Patent Publication Number: US-11649169-B2

Title: Method for manufacture of amorphous silica-alumina composition in the presence of ODSO

Description:
RELATED APPLICATIONS 
     Not applicable. 
     BACKGROUND OF THE INVENTION 
     Field of the Invention 
     The present invention relates to a method of making an amorphous silica-alumina composition. 
     Description of Related Art 
     Amorphous silica-alumina (ASA) is a catalytic material, or a support or co-support for a catalytic material, in many commercial applications. Numerous methods of manufacturing ASA are known, and it is appreciated that the physical and catalytic properties of ASA can be highly dependent upon the method by which it is manufactured. 
     Conventional processes for making ASA are known, for example as disclosed in U.S. Pat. Nos. 4,500,645, 8,795,513 and 6,399,530, all of which are incorporated by reference herein in their entireties. 
     Within a typical refinery, there are by-product streams that must be treated or otherwise disposed of. The mercaptan oxidation process, commonly referred to as the MEROX process, has long been employed for the removal of the generally foul smelling mercaptans found in many hydrocarbon streams and was introduced in the refining industry over fifty years ago. Because of regulatory requirements for the reduction of the sulfur content of fuels for environmental reasons, refineries have been, and continue to be faced with the disposal of large volumes of sulfur-containing by-products. Disulfide oil (DSO) compounds are produced as a by-product of the MEROX process in which the mercaptans are removed from any of a variety of petroleum streams including liquefied petroleum gas, naphtha, and other hydrocarbon fractions. It is commonly referred to as a ‘sweetening process’ because it removes the sour or foul smelling mercaptans present in crude petroleum. The term “DSO” is used for convenience in this description and in the claims, and will be understood to include the mixture of disulfide oils produced as by-products of the mercaptan oxidation process. Examples of DSO include dimethyldisulfide, diethyldisulfide, and methylethyldisulfide. 
     The by-product DSO compounds produced by the MEROX unit can be processed and/or disposed of during the operation of various other refinery units. For example, DSO can be added to the fuel oil pool at the expense of a resulting higher sulfur content of the pool. DSO can be processed in a hydrotreating/hydrocracking unit at the expense of higher hydrogen consumption. DSO also has an unpleasant foul or sour smell, which is somewhat less prevalent because of its relatively lower vapor pressure at ambient temperature; however, problems exist in the handling of this oil. 
     Commonly owned U.S. Pat. No. 10,807,94 which is incorporated by reference herein in its entirety discloses a controlled catalytic oxidation of MEROX process by-products DSO. The resulting oxidized material is referred to as oxidized disulfide oil (ODSO). As disclosed in U.S. Pat. No. 10,807,947, the by-product DSO compounds from the mercaptan oxidation process can be oxidized, preferably in the presence of a catalyst. The oxidation reaction products constitute an abundant source of ODSO compounds, sulfoxides, sulfonates, sulfinates and sulfones. The oxidant can be a liquid peroxide selected from the group consisting of alkyl hydroperoxides, aryl hydroperoxides, dialkyl peroxides, diaryl peroxides, peresters and hydrogen peroxide. The oxidant can also be a gas, including air, oxygen, ozone and oxides of nitrogen. The catalyst can be a homogeneous water-soluble compound that is a transition metal containing an active species selected from the group consisting of Mo (VI), W (VI), V (V), Ti (IV), and combinations thereof 
     The ODSO stream so-produced contains ODSO compounds as disclosed in U.S. Pat. No. 10,781,168 as a solvent (in general), in U.S. Pat. No. 10,793,782 as an aromatics extraction solvent, and in U.S. Pat. No. 10,927,318 as a lubricity additive, all of which are incorporated by reference herein in their entireties. In the event that a refiner has produced or has on hand an amount of DSO compounds that is in excess of foreseeable needs for these or other uses, the refiner may wish to dispose of the DSO compounds in order to clear a storage vessel and/or eliminate the product from inventory for tax reasons. 
     Thus, there is a clear and long-standing need to provide an efficient and economical process for the treatment of the large volumes of DSO by-products and their derivatives to effect and modify their properties in order to facilitate and simplify their environmentally acceptable disposal, and to utilize the modified products in an economically and environmentally friendly manner, and thereby enhance the value of this class of by-products to the refiner.
         a. Despite the known ways to produce ASA materials, there remains a need in the art for improved methods to produce ASA materials, in particular using DSO by-products in an economically and environmentally friendly manner.       

     SUMMARY 
     A method for the preparation of an amorphous silica-alumina composition is provided that advantageously utilizes ODSO as a component, for example derived from a waste refinery stream of disulfide oil. The amorphous silica-alumina is formed from an aqueous mixture of an aluminum source, a silica source, water soluble ODSO, an alkali metal source and optionally a structure directing agent. The aqueous mixture is heated under conditions and for a time effective to form the amorphous silica-alumina. 
     In certain embodiments of the present disclosure, the method for synthesizing ASA comprises: forming an aqueous mixture of an aluminum source, a silica source, water soluble ODSO, an alkali metal source and optionally a structure directing agent; heating the mixture under conditions and for a time effective to form amorphous silica-alumina as a precipitate suspended in a supernatant as an intermediate suspension; and recovering the amorphous silica-alumina composition from the intermediate suspension. 
     In certain embodiments, the recovered amorphous silica-alumina composition is calcined. In certain embodiments, the intermediate suspension has a pH of less than about 9, for example in the range of about 1-9. In certain embodiments, the alkali metal source is sodium and the mass ratio of ODSO to sodium is greater than about 9, for example in the range of about 9-75. In certain embodiments, the recovered amorphous silica-alumina composition has a silica-to-alumina ratio in the range of about 20-1500. 
     The aluminum source comprises aluminates, alumina, other zeolites, aluminum colloids, boehmites, pseudo-boehmites, aluminum hydroxides, aluminum salts, aluminum alkoxides or alumina gels. The silica source comprises sodium silicate (water glass), fumed silica, precipitated silica, colloidal silica, silica gels, zeolites, dealuminated zeolites, silicon hydroxides or silicon alkoxides. The optional structure directing agent can comprise quaternary ammonium cation compounds, bifunctional dicationic molecules containing a long aliphatic chain, dual-porogenic surfactants, silylated polyethylenimine polymers, amphiphilic organosilanes, or hydrophilic cationic polyelectroyltes/polymers. In certain embodiments, the structure directing agent can comprise quaternary ammonium cation compounds selected from the group consisting of tetramethylammonium (TMA) cation compounds, tetraethylammonium (TEA) cation compounds, tetrapropylammonium (TPA) cation compounds, tetrabutylammonium (TBA) cation compounds, cetyltrimethylammonium (CTA) cation compounds, and combinations thereof. In certain embodiments, the structure directing agent comprises bifunctional dicationic molecules selected from the group consisting of C 22-6-6 , C 22-6-3 , and poly(ethylene glycol). 
     In the above methods, the ODSO compounds can include 3 or more oxygen atoms; have 1 to 20 carbon atoms; have an average density greater than about 1.0 g/cc; and/or have an average boiling point greater than about 80° C. In certain embodiments the ODSO compounds are selected from the group consisting of (R-SOO-SO-R′), (R-SOO-SO-R′), (R-SO-SOO-OH), (R-SOO-SOO-OH), (R-SO-SO-OH), (R-SOO-SO-OH), and mixtures thereof, where R and R′ can be the same or different and are alkyl groups comprising 1-10 carbon atoms. 
     In the above methods, the homogeneous aqueous mixture can be formed by providing the silica source; and, combining with the silica source, the aluminum oxide source, the alkali metal source and optionally the structure directing agent, and the water soluble ODSO. The water soluble ODSO can be added after the aluminum oxide source, the alkali metal source, and optionally the structure directing agent, or the water soluble ODSO can first be combined with the aluminum oxide source, the alkali metal source and optionally the structure directing agent, and then the resulting mixture combined with the silica source. 
     In the above methods, the homogeneous aqueous mixture can be formed by providing the aluminum oxide source, the alkali metal source and optionally the structure directing agent as a first aqueous mixture; and combining the first mixture with the silica source and the water soluble ODSO. The water soluble ODSO can be added after the silica source; or the water soluble ODSO can first be combined with the silica source, and then the resulting mixture combined with the first mixture. 
     In the above methods, the homogeneous aqueous mixture can be formed by combining the water soluble ODSO with the silica source to form a first mixture; and combining with the first mixture the aluminum oxide source, the alkali metal source and optionally the structure directing agent. 
     In the above methods, the homogeneous aqueous mixture can be formed by combining the water soluble ODSO with the aluminum oxide source, the alkali metal source and optionally the structure directing agent to form a first mixture; and combining with the first mixture the silica source. 
     In the above methods, an effective quantity of water for the homogeneous aqueous mixture is provided by using a water-containing silica source, and/or by using an aqueous mixture of the aluminum oxide source, the alkali metal source and optionally the structure directing agent. 
     Still other aspects, embodiments, and advantages of these exemplary aspects and embodiments, are discussed in detail below. Moreover, it is to be understood that both the foregoing information and the following detailed description are merely illustrative examples of various aspects and embodiments, and are intended to provide an overview or framework for understanding the nature and character of the claimed aspects and embodiments. The accompanying drawings are included to provide illustration and a further understanding of the various aspects and embodiments, and are incorporated in and constitute a part of this specification. The drawings, together with the remainder of the specification, serve to explain principles and operations of the described and claimed aspects and embodiments. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The invention will be described in further detail below and with reference to the attached drawings in which the same or similar elements are referred to by the same number, and where: 
         FIG.  1    shows X-ray diffraction patterns of calcined amorphous silica-alumina materials synthesized using ODSO, wherein diffractograms are provided for different ratios of ODSO/Na; 
         FIG.  2    is a plot of thermogravimetric (TGA) and derivative thermogravimetric (DTG) mass loss profiles of the as-made amorphous silica-alumina products from Examples 1-2 using ODSO and water, and the as-made crystalline zeolite of comparative Example 1 using water only; 
         FIG.  3    is a plot of normalized yield as a function of ODSO/Na ratios, indicating crystalline or amorphous material; 
         FIG.  4    is a plot of ODSO/Na ratios against ODSO mass demonstrating transition between crystalline products and amorphous products; and 
         FIG.  5    shows scanning electron microscopy images of the calcined amorphous silica-alumina materials synthesized in the presence of ODSO and water. 
     
    
    
     DETAILED DESCRIPTION 
     Methods for the preparation of an ASA composition are provided. Effective quantities of water soluble ODSO, an aluminum source, a silica source, an alkali metal source, and an optional structure directing agent are formed as a homogeneous aqueous mixture. The components are mixed for an effective time and under conditions suitable to form the homogeneous aqueous mixture. The chronological sequence of mixing can vary, with the objective being a highly homogenous distribution of the components in an aqueous mixture. The homogeneous aqueous mixture is heated under conditions and for a time effective to form amorphous silica-alumina as a precipitate suspended in a supernatant. The amorphous silica-alumina composition is recovered from the intermediate suspension of the precipitate in the supernatant, for example by filtration, washing and drying. In certain embodiments, the recovered precipitate is calcined at a suitable temperature, temperature ramp rate and for a suitable period of time at to realize ASA. 
     In certain embodiments, the homogeneous aqueous mixture is formed by: providing the silica source; combining the aluminum oxide source, the alkali metal source and optionally the structure directing agent; and combining the water soluble ODSO. Alternatively, the water soluble ODSO is combined with the aluminum oxide source, the alkali metal source and optionally the structure directing agent, and that mixture is combined with the silica source. 
     In certain embodiments, the homogeneous aqueous mixture is formed by: providing the aluminum oxide source, the alkali metal source and optionally the structure directing agent as a mixture; combining the silica source; and combining the water soluble ODSO. Alternatively, the water soluble ODSO is combined with the silica source, and that mixture is combined with the aluminum oxide source, the alkali metal source and optionally the structure directing agent. 
     In certain embodiments, the homogeneous aqueous mixture is formed by: combining the water soluble ODSO with the silica source to form a mixture; and that mixture is combined with the aluminum oxide source, the alkali metal source and optionally the structure directing agent. 
     In certain embodiments, the homogeneous aqueous mixture is formed by: combining the water soluble ODSO with the aluminum oxide source, the alkali metal source and optionally the structure directing agent to form a mixture; and that mixture is combined with the silica source. 
     The homogeneous aqueous mixture of the aluminum source, silica source, ODSO and optional structure directing agent, formed from any of the above chronological sequences of component addition, is heated under conditions and for a time effective to form amorphous silica-alumina as a precipitate suspended in a supernatant. The amorphous silica-alumina composition is recovered from the intermediate suspension of the precipitate in the supernatant, for example by filtration, washing and drying. In certain embodiments, the recovered precipitate is calcined at a suitable temperature, temperature ramp rate and for a suitable period of time at to realize ASA. 
     An effective quantity of water for the aqueous environment compound can be provided by using a water-containing silica source such as colloidal silica, and/or by using an aqueous mixture of the aluminum oxide source, the alkali metal source and optionally the structure directing agent. These components are added with water to the reaction vessel prior to heating. Typically, water allows for adequate mixing to realize a more homogeneous distribution of the sol-gel components, which ultimately produces a more desirable product with uniform structural phases or morphologies. Insufficient mixing could result in undesirable “pockets” of highly concentrated sol-gel components and this may lead to impurities in the form of different structural phases or morphologies. Water also determines the yield per volume. 
     Certain ratios of materials are provided to attain the effective quantities of components. An effective SAR in the synthesized ASA includes but is not limited to ratios in the range of about 20-1500, 20-1000, 20-500, 25-1500, 25-1000, 25-500, 50-1500, 50-1000, 50-500, 100-1500, 100-1000 or 100-500. In certain embodiments, an effective amount of structure directing agent is used, for example at a molar ratio (normalized to 1 mole of Al 2 O 3 ) in the range of about 0-75, 0-50, 0-30, 0.1-75, 0.1-50, 0.1-30, 2.5-75, 2.5-50, 2.5-30, 5-75, 5-50 or 5-30. In addition, an effective amount of alkali metal is used so as to maintain a pH level of less than or equal to about 9, for example in the range of about 1-9, 2-9, 1-8 or 2-8 in the sol-gel solution (the amorphous silica-alumina as a precipitate suspended in a supernatant as an intermediate suspension). It is noted that in the process herein, the pH is reduced by the presence of ODSO, therefore, the quantity of the alkali metal source, such as sodium in the form of NaOH, can be adjusted accordingly to give the desired added to provide the desired pH. An effective mass ratio of ODSO/Na is greater than or equal to about 9, for example in the range of about 9-75. 
     The aluminum source can comprise, without limitation, one or more of aluminates, alumina, other zeolites, aluminum colloids, boehmites, pseudo-boehmites, aluminum salts such as aluminum sulfate and alumina chloride, aluminum hydroxides and alkoxides, alumina gels. For example, suitable materials as aluminum sources are commercially available from Sasol, for instance high purity aluminas (CERALOX) and alumina hydrates (PURAL and CAPITAL), boehmites (DISPERSAL and DISPAL), and silica-alumina hydrates (SIRAL) and the corresponding oxides (SIRALOX). 
     The silica source can comprise, without limitation, one or more of silicates including sodium silicate (water glass), fumed silica (typically pure silica in powder form), precipitated silica, colloidal silica (silica particles suspended in water), silica gels, zeolites, dealuminated zeolites, and silicon hydroxides and alkoxides. Silica sources resulting in a high relative yield are preferred. For instance, suitable materials as silica sources are commercially from Cabot (for example, fumed silica) and Ludox (for example, colloidal silica). 
     The disclosed processes for synthesizing ASA can occur in the absence or presence of a structure directing agent. Effective structure directing agents include one or more of quaternary ammonium cation compounds (including one or more of tetramethylammonium (TMA) cation compounds, tetraethylammonium (TEA) cation compounds, tetrapropylammonium (TPA) cation compounds, tetrabutylammonium (TBA) cation compounds, cetyltrimethylammonium (CTA) cation compounds. The cation can be paired with one or more of a hydroxide anion (for example, TPAOH or CTAOH), a bromide anion (for example, TPAB or CTAB), or an iodide anion. In certain embodiments the structure directing agents include bifunctional dicationic molecules containing a long aliphatic chain (for example C 22 H 45 -N + (CH 3 ) 2 -C 6 H 12 -N + (CH 3 ) 2 -C 6 H 13 , denoted C 22-6-6 , C 22 H 45 -N + (CH 3 ) 2 -C 6 H 12 -N + (CH 3 ) 2 -C 3 H 7 , denoted C 22-6-3 , or a poly(ethylene glycol)), dual-porogenic surfactants, silylated polyethylenimine polymers, amphiphilic organosilanes, or hydrophilic cationic polyelectroyltes/polymers such as poly(diallyldimethylammonium chloride) (PDADMAC). 
     The disclosed processes for synthesizing ASA occur in the presence of a mineralizer as the alkali metal source selected from the group consisting of NaOH, KOH, RbOH, LiOH, CsOH and combinations thereof. In certain embodiments a Na-based mineralizer is selected. Note that the alkali metal source is provide as a hydroxide, but in embodiments herein where the ratio is expressed based on the mass of the alkali, it is the metal itself. For instance, when the alkali is NaOH, the ODSO/Na ratio is determined by dividing the mass of the ODSO by the mass of the Na portion of NaOH, that is, about 57.5% of the NaOH mass. 
     In the process herein, one or more ODSO compounds are used in the synthesis of ASA. The one or more ODSO compounds can include compounds of the general formulae R-SOO-SO-R′, R-SOO-SOO-R′, R-SO-SOO-OH, R-SOO-SOO-OH, R-SO-SO-OH, R-SOO-SO-OH, and mixtures thereof, where R and R′ can be the same or different and are alkyl groups comprising 1-10 carbon atoms. In certain embodiments, the R and R′ are methyl and/or ethyl groups. The one or more ODSO compounds used in the synthesis of ASA generally include ODSO compounds having 3 or more oxygen atoms. In certain embodiments, one or more ODSO compounds used in the synthesis of ASA include ODSO compounds having 1 to 20 carbon atoms. In certain embodiments, one or more ODSO compounds used in the synthesis of ASA include ODSO compounds having an average density greater than about 1.0 g/cc. In certain embodiments, one or more ODSO compounds used in the synthesis of ASA include ODSO compounds having an average boiling point greater than about 80° C. 
     In certain embodiments ODSO compounds used in the synthesis of ASA comprise all or a portion of water-soluble ODSO compounds contained in an oxidation effluent stream that is obtained by oxidation of DSO compounds from a MEROX process, as disclosed in U.S. Pat. Nos. 10,807,947 and 10,781,168 and as incorporated herein by reference above. Table 1 identifies certain water-soluble ODSO compounds that are formed by oxidation of DSO obtained from MEROX by-products. 
     
       
         
           
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 ODSO Name 
                 Formula 
                 Structure Examples 
               
               
                   
               
             
            
               
                 Dialkyl-sulfonesulfoxide Or 1,2-alkyl-alkyl-disulfane 1,1,2-trioxide 
                 (R-SOO-SO-R’) 
                                   
 1,2-Dimethyldisulfane  1,1,2-trioxide 
               
               
                   
               
               
                 Dialkyl-disulfone Or 1,2 alkyl-alkyl-disulfane 1,1,2,2-tetraoxide 
                 (R-SOO-SOO-R’)  
                                   
 1,2-Dimethyldisulfane 1 ,1,2,2-tetraoxide 
               
               
                   
               
               
                 Alkyl-sulfoxidesulfonate 
                 (R-SO-SOO-OH) 
                                   
 Methylsulfanesulfonic acid oxide 
               
               
                   
               
               
                 Alkyl-sulfonesulfonate 
                 (R-SOO-SOO-OH) 
                                   
 1-Hydroxy-2-methyldisulfane 1,1,2,2-tetraoxide 
               
               
                   
               
               
                 Alkyl-sulfoxidesulfinate 
                 (R-SO-SO-OH) 
                                   
 1-Hydroxy-2-methyldisulfane 1,2-dioxide 
               
               
                   
               
               
                 Alkyl-sulfonesulfinate 
                 (R-SOO-SO-OH) 
                                   
 Methylsulfanesulfmic acid dioxide 
               
               
                   
               
               
                 R and R’ can be the same or different alkyl groups comprising 1-10 carbon atoms. 
               
            
           
         
       
     
     In certain embodiments, the ODSO compounds are contained in a mixture from oxidation of DSO compounds, comprising alkyl-sulfoxidesulfonate (R-SO-SOO-OH), alkyl-sulfonesulfonate (R-SOO-SOO-OH), alkyl-sulfoxidesulfinate (R-SO-SO-OH) and alkyl-sulfonesulfinate (R-SOO-SO-OH), for example, similar to those obtained as “Composition 2” in U.S. Pat. No. 10,781,168 as incorporated herein by reference above. 
     The below examples and data are exemplary. It is to be understood that other aluminum sources, silica sources, bases and structure directing agents can be used as compared to the example. 
     In the synthesis steps for producing ASA herein, the sequence of adding the components is described above, but can be varied. In certain embodiments, the aluminum source, the alkali metal source and optionally the structure directing agent are formed into an aqueous solution, to which the ODSO is added, and then the silica, since addition of the silica source forms a thick gel. In other embodiments, the ODSO can be added to the silica source, and that mixture is added to an aqueous solution of the aluminum source, the alkali metal source and the structure directing agent. In other embodiments, the aluminum source, alkali metal source and optionally the structure directing agent are formed into an aqueous solution, to which the ODSO is added and this mixture added to the silica source. In other embodiments, the ODSO can be added to the silica source to which that mixture receives an aqueous solution of the aluminum source, alkali metal source and optionally the structure directing agent. 
     The temperature and pressure conditions, and residence time, for the mixing steps described herein to produce the intermediate suspension of precipitate in the supernatant that is used for producing ASA are similar to those used in typical ZSM-5 synthesis, for example, where the sol-gel is prepared at ambient temperature and pressure (for instance about 20° C. and about 1 standard atmosphere). The mixing time is sufficient to realize a homogeneous distribution of the sol-gel components. In certain embodiments the sol-gel can be aged before being subjected to subsequent hydrothermal treatment, for example for a period of about 0-24, 0-5, 0.5-24 or 0.5-5 hours. Hydrothermal treatment is then carried out at a temperature in the range of about 100-180° C. and at atmospheric or autogenous pressure, and for a time period within the range of about 3 hours to 5 days. 
     The products are washed, for example with water at a suitable quantity, for example at about twice the volume of the sol-gel solution. The wash can be at a temperature of from about 20-80° C. at atmospheric pressure or under vacuum. The wash can continue until the pH of the filtrate approaches 7. The solids are recovered by filtration, for instance, using known techniques such as centrifugation, gravity, vacuum filtration, filter press, or rotary drums, and dried, for example at a temperature of up to about 110 or 150° C. 
     The conditions for calcination to produce ASA herein can include temperatures in the range of about 450-700, 450-600, 500-700 or 500-600° C., atmospheric pressure, and a time period of about 3-24, 3-18, 6-24 or 6-18 hours. Calcining can occur with ramp rates in the range of from about 0.1-10, 0.1-5, 0.1-3, 1-10, 1-5 or 1-3° C. per minute. In certain embodiments calcination can have a first step ramping to a temperature of between about 100-150° C. with a holding time of from about 2-24 hours (at ramp rates of from about 0.1-5, 0.1-3, 1-5 or 1-3° C. per min) before increasing to a higher temperature with a final holding time in the range of about 2-24 hours. 
     EXAMPLES 
     Comparative Example 1 
     Aluminum nitrate nonahydrate (0.2633 g) was weighed into a Teflon liner (45 ml). Thereafter, 0.7750 g of a 50 wt.% sodium hydroxide solution and 7.0469 g tetrapropylammonium hydroxide (TPAOH) were added and the mixture stirred. Next, distilled water (3.3005 g) was added and the mixture was maintained under stirring. Finally, the silica source, 5.2430 g of Ludox AS-50, SiO 2  content of 40 wt.%, was added and the mixture stirred until homogeneous. 
     The Teflon liner was positioned within an autoclave and transferred to an oven and heated to a temperature of 175° C. whilst rotating the autoclave. The autoclave was maintained at isothermal conditions for 18 hours. 
     The product was filtered and washed with distilled water before drying at 110° C. The dry mass was 1.3906 g. The inorganic content determined by thermogravimetric (TGA) analysis was 87.78%. Hence, a product (zeolite) yield of 1.2207 g was obtained. 
     The as-made sample from Comparative Example 1 was calcined at 550° C. (1° C./min ramp rate) for 8 hours to realize a porous ZSM-5 zeolite. 
     Example 1 
     Aluminum nitrate nonahydrate (0.2620 g) was weighed into a Teflon liner (45 ml). Thereafter, 0.7782 g of a 50 wt.% sodium hydroxide solution and 7.0381 g tetrapropylammonium hydroxide (TPAOH) were added and the mixture stirred. Next, ODSO (3.2703 g) was added and the mixture was maintained under stirring. The ODSO used in this example are those obtained as “Composition 2” in U.S. Pat. No. 10,781,168, incorporated herein by reference above. Finally, the silica source, 5.2634 g of Ludox AS-50, SiO 2  content of 40 wt.%, was added and the mixture stirred until homogeneous. 
     The Teflon liner was positioned within an autoclave and transferred to an oven and heated to a temperature of 175° C. whilst rotating the autoclave. The autoclave was maintained at isothermal conditions for 18 hours. 
     Thereafter, the product was filtered and washed with distilled water before drying at 110° C. The dry mass was 1.9532 g. The inorganic content determined by thermogravimetric (TGA) analysis was 91.65%. Hence, a product yield of 1.7901 g was obtained. 
     Example 2 
     Aluminum nitrate nonahydrate (0.2605 g) was weighed into a Teflon liner (45 ml). Thereafter, 0.7468 g of a 50 wt.% sodium hydroxide solution and 7.0192 g tetrapropylammonium hydroxide (TPAOH) were added and the mixture stirred. Next, distilled water (1.3271 g) and ODSO (1.9722 g) were added and the mixture was maintained under stirring. The ODSO used in this example are those obtained as “Composition 2” in U.S. Pat. No. 10,781,168, incorporated herein by reference above. Finally, the silica source, 5.2148 g of Ludox AS-50, SiO 2  content of 40 wt.%, was added and the mixture stirred until homogeneous. 
     The Teflon liner was positioned within an autoclave and transferred to an oven and heated to a temperature of 175° C. whilst rotating the autoclave. The autoclave was maintained at isothermal conditions for 18 hours. 
     Thereafter, the product was filtered and washed with distilled water before drying at 110° C. The dry mass was 2.1920 g. The inorganic content determined by thermogravimetric (TGA) analysis was 94.19%. Hence, a product yield of 2.0646 g was obtained. 
     The as-made samples from Examples 1 and 2 were calcined at 550° C. (1° C./min ramp rate) for 8 hours to realize porous ASA materials. 
       FIG.  1    shows the x-ray diffraction patterns of the calcined amorphous ASA materials from Examples 1 and 2. Both diffractograms show the amorphous nature of the materials since there are no sharp peaks and only a broad peak at approximately 25°/2θ, representative of amorphous silica. 
     Additionally, the product yield is increased for the ASA materials when compared with the product (zeolite) synthesized only in the presence of water in the absence of ODSO. The highest yield obtained is approximate to the transition region between crystalline and amorphous. Further increasing the ODSO/Na mass ratio reduces the product yield. Product yield is calculated based on the dry-mass of the as-made materials multiplied by the % of inorganic content determined from thermogravimetric analysis ( FIG.  2   ,  FIG.  3    and Table 2).  FIG.  4    shows the transition between crystalline products and amorphous products as a function of the ODSO/Na mass ratio. The morphology of the ASA materials is non-defined likely as a result of the amorphous nature, as shown in  FIG.  5   , which are scanning electron microscopy images of the calcined amorphous silica-alumina materials using ODSO. 
     The relative yields are 35% to 80% greater than the equivalent yield produced for the corresponding crystalline zeolite formed in the absence of any ODSO, that is, a water-only synthesis (see  FIG.  3   ). 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Normalized zeolite yield as a function of the ODSO/Na ratio. 
               
            
           
           
               
               
               
               
            
               
                   
                 ODSO/Na Ratio (w/w) 
                 Normalized Yield 
                 Phase 
               
               
                   
                   
               
            
           
           
               
               
               
               
            
               
                   
                 0 
                 1.00 
                 Zeolite 
               
               
                   
                 9.19 
                 1.69 
                 Amorphous silica- 
               
               
                   
                   
                   
                 alumina 
               
               
                   
                 14.62 
                 1.47 
                 Amorphous silica- 
               
               
                   
                   
                   
                 alumina 
               
               
                   
                   
               
               
                   
                 Normalized yield is based on the dry mass of the as-made materials multiplied by the inorganic content determined from thermogravimetric analysis. An ODSO/Na ratio = 0 is a water-only synthesis in the absence of ODSO. 
               
            
           
         
       
     
     The methods and compositions of the present invention have been described above and in the attached drawings; however, modifications will be apparent to those of ordinary skill in the art and the scope of protection for the invention is to be defined by the claims that follow.