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Manufacture of crystalline ZSM-23
~UTTI~RWQRTH ~'IEI I N E M A N N
PATENT REPORT As in p r e v i o u s issues, a selection of the m o r e interesting patents that have been p u b l i s h e d recently is given b e l o w u n d e r the headings: synthesis, catalysis, separation processes, detergents, and m i s c e l l a n e o u s applications.
J.A.
Barton
SYNTHESIS Cobalt (silico)-aluminophosphates B. Kraushaar-Czarnetzki; W.G.M. Hoogervorst Shell Canada Ltd. Can. Pat. Appl. 2,104,052, Feb. 18, 1994; EP Appl. Aug. 17, 1992 The preparation of Co aluminophosphates and silicophosphates is described, having in the anhydrous form the chemical cornposition rnR(CocSi~lqPx)02 (R = an organic template; m = 0.03-0.3, c = 0-0.4, s = 0-0.4, q = 0.3-0.6, and x = 0.3-0.6; c + s + q + x = 1 and c + s > 0). The (silico)-aluminophosphates are useful as catalysts, catalyst carriers, and molecular sieves.
Manufacture of crystalline, microporous, nonzeolitic molecular sieves S.J. Miller; C.R. Wilson Chevron Research and Technology Co. PCT Int. Appl. 94,10,086, May 11, 1994; US Appl. Nov. 2, 1992 The molecular sieves have a three-dimensional microporous framework structure comprising [AIO2] and [PO2] units. They are manufactured by preparing an aqueous reaction mixture containing />1 reactive sources of P, t>1 reactive sources of AI (AI203/P205 molecular ratio >0.3), and I>1 templating agents and maintaining the mixture at conditions suitable for the formation of crystalline molecular sieves. The addition of the P source, the AI source, and the templating agent is controlled such that the templating agent/P source molecular ratio is ~>0.05 before the AI/P molecular ratio reaches -0.5.
Manufacture of molded, crystalline aluminosilicate zeolites S.J. Millner Chevron Research and Technology Co. PCT Int. Appl. 94,13,584, June 23, 1994; U.S. Appl. Dec. 16, 1992 The method comprises preparing a reaction mixture containing >/1 source of active SiO2, >/1 source of active AI203, in SiO2/ AI203 molecular ratio >12, an organic templating agent, and water in an amount sufficient to mold the mixture and heating the mixture at crystallization conditions in the absence of an external liquid phase so that excess liquid need not be removed from the crystallized material prior to drying the crystals.
Process for improving the flowability of zeolite A powders
Manufacture of crystalline ZSM-23 A. Moini Mobil Oil Corp. U.S. 5,332,566, July 26, 1994; Appl. July 16, 1993 The process comprises preparing a reaction mixture containing a source of an alkali or alkaline earth metal (M), an oxide of a trivalent element (X), an oxide of a tetravalent element (Y), water, and a t e m p l a t i n g agent (R) having f o r m u l a M%N(CH2)3N(Me)2(CH2)3NMe3, in molecular ratio YO2/X203 30300, H20/YO2 20-100, OH-/YO2 0.1-0.4, M/YO2 0.05-1.0, and R/YO2 0.02-1.0, hydrothermally reacting the mixture at 150190°C, and recovering the R-containing crystalline material. The resulting zeolites ZSM-23 have X-ray diffraction as presented and are used as catalysts for converting organic compounds, for example, hydrocarbons.
Manufacture of crystalline zeolite L aluminosilicates J. Wu; D.M. Chapman; R.R. Gatte W.R. Grace and Co. U.S. 5,330,736, July 19, 1994; Appl. Dec. 7, 1992 The process comprises preparing an aqueous reaction mixture of SiO 2, AI203, and alkali metal hydroxides in molecular amounts Na20 0-8, K20 2-9, AI203 1, SiO 2 5-35, and H20 100600, adding approximately 0.1-10 wt% amorphous aluminosilicate seeding gel not containing zeolite L and having the molecular composition Na20 15 - 2, AI203 1, SiO2 14 +- 2, and H20 350 -+ 50, stirring the mixture to form a gel, and reacting the gel at 60-250°C for a duration sufficient to crystallize the zeolite L. When manufactured at a temperature <120°C the zeolite L has a disc-shaped morphology and is substantially free of offretitetype zeolite (zeolite T). Zeolite f i l m R.M. Dessau; R.K. Grasselli; R.M. Lago et al. Mobil Oil Corp. U.S. 5,316,661, May 31, 1994; Appl. July 8, 1992 A method for synthesizing a zeolite bonded to a substrate utilizes a reaction mixture having an H20/YO2 molar ratio >t25 where Y is a tetravalent element, particularly silicon. A structure made according to this method includes a film of interconnected zeolite crystals bonded to a substrate, and the structure is characterized by a value r representing the mg of zeolite/cm2 of substrate surface and a value e representing the coating efficiency as mg of bonded zeolite/mg of YO2 initially in the synthesis mixture, where r is >~0.5 and e is ~>0.05. Processes are described for separation, sorption, organic feedstock conversion, light paraffin dehydrogenation, and NOx conversion over the structure.
Ion exchange process for modifying molecular sieves
K. Meier; W. Lortz; W. Leonhardt Degussa A.-G.
J. Weitkamp; S. Ernst; T. Bock et al. Degussa A.-G. Ger. Often. 4,304,821, Aug. 18, 1994; Appl. Feb, 17, 1993
Eur. Pat. Appl. 609,712, Aug. 10, 1994; G Appl. Feb. 5, 1993 The process involves adding >~1 surfactant to an aqueous suspension ofthe zeolite powder, especially ofthe redispersed filter cake, and drying the powder. The powder has high bulk density and better flowability and does not need grinding.
The process involves introducing cations into molecular sieves by ion exchange with solids. The cations are selected from metals of group IB through VIII. For example, zeolite ZSM-58 was calcined, subjected to repeated ion exchange with excess NH4NO3 solution, and calcined to obtain zeolite HZSM-58, which
Zeolites 15:754-759, 1995 © Elsevier Science Inc. 1995 655 Avenue of the Americas, New York, NY 10010
0144-2449/95/$10.00 SSDI 0144-2449(95)00079-L
PATENT REPORT As in p r e v i o u s issues, a selection of the m o r e interesting patents that have been p u b l i s h e d recently is given b e l o w u n d e r the headings: synthesis, catalysis, separation processes, detergents, and m i s c e l l a n e o u s applications.
J.A.
Barton
SYNTHESIS Cobalt (silico)-aluminophosphates B. Kraushaar-Czarnetzki; W.G.M. Hoogervorst Shell Canada Ltd. Can. Pat. Appl. 2,104,052, Feb. 18, 1994; EP Appl. Aug. 17, 1992 The preparation of Co aluminophosphates and silicophosphates is described, having in the anhydrous form the chemical cornposition rnR(CocSi~lqPx)02 (R = an organic template; m = 0.03-0.3, c = 0-0.4, s = 0-0.4, q = 0.3-0.6, and x = 0.3-0.6; c + s + q + x = 1 and c + s > 0). The (silico)-aluminophosphates are useful as catalysts, catalyst carriers, and molecular sieves.
Manufacture of crystalline, microporous, nonzeolitic molecular sieves S.J. Miller; C.R. Wilson Chevron Research and Technology Co. PCT Int. Appl. 94,10,086, May 11, 1994; US Appl. Nov. 2, 1992 The molecular sieves have a three-dimensional microporous framework structure comprising [AIO2] and [PO2] units. They are manufactured by preparing an aqueous reaction mixture containing />1 reactive sources of P, t>1 reactive sources of AI (AI203/P205 molecular ratio >0.3), and I>1 templating agents and maintaining the mixture at conditions suitable for the formation of crystalline molecular sieves. The addition of the P source, the AI source, and the templating agent is controlled such that the templating agent/P source molecular ratio is ~>0.05 before the AI/P molecular ratio reaches -0.5.
Manufacture of molded, crystalline aluminosilicate zeolites S.J. Millner Chevron Research and Technology Co. PCT Int. Appl. 94,13,584, June 23, 1994; U.S. Appl. Dec. 16, 1992 The method comprises preparing a reaction mixture containing >/1 source of active SiO2, >/1 source of active AI203, in SiO2/ AI203 molecular ratio >12, an organic templating agent, and water in an amount sufficient to mold the mixture and heating the mixture at crystallization conditions in the absence of an external liquid phase so that excess liquid need not be removed from the crystallized material prior to drying the crystals.
Process for improving the flowability of zeolite A powders
Manufacture of crystalline ZSM-23 A. Moini Mobil Oil Corp. U.S. 5,332,566, July 26, 1994; Appl. July 16, 1993 The process comprises preparing a reaction mixture containing a source of an alkali or alkaline earth metal (M), an oxide of a trivalent element (X), an oxide of a tetravalent element (Y), water, and a t e m p l a t i n g agent (R) having f o r m u l a M%N(CH2)3N(Me)2(CH2)3NMe3, in molecular ratio YO2/X203 30300, H20/YO2 20-100, OH-/YO2 0.1-0.4, M/YO2 0.05-1.0, and R/YO2 0.02-1.0, hydrothermally reacting the mixture at 150190°C, and recovering the R-containing crystalline material. The resulting zeolites ZSM-23 have X-ray diffraction as presented and are used as catalysts for converting organic compounds, for example, hydrocarbons.
Manufacture of crystalline zeolite L aluminosilicates J. Wu; D.M. Chapman; R.R. Gatte W.R. Grace and Co. U.S. 5,330,736, July 19, 1994; Appl. Dec. 7, 1992 The process comprises preparing an aqueous reaction mixture of SiO 2, AI203, and alkali metal hydroxides in molecular amounts Na20 0-8, K20 2-9, AI203 1, SiO 2 5-35, and H20 100600, adding approximately 0.1-10 wt% amorphous aluminosilicate seeding gel not containing zeolite L and having the molecular composition Na20 15 - 2, AI203 1, SiO2 14 +- 2, and H20 350 -+ 50, stirring the mixture to form a gel, and reacting the gel at 60-250°C for a duration sufficient to crystallize the zeolite L. When manufactured at a temperature <120°C the zeolite L has a disc-shaped morphology and is substantially free of offretitetype zeolite (zeolite T). Zeolite f i l m R.M. Dessau; R.K. Grasselli; R.M. Lago et al. Mobil Oil Corp. U.S. 5,316,661, May 31, 1994; Appl. July 8, 1992 A method for synthesizing a zeolite bonded to a substrate utilizes a reaction mixture having an H20/YO2 molar ratio >t25 where Y is a tetravalent element, particularly silicon. A structure made according to this method includes a film of interconnected zeolite crystals bonded to a substrate, and the structure is characterized by a value r representing the mg of zeolite/cm2 of substrate surface and a value e representing the coating efficiency as mg of bonded zeolite/mg of YO2 initially in the synthesis mixture, where r is >~0.5 and e is ~>0.05. Processes are described for separation, sorption, organic feedstock conversion, light paraffin dehydrogenation, and NOx conversion over the structure.
Ion exchange process for modifying molecular sieves
K. Meier; W. Lortz; W. Leonhardt Degussa A.-G.
J. Weitkamp; S. Ernst; T. Bock et al. Degussa A.-G. Ger. Often. 4,304,821, Aug. 18, 1994; Appl. Feb, 17, 1993
Eur. Pat. Appl. 609,712, Aug. 10, 1994; G Appl. Feb. 5, 1993 The process involves adding >~1 surfactant to an aqueous suspension ofthe zeolite powder, especially ofthe redispersed filter cake, and drying the powder. The powder has high bulk density and better flowability and does not need grinding.
The process involves introducing cations into molecular sieves by ion exchange with solids. The cations are selected from metals of group IB through VIII. For example, zeolite ZSM-58 was calcined, subjected to repeated ion exchange with excess NH4NO3 solution, and calcined to obtain zeolite HZSM-58, which
Zeolites 15:754-759, 1995 © Elsevier Science Inc. 1995 655 Avenue of the Americas, New York, NY 10010
0144-2449/95/$10.00 SSDI 0144-2449(95)00079-L