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Ion exchange process for modifying molecular sieves
~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 was heat treated in He in admixture with solid PtCI2 to give zeolite PtZSM-58 and HCI.
Shaped CaX-type zeolites and their manufacture H. Sakuma; W. Inaoka; A. Harada Tosoh Corp. Jpn. Kokai Tokkyo Koho 94,183,727, July 5, 1994; Applo Dec. 22, 1992 The shaped CaX-type zeolites have a Ca2+ exchange ratio of 50-90% and a crystal content of ~>90%. The manufacturing process involves ion exchange of binderless shaped NaX-type zeolites with Ca2+. The zeolites are used as adsorbents for separation of O from mixtures containing N. Crystalline m i c r o p o r o u s m e t a l l o z i n c p h o s p h a t e molecular sieves R.L. Bedard UOPInc. U.S. 5,302,362, Apr. 12, 1994; Appl. Apr. 10, 1992 The molecular sieves have a three-dimensional microporous framework structure of ZnO2, PO2, and M'O2 tetrahedral units, an intracrystalline pore system, and molecular composition r M20 : sZnO : t M'On/2 : u P~Os (M is ~>one of alkali metal; M' is ~>one of Mg, Cu, Ga, AI, Si, Ge, Co, Cr, Fe, Mn, Ti; n = valence of M' and is 2, 3, or 4; r, s, t and u are dependent on the value of n and are defined as presented). The molecular sieves are prepared by hydrothermal crystallization of a reaction mixture containing reactive sources of P, Zn,/> 1 of M', ~>1 alkali metal, and water. 1.11 K20 : 0.30 GeO2 : 3.25 ZnO : P2Oswas prepared from KOH, Ge(Ac)4, H3PO4, and ZnCI 2, in the presence of Me4NOH. M a n u f a c t u r e of inorganic, ultralarge-pore, non-layered,
crystalline m a t e r i a l s J.S. Beck; K.D. Schmitt; J.C. Vartuli Mobil Oil Corp. U.S. 5,334,368, Aug. 2, 1994; U.S. Appl. Jan. 25, 1990 Cont.-in-part of U.S. 5,250,282 The process comprises preparing a reaction mixture containing a solution of/>1 source of ~>1 oxide selected from di-, tri-, tetra-, and pentavalent oxides; adding a gelling agent; adding an organic templating agent comprising an ion having general formula R1R2R3R4Q+ (Q = N or P; ~> 1 of R1-4 = aryl, Ce_38-alkyl, and the remainder of R1-4 selected from N and/or Cl-s alkyl); adding ~>1 solvent; maintaining the mixture under conditions of pH and temperature, and for a duration sufficient to form the title material; and recovering the material. The material has an X-ray diffraction pattern (presented) containing ~>1 peak at a position ~18 A d-spacing and C6H6 adsorption capacity 15 g/100 g at 50 torr and 25°C, and is used as a sorbent or a component for catalysts for converting organic and inorganic compounds. The material may have a hexagonal electron diffraction pattern that can be indexed with a dloo value greater than about 18 A and a hexagonal arrangement of uniformly sized pores with maximum perpendicular cross-section of ~13 A. The reaction mixture comprises Na silicate, HzSO4, AI2(SO4)3, or AI(NO3)3 as gelling agent, and Me4N silicate, D i v a l e n t transition metal aluminosilicate mazzite-like s t r u c t u r e
having
D.E.W. Vaughan; K.G. Strohmaier Exxon Research and Engineering Co. U.S. 5,338,526, Aug. 16, 1994; Appl. Aug. 8, 1985 Cont.-in-part of U.S. 5,185,137 A novel zeolitic aluminosilicate composition has AI, Si, and I>1 transition metals in the framework tetrahedral positions and a mazzite-like structure. The composition is prepared directly from a reaction mixture comprising an AI source, a SiO2 source,
a divalent transition metal source, a Na oxide source, an organic template, and a seed source, by mixing, maintaining at a temperature for crystallization, and recovering the crystals. The aluminosilicate is useful as a hydrocarbon conversion catalyst. M i c r o p o r o u s crystalline gallophosphate fluoride zeolites E. Benazzi; C. Darie; H. Kessler et al. Institut Francais du Petrole Fr. Demande 2,701,254; 2,701,255, Aug. 12, 1994; Appls. Feb. 5, 1993 and Feb. 9, 1993 The phosphates have general formula RrGaePpX~O2F~H20 (g = 0.4-0.5; p = 0.3-0.4; x --- 0-0.4; f = 0.01-0.3; r = 0.1-0.3; h = 0-0.5; R = an organic compound selected from diamines of type H2N(CH2)nNH2; X --- heteroatom selected from Li, Be, Co, Mg, Mn, Zn, AI, B, Cr, Fe, Ge, Si, Ti, As, and V). The crystalline phosphates are manufactured by forming a reaction mixture containing at least water, I>1 source of Ga, i>1 source of P, t>1 organic source selected from 91 diamine as above, 1>1 source of fluoride anions in mol ratio r' R:Ga203:p'P2Os:fYFy:h'H20 (r' = 1-15; p' = 0.3-1; f = 0.1-4; h' = 1-500; R as above; Y~+ = mineral or organic cation compensating the fluoride anions), and maintaining the reaction mixture at a temperature of 40250oc.
CATALYSIS C y c l o d i m e r i z a t i o n of 1,3-butadienes to 4-vinylcyclo-
hexenes R.W. Diesen; K.A. Burdett; R.S. Dixit et al. Dow Chemical Co. U.S. 5,329,057, July 12, 1994; Appl. Apr. 19, 1991 Cont.-in-part of U.S. 5,196,621 4-Vinylcyclohexenes are produced in a steady high rate formation, not possible with catalysts of the prior art. The process involves contacting butadiene with a copper (I)-aluminosilicate zeolite prepared by (1) an impregnation method, or (2) heating a solid mixture of a Cu salt and the zeolite, or (3) contacting vao pors of a Cu salt with the zeolite. The catalysts exhibit long life and good activity.
Preparation of ethylenediamine K. Segawa Tosoh Corp. Jpn. Kokai Tokkyo Koho 94,87,797, Mar. 29, 1994; Appl. Sept. 4, 1992 H2NCH2CH2NH2 (I) is prepared by gas phase treatment of H2NCH2CH2OH(11)with NH3 at a molecular ratio of NH3/II > 20 and ~<200 using H ion exchange-type mordenite catalysts. M o d i f i e d z e o l i t e HY catalysts for the preparation of phe-
nylalkanes from linear alkenes and benzene J.F. Joly; J.P. Boitiaux Institut Francais du Petrole Fr. Demande 2,697,246, Apr. 29, 1994; Appl. Oct. 28, 1992 2-, 3-, 4-, 5-, and 6-phenylalkanes (e.g., phenyldodecanes), useful as biodegradable surfactant intermediates, are prepared by the alkylation of C6He with />1 linear C9-1e olefin(s) (e.g., 1-dodecene) at <300°Cl1-10 MPa in the presence of a dealuminated zeolite HY catalyst, having Na content <0.25%, pore diameter <24.55 x 10 -18 m, and BET surface area >300 m2/g, while maintaining a C6H6/olefin molar ratio of 1:20.
Hydroxylation of phenolic compounds M. Costantini; D. Laucher; J.M. Popa Rhone Poulenc Chimie Fr. Demande 2,693,457, Jan. 14, 1994; Appl. July 10, 1992 Phenols and derivatives R'C6H4OR [R, R' = H, C1-4 alkyl, cyclohexyl, Ph] are hydroxylated by H202 in the presence of a US-Y zeolite catalyst with acidic properties and a ketone cocatalyst.
Zeolites 15:754-759, 1995
755
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 was heat treated in He in admixture with solid PtCI2 to give zeolite PtZSM-58 and HCI.
Shaped CaX-type zeolites and their manufacture H. Sakuma; W. Inaoka; A. Harada Tosoh Corp. Jpn. Kokai Tokkyo Koho 94,183,727, July 5, 1994; Applo Dec. 22, 1992 The shaped CaX-type zeolites have a Ca2+ exchange ratio of 50-90% and a crystal content of ~>90%. The manufacturing process involves ion exchange of binderless shaped NaX-type zeolites with Ca2+. The zeolites are used as adsorbents for separation of O from mixtures containing N. Crystalline m i c r o p o r o u s m e t a l l o z i n c p h o s p h a t e molecular sieves R.L. Bedard UOPInc. U.S. 5,302,362, Apr. 12, 1994; Appl. Apr. 10, 1992 The molecular sieves have a three-dimensional microporous framework structure of ZnO2, PO2, and M'O2 tetrahedral units, an intracrystalline pore system, and molecular composition r M20 : sZnO : t M'On/2 : u P~Os (M is ~>one of alkali metal; M' is ~>one of Mg, Cu, Ga, AI, Si, Ge, Co, Cr, Fe, Mn, Ti; n = valence of M' and is 2, 3, or 4; r, s, t and u are dependent on the value of n and are defined as presented). The molecular sieves are prepared by hydrothermal crystallization of a reaction mixture containing reactive sources of P, Zn,/> 1 of M', ~>1 alkali metal, and water. 1.11 K20 : 0.30 GeO2 : 3.25 ZnO : P2Oswas prepared from KOH, Ge(Ac)4, H3PO4, and ZnCI 2, in the presence of Me4NOH. M a n u f a c t u r e of inorganic, ultralarge-pore, non-layered,
crystalline m a t e r i a l s J.S. Beck; K.D. Schmitt; J.C. Vartuli Mobil Oil Corp. U.S. 5,334,368, Aug. 2, 1994; U.S. Appl. Jan. 25, 1990 Cont.-in-part of U.S. 5,250,282 The process comprises preparing a reaction mixture containing a solution of/>1 source of ~>1 oxide selected from di-, tri-, tetra-, and pentavalent oxides; adding a gelling agent; adding an organic templating agent comprising an ion having general formula R1R2R3R4Q+ (Q = N or P; ~> 1 of R1-4 = aryl, Ce_38-alkyl, and the remainder of R1-4 selected from N and/or Cl-s alkyl); adding ~>1 solvent; maintaining the mixture under conditions of pH and temperature, and for a duration sufficient to form the title material; and recovering the material. The material has an X-ray diffraction pattern (presented) containing ~>1 peak at a position ~18 A d-spacing and C6H6 adsorption capacity 15 g/100 g at 50 torr and 25°C, and is used as a sorbent or a component for catalysts for converting organic and inorganic compounds. The material may have a hexagonal electron diffraction pattern that can be indexed with a dloo value greater than about 18 A and a hexagonal arrangement of uniformly sized pores with maximum perpendicular cross-section of ~13 A. The reaction mixture comprises Na silicate, HzSO4, AI2(SO4)3, or AI(NO3)3 as gelling agent, and Me4N silicate, D i v a l e n t transition metal aluminosilicate mazzite-like s t r u c t u r e
having
D.E.W. Vaughan; K.G. Strohmaier Exxon Research and Engineering Co. U.S. 5,338,526, Aug. 16, 1994; Appl. Aug. 8, 1985 Cont.-in-part of U.S. 5,185,137 A novel zeolitic aluminosilicate composition has AI, Si, and I>1 transition metals in the framework tetrahedral positions and a mazzite-like structure. The composition is prepared directly from a reaction mixture comprising an AI source, a SiO2 source,
a divalent transition metal source, a Na oxide source, an organic template, and a seed source, by mixing, maintaining at a temperature for crystallization, and recovering the crystals. The aluminosilicate is useful as a hydrocarbon conversion catalyst. M i c r o p o r o u s crystalline gallophosphate fluoride zeolites E. Benazzi; C. Darie; H. Kessler et al. Institut Francais du Petrole Fr. Demande 2,701,254; 2,701,255, Aug. 12, 1994; Appls. Feb. 5, 1993 and Feb. 9, 1993 The phosphates have general formula RrGaePpX~O2F~H20 (g = 0.4-0.5; p = 0.3-0.4; x --- 0-0.4; f = 0.01-0.3; r = 0.1-0.3; h = 0-0.5; R = an organic compound selected from diamines of type H2N(CH2)nNH2; X --- heteroatom selected from Li, Be, Co, Mg, Mn, Zn, AI, B, Cr, Fe, Ge, Si, Ti, As, and V). The crystalline phosphates are manufactured by forming a reaction mixture containing at least water, I>1 source of Ga, i>1 source of P, t>1 organic source selected from 91 diamine as above, 1>1 source of fluoride anions in mol ratio r' R:Ga203:p'P2Os:fYFy:h'H20 (r' = 1-15; p' = 0.3-1; f = 0.1-4; h' = 1-500; R as above; Y~+ = mineral or organic cation compensating the fluoride anions), and maintaining the reaction mixture at a temperature of 40250oc.
CATALYSIS C y c l o d i m e r i z a t i o n of 1,3-butadienes to 4-vinylcyclo-
hexenes R.W. Diesen; K.A. Burdett; R.S. Dixit et al. Dow Chemical Co. U.S. 5,329,057, July 12, 1994; Appl. Apr. 19, 1991 Cont.-in-part of U.S. 5,196,621 4-Vinylcyclohexenes are produced in a steady high rate formation, not possible with catalysts of the prior art. The process involves contacting butadiene with a copper (I)-aluminosilicate zeolite prepared by (1) an impregnation method, or (2) heating a solid mixture of a Cu salt and the zeolite, or (3) contacting vao pors of a Cu salt with the zeolite. The catalysts exhibit long life and good activity.
Preparation of ethylenediamine K. Segawa Tosoh Corp. Jpn. Kokai Tokkyo Koho 94,87,797, Mar. 29, 1994; Appl. Sept. 4, 1992 H2NCH2CH2NH2 (I) is prepared by gas phase treatment of H2NCH2CH2OH(11)with NH3 at a molecular ratio of NH3/II > 20 and ~<200 using H ion exchange-type mordenite catalysts. M o d i f i e d z e o l i t e HY catalysts for the preparation of phe-
nylalkanes from linear alkenes and benzene J.F. Joly; J.P. Boitiaux Institut Francais du Petrole Fr. Demande 2,697,246, Apr. 29, 1994; Appl. Oct. 28, 1992 2-, 3-, 4-, 5-, and 6-phenylalkanes (e.g., phenyldodecanes), useful as biodegradable surfactant intermediates, are prepared by the alkylation of C6He with />1 linear C9-1e olefin(s) (e.g., 1-dodecene) at <300°Cl1-10 MPa in the presence of a dealuminated zeolite HY catalyst, having Na content <0.25%, pore diameter <24.55 x 10 -18 m, and BET surface area >300 m2/g, while maintaining a C6H6/olefin molar ratio of 1:20.
Hydroxylation of phenolic compounds M. Costantini; D. Laucher; J.M. Popa Rhone Poulenc Chimie Fr. Demande 2,693,457, Jan. 14, 1994; Appl. July 10, 1992 Phenols and derivatives R'C6H4OR [R, R' = H, C1-4 alkyl, cyclohexyl, Ph] are hydroxylated by H202 in the presence of a US-Y zeolite catalyst with acidic properties and a ketone cocatalyst.
Zeolites 15:754-759, 1995
755