Method for Producing Relating to Industrial Mass Production of High-Purity Artificial Zeolite

Abstract

A high-purity artificial zeolite is industrially mass produced by carrying out osmosis treatment of fly ash in an alkaline aqueous solution, subsequently carrying out the osmosis treatment again with an acidic aqueous solution of pH 1.0 or less obtained by adding acid to the osmotic aqueous solution of fly ash, then performing solid-liquid separation while water wash and dewatering in a centrifuge, thereby synthesizing a starting composition, and performing hydrothermal reaction treatment to this starting composition.

Claims

1. A method for producing an artificial zeolite in which a high-purity artificial zeolite is industrially mass produced, the method comprising carrying out osmosis treatment of fly ash in an alkaline aqueous solution, subsequently carrying out the osmosis treatment again with an acidic aqueous solution of pH 1.0 or less by adding acid to the osmotic aqueous solution of fly ash, then performing solid-liquid separation while water wash and dewatering in a centrifuge, thereby synthesizing a starting composition, and performing hydrothermal reaction treatment to the starting composition.

2. The method for producing the artificial zeolite in which the high-purity artificial zeolite is industrially mass produced as set forth in claim 1, wherein said artificial zeolite is an A-type artificial zeolite, in which the starting composition comprieses in molar ratios 1.0 to 2.0 for SiO.sub.2/Al.sub.2O.sub.3, 0.5 to 1.2 for Na.sub.2O/SiO.sub.2, and 40 to 60 for H.sub.2O/Na.sub.2O.

3. The method for producing the artificial zeolite in which the high-purity artificial zeolite is industrially mass produced as set forth in claim 1, wherein said artificial zeolite is an X-type artificial zeolite, in which the starting composition comprises in molar ratios 2.5 to 5.0 for SiO.sub.2/Al.sub.2O.sub.3, 0.5 to 1.2 for Na.sub.2O/SiO.sub.2, and 40 to 60 for H.sub.2O/Na.sub.2.

4. The method for producing the artificial zeolite in which the high-purity artificial zeolite is industrially mass produced as set forth in claim 1, wherein said artificial zeolite is an X-type artificial zeolite, in which the starting composition comprises in molar ratios 2.5 to 5.0 for SiO.sub.2/Al.sub.2O.sub.3, 0.5 to 1.2 for Na.sub.2O/SiO.sub.2, and 40 to 60 for H.sub.2O/Na.sub.2.

5. The method for producing the artificial zeolite in which the high-purity artificial zeolite is industrially mass produced as set forth in claim 1, wherein said artificial zeolite is an MOD-type artificial zeolite, in which the starting composition comprises in molar ratios 7.0 to 16 for SiO.sub.2/Al.sub.2O.sub.3, 2.6 for Na.sub.2O/SiO.sub.2, and 56 for H.sub.2O/Na.sub.2.

6. The method for producing the artificial zeolite in which the high-purity artificial zeolite is industrially mass produced as set forth in claim 1, wherein said artificial zeolite is an Na—P type artificial zeolite, in which the starting composition comprises in molar ratios 1.0 to 12 for SiO.sub.2/Al.sub.2O.sub.3, 0.5 to 1.2 for Na.sub.2O/SiO.sub.2, and 33 to 60 for H.sub.2O/Na.sub.2.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0018] FIG. 1 A flow chart of the method of the first alkaline solution treatment the second acid aqueous solution osmosis treatment with regards to removing impurities during artificial zeolite conversion.

[0019] FIG. 2 A flow chart of the manufacturing equipment device in the present invention (the present plant).

[0020] FIG. 3 A flow chart of hydrothermal synthesis with regards to the method for producing hydrophilic zeolite (A-type X-type artificial zeolite).

[0021] FIG. 4 A flow chart of hydrothermal synthesis with regards to the method for producing hydrophobic zeolite (Y MOD-type artificial zeolite).

[0022] FIG. 5 A flow chart of hydrothermal synthesis with regards to the method for producing hydrophilic hydrophobic zeolite (Na—P-type artificial zeolite).

[0023] FIG. 6 A comparison diagram of the X-ray analysis data diagram of high-purity A-type artificial zeolite and low-purity A-type artificial zeolite. The relationship between lattice constant intensity and reaction time is graphed.

[0024] FIG. 7 A comparison diagram of the X-ray analysis data diagram of high-purity X-type artificial zeolite and low-purity X-type artificial zeolite. The relationship between lattice constant intensity and reaction time is graphed.

[0025] FIG. 8 A technical material of crystal structure analysis (Rietveld refinement) of zeolite.

DETAILED DESCRIPTION OF THE INVENTION

EXAMPLES

Example 1

[0026] The below-mentioned is the method for producing a representative hydrophilic A-type artificial zeolite.

[0027] As the production condition for making the A-type artificial zeolite a single crystalline phase, for the starting composition, the A-type starting composition is made to comprise in molar ratios 2.0 for SiO.sub.2/Al.sub.2O.sub.3, 1.0 for Na.sub.2O/SiO.sub.2, 56 for H.sub.2O/Na.sub.2O.

[0028] The ratio of the four components is made up of SiO.sub.2 obtained by removing impurities as silica raw material (ignoring the trace amount of alkali Na.sub.2O), sodium hydroxide as alkali raw material, aluminum hydroxide as alumina raw material, and water.

[0029] 20.2 kg of fly ash from which impurities were removed (SiO.sub.2 is 11.85 kg since the SiO.sub.2 concentration of fly ash is 58.7%) was added to 100 liters of 2.0N alkaline aqueous solution (8.0 kg of NaOH and 92.0 liters of H.sub.2O), stirred for 0.3 to 1 hour, and a translucent solution was obtained. Then, 16.9 kg of aluminum hydroxide (Al.sub.2O.sub.3 is 10.05 kg since Al.sub.2O.sub.3 is contained of 59.5% in the above-mentioned aluminum hydroxide) was added to this solution, stirred until it became a white turbid solution, then the gel slurry solution kept at 60 to 40° C. was transferred to an autoclave, and with the setting of 100° C. temperature and 4 hours reaction time, hydrothermal reaction treatment was performed and the gel slurry of A-type artificial zeolite composition was obtained. After performing cooling precipitation for 1 to 24 hours to the gel slurry of the A-type composition, tap water was removed and while washing, solid liquid separation and dewatering at pH 10 or less was performed in a centrifuge, subsequently dried in an electric furnace at 100° C. for 7 hours, and crystallization of hydrophilic white A-type artificial zeolite was obtained. Regarding lattice constant (A) upon XRD analysis of the obtained crystal composition, high-purity A-type artificial zeolite was industrially mass produced (42.29 kg per batch).

[0030] Further, a comparison diagram of the X-ray analysis data diagram of the A-type artificial zeolite of Example 1 is shown in FIG. 6. This graphs the relationship between lattice constant intensity and reaction time. The X-ray analysis data are shown in FIG. 6-a for the A-type artificial zeolite of Example 1 of the present application and in FIG. 6-b for the conventional A-type artificial zeolite as Comparative Example 1.

[0031] The lattice constant intensity (CPS) of Example 1 of the present application of FIG. 6-a is 240000. On the other hand, the lattice constant intensity (CPS) of Comparative Example FIG. 6-b is 165000.

[0032] The ratio of the lattice constant intensity of Comparative Example and Example 1 is 165000/240000=0.666.

[0033] Therefore, the lattice constant intensity of FIG. 6-b is low and the conventional A-type artificial zeolite cannot be called high-purity artificial zeolite.

[0034] Out of the above-mentioned molar ratios, SiO.sub.2/Al.sub.2O.sub.3 becomes 1.0 for the below-mentioned reason.

[0035] Since the mass of SiO.sub.2 is 11.85 kg, and the molecular weight of SiO.sub.2 is 60, 11.85/60 is 0.1975.

[0036] Since the mass of Al.sub.2O.sub.3 is 10.05 kg, and the molecular weight of Al.sub.2O.sub.3 is 102, 10.05/102 is 0.09852.

[0037] Therefore, the molar ratio SiO.sub.2/Al.sub.2O is 0.1975/0.09852, namely 2.0.

[0038] Out of the above-mentioned molar ratios, Na.sub.2O/SiO.sub.2 becomes 1.0 for the below-mentioned reason.

[0039] Since 99 percent of 8.0 kg of NaOH becomes Na.sub.2O, the mass of Na.sub.2O is 7.92 kg. Replaced with NaOH, since the molecular weight of NaOH is 40, 7.92/40 is 0.198.

[0040] Since the mass of SiO.sub.2 is 11.85 kg, and the molecular weight of SiO.sub.2 is 60, 11.85/60 is 0.1975.

[0041] Therefore, the molar ratio Na.sub.2O/SiO.sub.2 is 0.198/0.1975, namely 1.0.

[0042] Out of the above-mentioned molar ratios, H.sub.2O/Na.sub.2O becomes 56 for the below-mentioned reason.

[0043] Since the alkaline solution is an alkaline solution of 2.0N in Example 1, H.sub.2O/Na.sub.2O is 56 with regards to the concentration of 2.0N of NaOH from the below-mentioned table 3. Table 3 is a chart of molar ratios.

TABLE-US-00003 TABLE 3 Na2O (NaOH) alkaline aqueous solution concentration NaOH 1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0 H2O/Na2O 79.0 76.7 74.4 72.1 89.8 67.5 55.2 82.9 60.5 58.3 56.0 molar ratio NaOH 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.0 H2O/Na2O 5 .7 51.4 48.1 45. 44.5 42.2 39. 37.5 35.3 33.0 molar ratio From the molar ratio chart, the concentration of N of NaOH is H2O/Na2O (58). indicates data missing or illegible when filed

Example 2

[0044] The below-mentioned is the method for producing a representative hydrophilic X-type artificial zeolite.

[0045] As the production condition for making the X-type artificial zeolite a single crystalline phase, for the starting composition, the X-type starting composition is made to comprise in molar ratios 5.0 for SiO.sub.2/Al.sub.2O.sub.3, 0.8 for Na.sub.2O/SiO.sub.2, 40 for H.sub.2O/Na.sub.2O.

[0046] The ratio of the four components is made up of SiO.sub.2 obtained by removing impurities as silica raw material (ignoring the trace amount of alkali Na.sub.2O), sodium hydroxide as alkali raw material, aluminum hydroxide as alumina raw material, and water.

[0047] 30.6 kg of fly ash from which impurities were removed (SiO.sub.2 is 17.96 kg since the SiO.sub.2 concentration of fly ash is 58.7%) was added to 100 liters of 2.7N alkaline aqueous solution (10.0 kg of NaOH and 90.0 liters of H.sub.2O), stirred for 0.3 to 1 hour, and a translucent solution was obtained. Then, 10.2 kg of aluminum hydroxide (Al.sub.2O.sub.3 is 6.069 kg since Al.sub.2O.sub.3 is contained of 59.5% in the above-mentioned aluminum hydroxide) was added to solution (A), stirred until it became a white turbid solution, then the gel slurry solution (B) kept at 60 to 40° C. was transferred to an autoclave and with the setting of 100° C. temperature 5 hours reaction time, hydrothermal reaction treatment was performed and the gel slurry of X-type artificial zeolite product was sought. After performing cooling precipitation for 1 to 24 hours to the gel slurry of the X-type product, tap water was removed and while washing, solid liquid separation and dewatering at pH (10 or less) was performed in a centrifuge, subsequently dried in an electric furnace (100° C. 7 hours), and crystallization of hydrophilic white X-type artificial zeolite was obtained. Regarding lattice constant (A) upon powder XRD analysis of the obtained crystal product, high-purity X-type artificial zeolite (table 2) was industrially mass produced (46.51 kg per batch).

[0048] Further, a comparison diagram of the X-ray analysis data diagram of the

[0049] X-type artificial zeolite of Example 2 is shown in FIG. 7. This graphs the relationship between lattice constant intensity and reaction time.

[0050] The X-ray analysis data are shown in FIG. 7-a for the X-type artificial zeolite of Example 2 of the present application and in FIG. 7-b for the conventional X-type artificial zeolite as Comparative Example 2.

[0051] The lattice constant intensity (CPS) of Example 2 of the present application of FIG. 7-a is 350000. On the other hand, the lattice constant intensity (CPS) of Comparative Example 2 of FIG. 7-b is 230000.

[0052] The ratio of the lattice constant intensity of Comparative Example 2 and Example 2 becomes 230000/350000=0.657.

[0053] Therefore, the lattice constant intensity of Comparative Example 2 of FIG. 7-b is low and the conventional X-type artificial zeolite cannot be called high-purity artificial zeolite.

[0054] Further, the calculation of molar ratio of X-type artificial zeolite starting composition of Example 2 is the same with the method of calculation of A-type artificial zeolite of Example 1. The same applies to the following.

Example 3

[0055] The below-mentioned is the method for producing a representative hydrophobic Y-type artificial zeolite.

[0056] As the production condition for making the Y-type artificial zeolite a single crystalline phase, for the starting composition, the Y-type starting composition is made to comprise in molar ratios 10 for SiO.sub.2/Al.sub.2O.sub.3, 0.5 for Na.sub.2O/SiO.sub.2, 44.5 for H.sub.2O/Na.sub.20. Similar to the description in Example 1, the ratio of the four components is made up of SiO.sub.2 obtained by removing impurities as silica raw material (ignoring the trace amount of alkali Na.sub.2O), aluminum hydroxide as alkali raw material, aluminum hydroxide as alumina raw material, and water. 50.5 kg of fly ash from which impurities were removed (SiO.sub.2 is 29.64 kg since the SiO.sub.2 concentration of fly ash is 58.7%) was added to 50 liters of 2.5N NaOH aqueous solution (5 kg of NaOH and 45 liters of H.sub.2O), stirred for 0.5 to 1 hour, and a translucent solution is obtained. Next, 8.4 kg of aluminum hydroxide (Al.sub.2O.sub.3 is 4.998 kg since Al.sub.2O.sub.3 is contained of 59.5% in the above-mentioned aluminum hydroxide) was added, stirred until it became a white turbid solution and a gel slurry solution was obtained, then a translucent solution was added to the gel slurry solution, transferred to an autoclave, and after being aged for 12 to 24 hours keeping 60 to 50° C., with the setting of 100° C. temperature and 24 hours reaction time, hydrothermal reaction treatment was performed and the gel slurry of Y-type artificial zeolite composition was sought. After performing cooling precipitation for 1 to 24 hours to the gel slurry of the Y-type composition, tap water was removed and while washing, solid liquid separation and dewatering at pH (10 or less) was performed in a centrifuge, subsequently dried in an electric furnace (100° C., 7 hours), and crystallization of hydrophilic white Y-type artificial zeolite was obtained. Regarding lattice constant (A) upon powder XRD analysis of the obtained crystal composition, high-purity Y-type artificial zeolite was industrially mass produced (67.1 kg per batch).

Example 4

[0057] The below-mentioned is the method for producing a representative hydrophobic MOD-type artificial zeolite.

[0058] As the production condition for making the MOD-type artificial zeolite a single crystalline phase, for the starting composition, the MOD-type starting composition is made to comprise in molar ratios 15.6 for SiO.sub.2/Al.sub.2O.sub.3, 0.3 for Na.sub.2O/SiO.sub.2, 56 for H.sub.2O/Na.sub.2O. The ratio of the four components is made up of SiO.sub.2 obtained by removing impurities as silica raw material (ignoring the trace amount of alkali Na.sub.2O), sodium hydroxide as alkali raw material, aluminum hydroxide as alumina raw material, and water.

[0059] 33.7 kg of fly ash from which impurities were removed (SiO.sub.2 is 19.78 kg since the SiO.sub.2 concentration of fly ash is 58.7%) was added to 50 liters of 2.0N alkaline aqueous solution (4.0 kg of NaOH and 46.0 liters of H.sub.2O), stirred for 0.3 to 1 hour, and a translucent solution was obtained. Then, 3.6 kg of aluminum hydroxide (Al.sub.2O.sub.3 is 2.142 kg since Al.sub.2O.sub.3 is contained of 59.5% in the above-mentioned aluminum hydroxide) was added to this solution, stirred until it became a white turbid solution and a gel slurry solution (B) was obtained, then a translucent solution (A) is added to the gel slurry solution (B), transferred to an autoclave, and after being aged for 12 to 24 hours keeping 60 to 50° C., with the setting of 175° C. temperature.Math.16 hours reaction time, hydrothermal reaction treatment was performed and the gel slurry of MOD-type artificial zeolite product was sought. After performing cooling precipitation for 1 to 24 hours to the gel slurry of MOD-type product, tap water was removed and while washing, solid liquid separation and dewatering at pH (10 or less) was performed in a centrifuge, subsequently dried in an electric furnace (100° C., 7 hours), and crystallization of hydrophilic white MOD-type artificial zeolite was obtained. Regarding lattice constant (Å) upon powder XRD analysis of the obtained crystal product, high-purity MOD-type artificial zeolite was industrially mass produced (42.5 kg per batch).

[0060] The below-mentioned is the method for producing Na—P type artificial zeolite which can produce both a representative hydrophilic and hydrophobic.

Example 5

[0061] As the production condition for making the hydrophilic Na—P type artificial zeolite a single crystalline phase, for the starting composition, the hydrophilic Na—P type starting composition is made to comprise in molar ratios 2 for SiO.sub.2/Al.sub.2O.sub.3, 1.0 for Na.sub.2O/SiO.sub.2, 33 for H.sub.2O/Na.sub.2O. Similar to the description in Example 1, the ratio of the four components is made up of SiO.sub.2 obtained by removing impurities as silica raw material (ignoring the trace amount of alkali N.sub.2O), aluminum hydroxide as alkali raw material, aluminum hydroxide as alumina raw material, and water.

[0062] 30.7 kg of fly ash from which impurities were removed (SiO.sub.2 is 18.02 kg since the SiO.sub.2 concentration of fly ash is 58.7%) was added to 100 liters of 3N NaOH aqueous solution (12 kg of NaOH and 88 liters of H.sub.2O), stirred for 0.5 to 1 hour, and a translucent solution was obtained. Next, 25.4 kg of aluminum hydroxide (Al.sub.2O.sub.3 is 15.11 kg since Al.sub.2O.sub.3 is contained of 59.5% in the above-mentioned aluminum hydroxide) was added to the solution, stirred until it became a white turbid solution and a gel slurry solution was obtained, then transferred to an autoclave keeping the state of 60 to 40° C. temperature, and with the setting of 175° C. temperature and 1.5 hours reaction time, hydrothermal reaction treatment was performed and the gel slurry of Na—P type artificial zeolite composition was obtained. After performing cooling precipitation for 1 to 24 hours to the gel slurry of the Na—P type artificial zeolite composition, tap water was removed and while washing, solid liquid separation and dewatering at pH (10 or less) was performed in a centrifuge, subsequently dried in an electric furnace (100° C., 7 hours), and crystallization of hydrophilic white Na—P type artificial zeolite was obtained. The obtained crystal composition was a crystal of hydrophilic high-purity Na—P type artificial zeolite having high lattice constant (A) upon powder XRD analysis.

Example 6

[0063] As the production condition for making the hydrophobic Na—P type artificial zeolite a single crystalline phase, for the starting composition, the hydrophobic Na—P type starting composition is made to comprise in molar ratios 10 for SiO.sub.2/Al.sub.2O.sub.3, 0.5 for Na.sub.2O/SiO.sub.2, 56 for H.sub.2O/Na.sub.2O. Similar to the description in Example 1, the ratio of the four components is made up of SiO.sub.2 obtained by removing impurities as silica raw material, sodium hydroxide of Na.sub.2O, which tends to be deficient, as alkali raw material, aluminum hydroxide as alumina raw material, and water.

[0064] 40.4 kg of fly ash from which impurities were removed (SiO.sub.2 is 23.71 kg since the SiO.sub.2 concentration of fly ash is 58.7%) was added to 50 liters of 2N NaOH aqueous solution (NaOH (4.0 kg) and H.sub.2O (45 liters)), stirred for 0.5 to 1 hour, and a translucent solution was obtained. Next, 50 liters of 2N NaOH aqueous solution (4 kg of NaOH and 45 liters of H.sub.2O), 6.77 kg of aluminum hydroxide (Al.sub.2O.sub.3 is 4.02 kg since Al.sub.2O.sub.3 is contained of 59.5% in the above-mentioned aluminum hydroxide) was added, stirred until it became a white turbid solution and a gel slurry solution was obtained. A translucent solution was added to the gel slurry solution and transferred to an autoclave keeping the state of 60 to 40° C. temperature, and with the setting of 110° C. temperature and 6 hours reaction time, hydrothermal reaction treatment was performed and the gel slurry of Na—P type artificial zeolite composition was obtained. After performing cooling precipitation for 1 to 24 hours to the gel slurry of the Na—P type composition, tap water was removed and while cleaning, solid liquid separation and dewatering at pH (10 or less) was performed in a centrifuge, subsequently dried in an electric furnace (100° C., 7 hours), and crystallization of hydrophobic white Na—P type artificial zeolite was obtained. The obtained crystal composition was a crystal of hydrophobic high-purity Na—P type artificial zeolite having high lattice constant (A) upon powder XRD analysis.

[0065] From the above-mentioned, in the production for making the A-type artificial zeolite a single crystalline phase, the A-type starting composition is preferrable to comprise in molar ratios 1.0 to 2.0 for SiO.sub.2/Al.sub.2O.sub.3, 0.5 to 1.2 for Na.sub.2O/SiO.sub.2, 40 to 60 for H.sub.2O/Na.sub.2O.

[0066] In the production for making the X-type artificial zeolite a single crystalline phase, the X-type starting composition is preferrable to comprise in molar ratios 2.5 to 5.0 for SiO.sub.2/Al.sub.2O.sub.3, 0.5 to 1.2 for Na.sub.2O/SiO.sub.2, 40 to 60 for H.sub.2O/Na.sub.2O.

[0067] In the production for making the Y-type artificial zeolite a single crystalline phase, the X-type starting composition is preferrable to comprise in molar ratios 10 to 27 for SiO.sub.2/Al.sub.2O.sub.3, 0.5 for Na.sub.2O/SiO.sub.2, 40 to 60 for H.sub.2O/Na.sub.2O.

[0068] In the production for making the MOD-type artificial zeolite a single crystalline phase, it is preferrable to comprise 7.0 to 16 for SiO.sub.2/Al.sub.2O.sub.3, 2.6 for Na.sub.2O/SiO.sub.2, 56 for H.sub.2O/Na.sub.2O.

[0069] In the production for making the Na—P type artificial zeolite a single crystalline phase, the Na—P type starting composition is preferrable to comprise in molar ratios 1.0 to 12 for SiO.sub.2/Al.sub.2O.sub.3, 0.5 to 1.2 for Na.sub.2O/SiO.sub.2, 33 to 60 for H.sub.2O/Na.sub.20.

[0070] Further, FIG. 8 is a technical material of crystal structure analysis (Rietveld refinement) of zeolite.

[0071] Zeolites have a pore structure called a channel in the crystal structure and can adsorb cations and water molecules in the internal cavity. By these features, zeolites are widely used industrially as catalysts, molecular sieves, adsorbents, and the like.

[0072] Information on crystal structure and ion is important in zeolite development, so information is obtained using powder X-ray (XRD Rietveld refinement) and the XRD pattern is simulated from lattice constant and atomic coordinates, and fitting of the actual measured powder XRD pattern is performed.

[0073] Herewith, evaluation decision of various zeolites is made by the coordinates, occupancy of the atom (ion).

[0074] As above, the present invention regards to a method for producing an artificial zeolite in which a high-purity artificial zeolite is industrially mass produced by carrying out osmosis treatment of fly ash in an alkaline aqueous solution, subsequently carrying out the osmosis treatment again with an acidic aqueous solution of pH 1.0 or less obtained by adding acid to the osmotic aqueous solution of fly ash, then performing solid-liquid separation while water wash and dewatering in a centrifuge, thereby synthesizing a starting composition, and performing hydrothermal reaction treatment to this starting composition. Therefore, it is a method for producing suited for mass production in industrial scale, not laboratory scale, and moreover, was able to provide an artificial zeolite of which the obtained crystal composition is high-purity.