate materials. 
     SUMMARY OF THE INVENTION 
     In view of the above mentioned difficulties in producing useful industrial products by the conventional processing of waste material sludges, it is an object of the present invention to provide a method for converting such waste materials to a crystallized glass of a sufficiently high quality to be useful as a high-grade building material for use in architectural applications for interior finishing, exterior walls, flooring as well as for interior decorations. 
     Accordingly, a processing method is presented for utilizing incineration ashes from waste material sludges using a reduced amount of additives, not for the purpose of producing aggregate materials but to produce crystallized glasses of superior mechanical and aesthetic properties. 
     One aspect of the present invention is directed to providing a method for manufacturing crystallized glass comprising the steps of: 
     (a) preparing a feed material including at least one of waste and incineration ashes, so as to have a feed material of a composition: 35% to 55% by weight of SiO 2  ; 5% to 20% by weight of Al 2  O 3  ; 2% to 15% by weight of Fe 2  O 3  ; 5% to 30% by weight of CaO; 0.2% to 5% by weight of carbon (C); and 0.2% to 6% by weight of sulfur (S), in which the ratio of CaO/(SiO 2  +Al 2  O 3 ) is in a range of 0.15 to 0.7; 
     (b) melting the feed material at 1300° C. to 1500° C. to form a melted material; 
     (c) cooling the melted material to form a glassy material; and 
     (d) subjecting the glassy material to heat treatment to form a crystallized glass, containing at least one of anorthite and β-wollastnite phases which is infiltrated with a vitreous material. 
     The objectives, effects, features, and the advantages of the present invention will become more apparent from the following descriptions of preferred embodiments thereof. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING 
     FIG. 1 is a X-ray diffraction chart of a crystallized glass obtained in an embodiment according to the present invention; 
     FIG. 2 is an embodiment of the thermal expansion test results on the base glass from which crystallized glasses are obtained. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     According to the present invention, a method for manufacturing crystallized glass is provided which comprises the steps of: 
     (a) preparing a feed material including at least one of waste and incineration ashes, so as to have a feed material of a composition: 35% to 55% by weight of SiO 2  ; 5% to 20% by weight of Al 2  O 3  ; 2% to 15% by weight of Fe 2  O 3  ; 5% to 30% by weight of CaO; 0.2% to 5% by weight of carbon (C); and 0.2% to 6% by weight of sulfur (S), in which the ratio of CaO/(SiO 2  +Al 2  O 3 ) is in a range of 0.15 to 0.7; 
     (b) melting the feed material at 1300° C. to 1500° C. to form a melted material; 
     (c) degassing the melted material as much as possible at 1200° C. to 1400° C. to form a degassed material; 
     (d) cooling the degassed material to form a vitreous material; and 
     (e) subjecting the vitreous material to heat treatment to form a crystallized glass containing at least one of anorthite and β-wollastnite phases. It is preferable to maintain the vitreous material a 800 ° C. to 900° C. for longer than 15 minutes, for example, to precipitate a colloidal crystal such as FeS, and successively maintaining the colloidal crystal at 1000° C. to 1200° C. for at least 15 minutes to precipitate needle shaped crystals including anorthite (CaO.Al 2  O 3 .2SiO 2 ) or β-wollastnite (CaO.SiO 2 ) using the above described colloidal crystal as nucleus, thus obtaining a crystallized glass infiltrated with 40% to 60% of a vitreous constituent. 
     The feed material according to the present invention is derived from waste materials such as sludges or municipal wastes, or incinerated ashes from the wastes or other combustibles. These ashes comprise mainly SiO 2 , Al 2  O 3 , CaO, MgO, Fe 2  O 3 , P 2  O 5 , Na 2  O, K 2  O, and the like, similar to the ashes produced from the sludge cakes precipitated with the aid of polymer flocculants. One such typical example is shown in Table 1. The melt properties of an ash of such a composition, such as its melting temperature or the flow temperature, depend on the composition ratio of the ash. For example, if the ratio of CaO/SiO is in the range of 0.8 to 1.2, the melted material can flow out from the furnace at temperatures 1400° C. or less. 
     
                       TABLE 1______________________________________Ingredients, % by weight______________________________________   SiO.sub.2         40.72   Al.sub.2 O.sub.3         14.80   CaO   8.24   MgO   2.97   Fe.sub.2 O.sub.3         9.56   P.sub.2 O.sub.5         12.97   Na.sub.2 O         1.25   K.sub.2 O         1.44   others         8.05______________________________________ 
    
     Heretofore, it has been believed that setting the ratio of CaO/SiO in the range of 0.8 to 1.2 is crucial to crystallize the melted material of such waste or incinerated ash. Various studies by the present inventors showed that needle-shaped crystals such as anorthite (CaO.Al 2  O 3 .2SiO 2 ) or β-wollastnite (CaO SiO 2 ) can be precipitated by carrying out the successive steps of: 
     (a) preparing a feed material including at least one of waste and incineration ashes, so as to have a feed material of a composition: 35% by weight to 55% by weight of SiO 2  ; 5% by weight to 20% by weight of Al 2  O 3  ; 2% by weight to 15% by weight of Fe 2  O 3  ; 5% by weight to 30% by weight of CaO; 0.2% by weight to 5% by weight of carbon (C); and 0.2% by weight to 6% by weight of sulfur (S), and the feed material having a ratio of CaO/(SiO 2  +Al 2  O 3 ) in a range of 0.15 to 0.7; 
     (b) melting the feed material at 1300° C. to 1500° C. to form a melted material; 
     (c) degassing the melted material as much as possible at 1200° C. to 1400° C. to form a degassed material; 
     (d) cooling the degassed material to form a vitreous material; and 
     (e) subjecting the vitreous material to heat treatment to form a crystallized glass including at least one of anorthite and β-wollastnite phases. 
     It is preferable to maintain the vitreous material at 800° C. to 900° C. for at least 15 minutes, for example, to precipitate a colloidal crystal such as FeS, and to subsequently maintain the colloidal crystal at 1000° C. to 1200° C. for at least 15 minutes to precipitate the desired needle-shaped crystals such as anorthite (CaO.Al 2  O 3 .2SiO 2 ) or β-wollastnite (CaO.SiO 2 ). 
     In addition, in order to obtain a crystallized glass having superior mechanical, thermal, and chemical properties, acceptable for use as a high-grade building material, the crystallization process should begin not from the surface regions but from within the melt and progress uniformly throughout the melt. It is known that a nucleating agent aids the crystallization process. In order to precipitate crystals such as anorthrite or β-wollastnite, sulfur compounds such as FeS or ZnS are suitable as nucleating agents. However the iron or sulfur component in the feed material is usually present in the form of oxides such as Fe 2  O 3 , Na 2  SO 4 , or the like. Since the desirable FeS or ZnS cannot be obtained simply by melting the waste or the ash content, the carbon (C) component which is present in the feed material can function as a reducing agent to reduce the abundances of oxides such as Fe 2  O 3 , Na 2  SO 4  and the like described above. For this reason, the desired FeS can be produced from Fe 3  + or Fe 2  + obtained in the reduction reaction described above. 
     The feed material including at least one of waste and incineration ashes, having the above-described composition, is melted at 1300° C. to 1500° C. to form a melted material. The melted material is degassed as much as possible at 1200° C. to 1400° C. to form a degassed material. The degassed material is poured into a cast-iron mold while the viscosity of the material is maintained at a temperature between 1200° C. to 1300° C. to enable the degassed material to flow from the opening of the furnace. The cast material in the mold is cooled to form a vitreous material. The vitreous material is heat treated in a heat-treatment furnace, preferably at 800° C. to 900° C. for 15 minutes or longer to form a colloidal crystal, and the material is subsequently heat treated at 1000° C. to 1200° C. for 15 minutes or more, preferably 30  wollastnite having the colloidal crystals as a nucleating agent. 
     The reason for setting the range of SiO 2  between 35 to 55% by weight is that at concentrations less than 35% by weight, the amount is insufficient to form the structure of the crystallized glass including anorthite or β-wollastnite. If the amount of SiO 2  is more than 55% by weight, the quality of the heat-treated crystallized glass deteriorates because the molten material does not flow out from the furnace readily due to the increased viscosity of the molten charge. 
     In addition, if the amount of Al 2  O 3  is less than 5% by weight, a large amount of additives must be added. If the amount of Al 2  O 3  is more than 20% by weight, the precipitation of the crystals other than anorthite and β-wollastnite is increased, leading to the deterioration the mechanical properties of the resulting product. 
     If the amount of CaO is outside the range of 5% to 30% by weight, the precipitation of the crystals other than anorthite and β-wollastnite is increased. Furthermore, if the amount of CaO is more than 30% by weight, the amount of additives needed, such as lime, calcium carbonate, or the like is proportionally increased. 
     If the amount of Fe 2  O 3 , although serving an important function as a flux or a nucleating agent, exceeds 15% by weight, it has an adverse effects on crystallization. If the amount of Fe 2  O 3  is less than 2% by weight, the fluxing effect is reduced, and for this reason, other additives are added or their quantity has to be increased. 
     The reason for adopting the carbon concentration of 0.2 to 5% is that there is little reduction action at concentrations below 0.2% while there is no additional benefit gained by using concentrations above 5%. 
     The reason for adopting the sulphur concentration of 0.2 to 6% is that 0.2% is insufficient to provide the needed amount of nucleating agent, including evaporative losses, while over 6% is excessive. 
     The reason for making the ratio of CaO/(SiO 2  +Al 2  O 3 ) between 0.15 to 0.7 is to precipitate out the crystals of anorthite and β-wollastnite and to leave about 40 to 60% of the vitreous material as a matrix. 
     The reason for setting the melting temperatures of the feed materials to be 1300 to 1500° C. is that at temperatures below 1300° C., it becomes difficult to completely melt the feed material, leading to high viscosity, poor fluidity, and premature precipitation of crystallized materials, thus leading to difficulties in producing vitreous materials. At temperatures above 1500° C., erosion of furnace linings becomes a problem as well as increased radiative losses, thus leading to an uneconomic process. 
     The reason for performing degassing at temperatures between 1200 and 1400° C. is that at 1200° C., the viscosity of the melt becomes too high for good fluidity while over 1400° C. is uneconomic because of the excessive heating required. 
     Further, the reason for setting the temperature for colloidal crystals formation at 800 to 900° C. is that these crystals form at temperatures between the transition temperature and the melting temperature, but at temperatures below 800° C., there is little growth of Fe-containing crystals while at temperatures over 900° C., other crystals begin to precipitate, and therefore the FeS colloidal crystals are not being used effectively as a nucleating agent. The annealing conditions are set at temperature of 1000 to 1200° C. for 15 minutes or more, because at temperatures below 1000° C., the growth of anorthite and β-wollastnite is insufficient while above 1200° C. the growth process becomes unstable because of remelting of parts of precipitated crystals and other undesirable effects. The time at temperature is set at 15 minutes, because the crystallization process is incomplete when the holding time is shorter. 
     The glass crystals thus produced have high strength and are stable against chemicals, because the needle-shaped crystals of anorthite and β-wollastnite are infiltrated with vitreous materials. The crystallized glass material can be melted and poured into a mold to produce a shape, and after stress relieving heat treatment, it can be ground and polished to produce a translucent article of a high product value. 
     PREFERRED EMBODIMENTS OF THE PRESENT INVENTION 
     The waste ashes obtained from the sewage treatment plants were converted to feed materials having the compositions shown in Table 2 below. 
     They were held at their respective melting temperatures, between 1300 to 1500° C., for four hours. This treatment was followed further by degassing at 1200 to 1400° C., and the molten material was poured into a steel container or into water to produce small glass globules. They were placed in a heat treating furnace, and heated to around 800 to 900° C., and after holding for a given period of time, the temperature was raised to 1000 to 1200° C. for further annealing treatment for a fixed time period. The results are summarized in Table 3 (Processing Conditions) and Table 4 (Properties) for the various compositions 1 to 12. 
     Comparative test examples 13 to 15 were produced from the feed materials blended t outside the compositions of the present invention. They were processed under the same processing conditions of melting, degassing, rapid cooling and annealing treatment as the foregoing twelve embodiment samples. The results from the comparative test samples are also shown in Tables 2, 3 and 4. The results of X-ray diffraction analyses are shown in FIG. 1, which demonstrated that for the compositions 1 to 8, anorthite crystals were present, and for the compositions 9 to 12, the presence of β-wollastnite crystals was confirmed. Thermal expansion tests were performed on the base glass, and as a representative example, the results of measurements from embodiment No. 5 are shown in Table 2. The coefficient of expansion a was 81×10 -7  which is lower than that for ordinary glasses. The transition temperature and the softening temperature were also higher than those for ordinary glasses by about 100° C. These are good indications of a glass material having high thermal stability. Table 4 shows the results of testing of the produced samples for their strength, hardness (Moh&#39;s hardness), acid resistance and alkaline resistance. 
     Three point bending tests were performed on specimens of 100×100×8 mm (length×width×thickness), by placing a specimen on two rods of 10 mm diameter, and applying the load through a rod of the same diameter placed at the top midpoint of the specimen. The acid resistance tests were performed with an aqueous solution containing 1% sulfuric acid, and the alkaline resistance tests were performed with an aqueous solution containing 1% sodium hydroxide. A sample measuring 15×15×10 mm size were immersed in respective solutions for 650 hours at 25° C. 
     The tests results for the comparative samples ar also shown in Table 4 to demonstrate the superiority of the test samples. For example, the results confirmed that the test samples (1-12) were superior to the comparative samples (13-15) or to natural rock (16) in their mechanical strength, impact and chemical stability. 
     
                       TABLE 2______________________________________A Summary Table Of Compositions OfEmbodiments And Comparative SamplesTest  Composition, % by weightNo.   SiO.sub.2        Al.sub.2 O.sub.3                  Fe.sub.2 O.sub.3                        CaO    C   S     A______________________________________1     39.3   15.3      7.0   21.6   1.0 2.0   0.402     45.3   10.8      5.0   21.9   0.2 0.2   0.393     35.0   19.8      6.4   28.0   5.0 5.0   0.514     52.7   11.2      2.4   25.3   3.0 3.0   0.405     42.9   12.7      2.9    8.5   2.9 5.1   0.156     43.2   11.8      10.1  20.3   5.0 3.2   0.377     39.5   10.8      5.0   21.8   0.5 0.9   0.438     44.9   12.3      8.8   15.0   4.0 4.5   0.269     46.6    5.1      5.9   14.3   1.0 3.2   0.2810    40.4    8.7      5.1   22.4   4.5 4.5   0.4611    48.2    6.5      4.1   26.9   0.8 3.2   0.4912    39.5    8.5      3.1   18.5   3.3 2.5   0.3913    40.7   14.8      9.6    8.2   --  --    0.1514    35.6    9.7      3.0   35.5   5.0 3.0   0.7815    40.1   15.6      7.2    3.4   4.0 2.5   0.06______________________________________ Note: A: CaO/(SiO + Al.sub.2 O.sub.3) 
    
     
                       TABLE 3______________________________________A Summary Table Of Heat Treating ConditionsHeat Treatment ConditionsTest  Melting Temp Primary      SecondaryNo.   °C.   °C.                      Time   °C.                                   Time______________________________________1     1450         800     1   hr   1100  2   hr2     1500         900     15  min  1000  4   hr3     1400         850     20  min  1050  15  min4     1450         850     1   hr   1050  1   hr5     1400         900     30  min  1000  3   hr6     1450         800     2   hr   1050  20  min7     1500         900     2   hr   1000  30  min8     1450         850     1   hr   1200  1   hr9     1400         800     30  min  1050  2   hr10    1450         850     1   hr   1000  4   hr11    1450         900     2   hr   1050  1   hr12    1500         800     1   hr   1100  2   hr13    1450         --      --       1050  4   hr14    1450         850     2        1050  115    1400         900     1        1200  3   hr______________________________________ 
    
     
                       TABLE 4______________________________________A Summary Comparison Of Properties Of GlassesIn Embodiments And Comparison Tests       Properties ComparisonTest Precip.    Bend       Moh&#39;s Acid    AlkalNo.  An      Wol    (Kg/cm.sup.2)                        Hard. (%)     (%)______________________________________1    ◯  550      6.0   0.10    0.052    ◯  700      6.5   0.08    0.053    ◯  400      4.8   0.15    0.084    ◯  480      5.3   0.60    0.095    ◯  600      6.2   0.07    0.066    ◯  450      5.5   0.13    0.107    ◯  470      5.7   0.11    0.098    ◯  520      5.9   0.10    0.089            ◯               650      6.7   0.08    0.0910           ◯               750      7.0   0.05    0.0611           ◯               640      6.3   0.09    0.0712           ◯               730      6.8   0.07    0.0513   X       X       30      0.8   1.00    0.1014   X       X       45      1.2   0.80    1.1015   X       X       40      0.5   2.00    1.8016   Marble     180        4.5   10.10    0.25______________________________________ Note: An: anorthite Wol: wollastnite ◯: crystals present X: crystals not present