PATENT REPORT

As in prev ious issues, a select ion of the m o r e in terest ing patents wh ich have been pub l ished recent ly is g iven b e l o w under the head ings: synthesis, catalysis, separa- t ion processes, detergents , and misce l laneous appl ica- t ions.

J.A. Barton

SYNTHESIS

Process for the modification of zeolites A. Tissler; K.K. Unger; H. Schmidt Vereinigte Aluminiurn Werke A.-G. Eur. Pat. Appl. 330,855, Sept. 6, 1989; Ger. Appl. Mar. 3, 1988 Zeolites, prepared by crystallization at elevated temperatures and pressures, filtration, ion-exchange, drying, and, optionally, thermal activation, are modified by thermal pretreatment in the alkaline state, after which the ion-exchange and activation steps are carried out. Using this method, the form-selective properties and service life of different types of zeolites are increased, while their activity is not significantly affected.

Manufacture of crystalline zeolites S. Krishnamurthy; D.J. Klocke Mobil Oi/ Corp. U.S. 4,849,194, July 18, 1989; Appl. May 26, 1987 A method of synthesizing crystalline zeolites from a crystallization mixture, including a source of $iO2, comprises (a) establishing a relationship between the specific electrical conductivity of the crystallization mixture and the crystallinity of the zeolites, (b) crystallizing the zeolite from the mixture, (c) measuring the specific electrical conductivity of the crystallization mixture, (d) continuing to crystallize the mixture until the specific electrical conductivity reaches a value which, using the above relationship, is indicative of a selected crystallinity, and (e) terminating the crystallization when that value has been reached. The continuous crystallization of zeolites comprises a and controlling the crystallization conditions in response to the specific electrical conductivity.

Method for removing organic residue from as- synthesized zeolites F.X. Ryan Mobil Oil Corp. U.S. 4,851,200, July 25, 1989; Appl. Jan. 4, 1988 A 3 step method for removing the residue of an organic directing agent from as-synthesized zeolites, e.g., ZSM-18, involves (1) contacting the as-synthesized zeolite with an aqueous solution of a fluorosilicate salt such as (NH4)2SiF6, (2) ion-exchanging the zeolite with an alkali or alkaline earth metal salt such as KC1, and (3) calcining the ion-exchanged zeolite in a NH3-containing atmosphere. The organic directing agent is 1,3,4,6,7,9-hexahydro*2,2,5,5,8,8- hexamethyl-2H-benzo(1,2,-C:-3,4-C':5,6-C") tripyrolium trihydroxide.

Manufacture of synthetic zeolite molded body without using binders T. Taga Tosoh Corp. Jpn Kokai Tokkyo Koho 89,103,917, Apr. 21, 1989; Appl. July 15, 1987 A mixture containing SiO2 source, AI203 source, alkali source, and water is molded, dried or fired, and the dried or fired molded body is dipped in a solution containing 9--27 wt.% SiO2 and 3-8.5 wt.% Na20 as a crystallization solution, to impregnate with the solution,

and crystallized to give a synthetic zeolite (or mordenite) molded body useful for catalyst, adsorbent, and ion-exchanger.

Preparation and use of selective absorbents W. Lukas; P. Hantschel; H. Hamm et al. Knauf, Gebr., Westdeutsche Gipswerke Ger. Often. 3,824,514, Feb. 2, 1989; Appl. July 23, 1987 The absorbents are prepared by hydrothermal conversion of glassy residues (e.g., fly ash) from combustion of solid fossil fuels with acqueous alkalies, optionally alkaline earths. The combustion waste (particle size < 60 microns) is mixed with additives to obtain a SIO2/AI203 mol ratio of (2-5):1 and with aqueous alkalies, optionally in a mixture with alkaline earths and/or organic or inorganic ammonium compounds to obtain a M~nO/AI203 mol ratio of (1-8):1 (M = Group I or Group II element; n = valency) and H20/AI203 rnol ratio of (50-300):1, and reacted. After separation, rinsing, drying and modification, the absorbents are especially suitable for purification of waste gases, wastewater treatment, and drinking water purifica- tion.

Manufacture of zeolite bodies with high strength and water resistance S. Kikuchi Showa Senfu Co. Ltd. Jpn Kokai Tokkyo Koho 88,297,282, Dec. 5, 1988; Appl. May 29, 1987 The title bodies are manufactured by adding 5-15 wt. parts combustible powder (CP) to 100 wt. parts zeolite powder, moulding and firing. CP is preferably C-containing fibres, plastics, coal, coke, pulp, plants, starch, or synthetic glue. The burning and gasification of CP during the firing increases the porosity, strength, and water resistance of the zeolite. This process allows the recycling of zeolite waste. The porous zeolite bodies are used for wastewater purifica- tion, as deodorants, absorbents, filtering agents, and catalysts.

Manufacture of crystalline, potassium- and calcium- containing zeolite A L. Puppe; M. Mengel Bayer A.-G. Eur. Pat. Appl. 310,916, Apr. 12, 1989; Ger. Appl. Oct. 7, 1987 The title process comprises precipitating and crystallizing K/Ca- containing aluminosilicate gels in the presence of an essentially x-ray-amorphous, Na aluminosilicate gel. The K~O, CaO or (MgO) components are present as K, Ca (and/or Mg) compounds, and further processing, after completion of the crystallization, is carried out such that the final zeolite powder has pH -< 11. These zeolites are used for drying in noncellular polyurethane systems.

Method for the preparation of titanium-silicalite catalysts M. Padovan; G. Leofanti; P. Roffia Montedipe S.p.A. Eur. Pat. Appl. 311,983, Apr. 19, 1989; IT. Appl. Oct. 12, 1987 In a method for the preparation of Ti silicalite catalysts in the presence of a templating agent, a preformed TiO2-SiO~ coprecipi- tate is impregnated with an aqueous solution of the templating agent, and the impregnated material is made to acquire the zeolitic structure of Ti the silicates by hydrothermal synthesis.

Method for incorporating small crystalline cata ly t ic ingredients into an attrition-resistant matrix T.J. Velten; E.J. Demmel Intercat Inc. PCT. Int. Appl. 89,01,362, Feb. 2,3, 1989; U.S. Appl. Aug. 12, 1987 High concentrations of small (< 4 microns) crystalline catalyst

ZEOLITES, 1990, Vol 10, September~October 707

Patent report

ingredients such as zeolite ZSM-5, low-soda exchanged Y zeolite, ultrastable Y zeolite, etc., can be incorporated into a durable matrix by use of binder .formulations prepared from amorphous silica, alumina and zirconia, especially those of colloidal dimensions. The binder formulations are slurried and associated with > 1 active catalyst ingredient, which preferably is < 60% ZSM-5. The resulting material is then spray dried and calcined to form binder matrixes which are especially resistant to attrition and particle d. change. The catalysts can be used in petroleum cracking processes.

Synthetic crys ta l l ine s i l icates M.K. Rubin Mobile Oil Corp. U.S. 4,820,502, Apr. 11, 1989; Appl. Feb. 20, 1987 A synthetic crystalline bikitaite-type material is prepared for use in the catalytic conversion of organic compounds and comprises oxides in the ratio (0.8-1.0)CS20: (0-0.02)Na20:AI203:xSiO2, where x_>10.

ZSM-5 and its synthesis D.J. Klocke, S. Krishnomurthy Mobile Oil Corp. Eur. Pat. Appl. 306,238, Mar. 8, 1989; U.S. Appl. Sept. 2, 1987 ZSM-5 having a mesitylene sorption capacity of > 3.0 wt.% is prepared from a nonorganic reaction mixture having -> 35 wt.% solids content and a OH-/SiO2 mol ratio of -> 0.11:1. The ZSM-5 can be used, e.g., as a catalyst for the conversion of MeOH to gasoline.

CATALYSIS

Cata ly t ic reforming using Group VIII noble metal high- silica fau jas i tes D.E.W. Vaughan; A.K. Ghosh U.S. 4,832,824, May 23, 1989; Appl. Dec. 19, 1986 A process for the reforming (especially aromatization and isomeriza- tion) of alkanes to produce aromatics and isoalkanes comprises using a high-silica faujasite-type zeolite (10-80:1 SIO2/AI203 ratio), which contains a catalytic amount of --- 1 Group VIII noble metals, especially Pt, within the pores of the zeolite.

Noble metal containing zeo l i te ca ta lys ts of improved s tab i l i t y R.P.L. Absil; Y.Y. Huang Mobil Oil Corp. U.S. 4,837,397, June 6, 1989; Appl. Dec. 11, 1987 The addition of a compound containing a complex cation of Zr to a zeolite improves the properties of the zeolite and also improves the dispersibility characteristics of noble metal components supported in the zeolite. The preferred Zr compounds are hydroxychlorides of Zr and of Zr and AI. The zeolites include ZSM-5, ZSM-23 and zeolite beta. The catalysts may be used in hydrogenation and dehydrogena- tion, hydroprocessing, and reforming.

Preparation of alkylbenzenes K. Honna Idemitsu Kosan Co. Ltd. Jpn Kokai Tokkyo Koho ~9, 135,728, May 29, 1989; Appl. Nov. 20, 1987

Alkylbenzenes are prepared by transalkylation of CeH4R2 (R = C1-4 alkyl) and benzene in the presence of Fe-containing Y zeolite catalysts.

Preparation of tetrahydrofurans from 1,4-butanediols W. Hoelderich; M. Schwarzmann BASF A.-G. Eur. Pat; Appl. 309,911, Apr. 5, 1989; Ger. Appl. Sept. 30, 1987 Tetrahydrofurans are prepared by the gas-phase cyclodehydration of 1,4-butanediols over boron- and iron-substituted zeolite catalysts.

Zeo l i te ca ta lys ts for the alkylation of a l ky l a roma t i c compounds D. Barthomeuf; V. Quenach de Quivillic Centre National de la Recherche Scientifique; Soci~td Nationale ELF Aquitaine PCT Int. Appl. 89,04,716, June 1, 1989; Ft. Appl. Nov. 23, 1987 Catalysts useful for the alkylation of alkylaromatic compounds, especially for the preparation of (un)substituted styrenes, are based on an alkali aluminosilicate or gallosilicate of faujasite structure (having a Si/AI or Si/Ga ratio of < 1.5) and have -> 10% of their alkali cations as K, Rb, and/or Cs, and contain -> 1 alkali metal.

Preparation of i sop ropano l by ca ta ly t i c hydration of propylene D.O. Marler; C.M. Sorensen; P. Varghese Mobil Oil Corp. Eur. Pat. Appl. 323,269, July 5, 1989; U.S. Appl. Dec. 30, 1987 Propylene (I) is converted to iso-PrOH by contacting a feed containing I with H20 at H20:I mole ratio 0.1-1 in the vapor and/or liquid phase in the presence of zeolite ZSM-35 catalyst.

Production of ethers and alcohols from light olefins T.J.H. Huang; R.B. Lapierre; S.A. Tabak Mobil Oil Corp. Eur. Pat. Appl. 323,137, July 5, 1989; U.S. Appl. Dec. 30, 1987 Ethers and alcohols, useful as solvents and octane-increasing gasoline blending stocks, are prepared by contacting --> 1 light olefins with water in an olefin conversion unit in the presence of an acidic zeolite catalyst, e.g., zeolite beta, to provide an aqueous mixture of an alcohol and an ether (the olefin conversion unit is operated under conditions effective to provide the alcohol by hydration of the olefin and the ether by the dehydration of the alcohol and/or by the addition reaction of the olefin and the alcohol). The aqueous mixture of alcohol and ether is separated by distilla- tion.

Co-production of aromatics and olefins from paraf f in ic feedstocks M. Nemet-Mavrodin Mobil Oil Corp. Eur. Pat. Appl. 323,736, July 12, 1989; U.S. Appl. Jan. 4, 1988 A Cs-lo-paraffinic feedstock is converted into other hydrocarbons including Cs-s aromatics, C2~ olefins, C9+ aromatics and C1-3 paraffins, by using a catalyst comprising a binder and ZSM-5 or ZSM-11, the catalyst having low acid catalytic activity by an alpha value of < 25. The low alpha value of the catalyst may be achieved by deactivating the catalyst under conditions comprising steaming, high temperature calcining and/or cracking. The selectivity to the more desired Cs-s aromatics and C2-4 olefins is increased.

Ga l los i l i ca te a r o m a t i z a t i o n ca ta lys ts C.T.W. Chu; S. Han Mobil Oil Corp. Eur. Pat. Appl. 327,189, Aug. 9, 1989; U.S. Appl. Jan. 7, 1988 ZSM-5 catalysts containing Ga primarily present in the framework of the zeolite with little or no non-framework Ga present are synthe- sized with varying reaction ratios of SiO2/Ga203. They are useful in aromatization, especially of light paraffin feeds to high-octane gasoline products.

Hydrocarbon production from methane feed w i t h me ta l oxide-zeolite dua l ca ta lys ts A.M. Gaffney Atlantic Richfield Co. U.S. 4,849,571, July 18, 1989; Appl. May 20, 1988 In the conversion of CH4 to higher hydrocarbons (e.g., C2+ hydrocarbons, especially those boiling in the gasoline range), CH4 is first oxidatively coupled to form a product mixture containing C2H4, H2, and CO, and this product mixture is reacted over a dual catalyst comprised of a metal oxide effective for the hydrogenation of CO and a zeolite component (e.g., ZSM-5) effective for the oligomeriza-

708 ZEOLITES, 1990, Vol 10, September~October

tion of C2H4. Suitable metal oxides include oxides of Co, Ru, Cu, Zn, Cr and AI.

Producing hydrocarbon oils from plastic waste T. Fukuda; K. Saito; S. Suzuki et al. Mobil Oil Corp. U.S. 4,851,601, July 25, 1989; Appl. Jan. 19, 1988 Plastic scrap, especially of polyolefinic plastics, is converted to low-pour-point oils by thermal cracking in the liquid phase, followed by catalytic conversion of the vaporous cracking products over an intermediate pore size zeolite such as ZSM-5. The hydrocarbon oils are useful as the raw material for the production of gasoline.

A r o m a t i z a t i o n ca ta lys ts N.Y. Chen; S.B. McCullen Mobil Oil Corp. U.S. 4,827,068, May 2, 1989; Appl. Dec. 29, 1987 Aromatic hydrocarbons were prepared by contacting 1 or more non-aromatic compounds with a titanosilicate having the structure of zeolite beta in which a noble metal has been incorporated.

Aromatization catalysts and their use J. Kanai; T. Katsuno Technology Research Association for New Application Develop- ment for Light-Weight Fractions Jpn Kokai Tokkyo Koho 89,127,043, May 19, 1989; Appl. Nov. 12, 1987

Aromatic hydrocarbons are prepared by treating paraffins, olefins, acetylenes, cycloparaffins, and/or cycloolefins with catalysts con- taining L-type zeolites, halogens, alkaline earth metals, and Pt.

Method for producing 1,2,4-trichlorobenzene J.E. Milam; W.E. Wimer PPG Industries Inc. U.S. 4,835,327, May 30, 1989, Appl; Dec. 5, 1986 1,2,4-Trichlorbenzene (I) is prepared by treating o-dichlorobenzene with chlorine in the presence of zeolite Y as catalyst. | is a known termite exterminator and is also an agrochemical intermediate, a dielectric fluid, and a lubricating oil additive.

Preparation of p-ethylphenol T. Yamagishi; T. Idai; E. Takahashi Maruzen Petrochemical Co. Ltd. Eur. Pat. Applo 320,936, June 21, 1989; Jpn. Appl. Dec. 18, 1987 4-EtCsH4OH is prepared with high selectivity by ethylation of PhOH in the vapor phase over an alkoxysilane-modified H-ZSM-5 zeolite.

Zeo l i te ca ta lys ts su i tab le for hydrocarbon conversion T. Knox British Petroleum Co. PIc. Eur. Pat. Appl. 327,764, Aug. 16, 1989; U.K. Appl. Feb. 11, 1988 A catalyst composition comprising a crystalline aluminosilicate zeolite (SIO2/AI203 mol ratio < 5:1), Ga and Ag, is useful in the conversion of a C2-12 hydrocarbon feedstock to aromatic hydrocar- bons at elevated temperatures.

Conversion of methane into higher hydrocarbons T. Imai; P.T. Barger; A.H. Eck UOP Inc. U.S. 4,795,843, Jan. 3, 1989; Appl. Aug. 26, 1985

Useful organic compounds, e.g. C6H6, PhMe, are prepared in a two- step process by treating CH4 with a halogenating agent and contact- ing the Me halide with a silicalite catalyst.

Removal of alkyl compound impurities from a r o m a t i c hydrocarbons w i t h zeo l i te ca ta lys ts and oxygen M. Rule; GoC. Tustin; R.M. Moncier et al. Eastman Kodak Co. U.S. 4,814,545, Mar. 21, 1989; Appl. Sept. 19, 1988 Alkylaromatic compounds, alkyl compounds, and cycloalkyl corn-

Patent report

pounds are removed from aromatic hydrocarbon streams by pas- sing the contaminated aromatic stream with O over a zeolite catalyst (having pore diam. > 6 A°), e.g., NaX, causing the contaminating compounds to be decomposed to CO2, CO, and H20.

Virgin catalyst treatment by reductive and oxidative washing to promote hydrocarbon cracking F.J. Elvin ChemCat Corp. U.S. 4,806,512, Feb. 21, 1989; Appl. May 18, 1987 A process for treating a virgin catalyst, e.g., rare earth metal ion-exchanged USY synthetic zeolite, useful to ~)romote hydrocar- bon conversion, e.g., in fluid catalytic cracking, comprises contact- ing the catalyst with a liquid reductive wash medium and contacting the washed catalyst with a liquid oxidative wash medium to produce a washed catalyst with improved catalytic property. The treated virgin catalyst improves the gasoline yield while advantageously reducing the coke and gas producing factors (ASTM D 3907-80).

Process for upgrading light paraffins toaromatic hydro- carbons V.K. Shum Amoco Corp. U.S. 4,806,701 ; 4,808,763, Feb. 21 and Feb. 28, 1989; Appls. Aug. 5, 1987

A gaseous hydrocarbon feed containing C2--s paraffins (especially C3HB) is converted to aromatic hydrocarbons under conversion conditions in the presence of a catalyst comprising e gallosilicate zeolite, a Group VIII metal component, and a Group IB metal component. The aromatics can be used to increase the octane no. of gasoline or as raw materials in the petrochemical industry. The addition of Cu (or Au and chloride) to a Pt galiosilicate increased the conversion per pass and the selectivity of the reaction to aromatics without affecting the undesirable selectivity for cracked products, i.e., C1 and C2 formation.

Cata ly t ic dewaxing process using binder-free cata lys t E. Bowes Mobil Oil Corp. Eur. Pat. Appl. 304,252, Feb. 22, 1989; Appl. Aug. 20, 1987 A waxy hydrocarbon feed is dewaxed over a binder-free zeolite dewaxing catalyst. The absence of binder reduces catalyst aging. The process is especially useful with lubricating oil stocks where aging problems are particularly severe, typically highly waxy stocks or stocks containing a high level of N. Preferred catalysts are the intermediate pore size zeolites such as ZSM-5, ZSM-11 and ZSM-23.

Process for dewaxing hydrocarbon feedstock N.Y. Chen; D.E. Walsh Mobil Oil Corp. U.S. 4,808,296, Feb. 28, 1989; Appl. Oct. 18, 1985 A wax-containing hydrocarbon feedstock is dewaxed by contacting the feedstock with a zeolite catalyst in combination with a Group VIII metal hydrogenation-dehydrogenation component, e.g., Pt. A pre- ferred catalyst is Pt/ZSM-5. The catalyst exhibits resistance to poisoning by components such as N and provides a high yield of low pour-point product.

Process for production of aromatic hydrocarbons from naphtha Y. Takashi; Y. Toshikazu; K. Hisashi et al. Research Association for Utilization of Light Oil Eur. Pat. Appl. 303,097, Feb. 15, 1989; Jpn. Appl. July 30, 1987 Aromatic hydrocarbons are produced by reforming a naphtha frac- tion with a catalyst comprising a large pore zeolite (e.g., zeolite L) containing > 1 of Group VIII metals, in which the cyclopentane content or methylpentane content of the naphtha fraction is control- led to < 1 wt.% and < 10 wt.%, respectively. The invention increases the yield of aromatic hydrocarbons, and the catalyst service life is greatly extended.

ZEOLITES, 1990, Vol 10, September/October 709

Patent report

Cata lysts for simultaneous desulphurization and d e w a x - ing of petroleum residues S.M. Oleck Mobil Oil Corp. U.S. 4,808,560, Feb. 28, 1989; Appl. Oct. 1, 1981 The title catalysts comprise 1-10 wt.% Ni~r Co oxide or sulfide component and 2-20 wt.% Mo on a support containing a ZSM-5 type zeolite (e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-35 or ZSM-38).

N i t ra t i on of halobenzenes using Mg-con ta i n i ng a l um ino - s i l icate ca ta lys ts M. Furuya; H. Nakajima Technology Research Association for New Application Develop- ment for. Light-Weight Fractions Jpn Kokai Tokkyo Koho 88,303,957, Dec. 12, 1988; Appl. June 3, 1987 Halobenzenes are treated with a nitrating agent in zhe vapor phase in the presence of a crystalline aluminosilicate having mol ratio SiO2/ AI203 ~ 20, e.g., H-type ZSM-5 zeolite, and containing 0.5-5% Mg for selective nitration at the para-position.

Manufacture of 4-hydroxy-alpha-methylbenzyl alcohol and p-hydroxymethylphenol T. Kiyora , Mitsui Toatsu Chemicals Inc. Jpn Kokai Tokkyo Koho 88,307,834; 88,307,835, Dec. 15, 1988; Appls. June 8, 1987 The title compounds, useful as synthetic intermediates, are manu- factured by treating PhOH with MeCHO/HCHO or paraldehyde in the presence of zeolites, e.g., H-type zeolite Y.

Preparation of 2,6-diisopropylnaphthalene Y. Shirato; K. Shimokawa; Y. Hoshino et al. Chiyoda Chemical Engineering and Construction Co. Ltd. Jpn Kokai Tokkyo Koho 88,243,041; 88,243,043, Oct. 7, 1988; Appls. Mar. 30, 1987 The title compound (2,6-1), useful as polyester material, is prepared by isopropylation of naphthalene, and distillation of the resulting product mixtures to recover is, omeric I mixtures.

Cata lys ts for dehydrogenation and isomerization of a lky l te t ra l i n K. Maeda Sumikin Coke and Chemicals Co. Ltd. Jpn Kokai Tokkyo Koho 88,267,443, Nov. 4, 1988; Appl. Apr. 24, 1987 The title catalysts for manufacture of dialkylnaphthalenes with high selectivity are prepared by alkali treatment of Y zeolites containing -> 1 transition metals (At. No. 22-30) and, optionally, deposition of -> 1 Pt, Pd, Ru and Rh.

Ha logena t i on of C1-4 a lky lbenzenes in the manufacture of 4-haloalkylbenzenes Y. Higuchi Ihara Chemical Industry Co. Ltd, U.S. 4,794,201, Dec. 27, 1988; Appl. Dec. 22, 1983 4-XCsH4R (R = C1-~ allo/I; X = halogen) are prepared in high yields and increased selectivity by the halogenation of PhR in the presence of a halogenation agent and an L-type zeolite containing -> 1 exchangeable metal cation selected from alkali metals, alkaline earth metals, or Group IliA, IVA, and VA metals.

Liquid-phase process and zeo l i te ca ta lys ts for the oxy- i od ina t i on of naphthalene S.L. Cook; G.G. Mayfield Eastman Kodak Co. U.S. 4,810,826, Mar. 7, 1989; Appl. Mar. 17, 1988 The liquid-phase oxyiodination of naphthalene (I) is conducted by contacting a liquid feed mixture, containing I and iodine, or a

mixture containing iodine, I, and an iodonaphthalene, with a zeolite catalyst (especially type-X zeolites in the K form) in the presence of an O2(g) source, and removing the water from the iodinated product mixture by purging it with O2(g). This process offers reduced energy consumption and a higher 2,6-diiodonaphthaiene/2,7-diiodonaph- thalene molar ratio than does the corresponding gas-phase oxy- iodination reaction.

Preparation of m-xylene by o-xylene isomerization T. Onodera; A. Namatame Teijin Petrochemical Industries Ltd. Eur. Pat. Appl. 310,991, Apr. 12, 1989; Jpn. Appl. Oct. 5, 1987 The process involves isomerizing a hydrocarbon stream containing mainly o-xylene over ZSM-4 zeolite and/or omega zeolite and recovering by distillation m-xylene, which is virtually inseparable in the conventional isomerization of Ce aromatic hydrocarbons.

Process and zeolite catalysts for alkylation of aromatic hydrocarbons by olefins Y.F. Chu; D.O. Marler; J.P. McWilliams Mobil Oil Corp. Eur. Pat. Appl. 308,099, Mar. 22, 1989; U.S. Appl. Sept. 2, 1987 Aromatic hydrocarbons are alkylated by olefins over ZSM-5 zeolite catalysts with alpha-value < 100 and diffusion rate constant -> 100 s -1, which minimize formation of o-xylene in PhEt manufacture.

Process and catalysts for the manufacture of aromatic hydrocarbons from C=-s aliphatic hydrocarbons T.Y. Yan Mobil Oil Corp. U.S. 4,804,801, Feb. 14, 1989; Appl. Sept. 8, 1986 Aromatic hydrocarbons are prepared by contacting C2-6 aliphatic hydrocarbons with a ZSM-5 zeolite catalyst containing 0.5-20% Zn and a Group IB element.

Conversion of methane to higher-molecular-weight hy- drocarbons via sulphur-containing intermediates C.A. Audeh; W.K. Bell; S. Hen et al. Mobil Oil Corp. U.S. 4,822,938, Apr. 18, 1989; Appl. May 3, 1988 Methane is converted to C_>2 hydrocarbons by reacting methane with S to form CS2, reacting the CS2 with H and methane to form MESH, and contacting the MeSH with a crystalline zeolite catalyst to produce the hydrocarbons and H2S. This process allows the use of natural gas (a significant source of methane) in the manufacture of higher-molecular-weight hydrocarbons.

SEPARATION PROCESSES

Zeo l i te adsorbents for the separation of 2,4- and 2,6-TDI

H.A. Zinnen UOP Inc. Eur. Pat. Appl. 324,215, July 19, 1989; Appl. Jan. 13, 1988 2,4- and 2,6-Toluene diisocyanate isomers are separated by contact- ing the mixture with a ~'-zeolite cation-exchanged with K, which selectively adsorbs 2,6-TDI, or with a Y-zeolite cation-exchanged with Na, Ca, Li, and/or Mg, which selectively adsorbs 2,4-TDI. The TDI is eluted with PhMe.

Separation process for purifying 2,6-dimethylnaph- thalene S.H. Hobbs; T.J. Barder UOP Inc. U.S. 4,835,334, May 30, 1989; Appl. Mar. 29, 1988 2,6-Dimethylnaphthalene (I) is separated from eutectic-forming dimethylnaphthalene isomers by a 2 stage adsorptive separation

710 ZEOLITES, 1990, Vol 10, September/October

process in which an I-containing isomer mixture is first contacted with a K-exchanged X zeolite adsorbent under conditions which do not promote I adsorption, to adsorb isomers other than I, and the raffinate is sent to a second stage adsorbent comprising a carbon material and operated under I-adsorbing conditions. The adsorbed I is removed with a desorbing agent such as PhMe or PhCI.

Gas separation S. Moreau; E. Vansant; J. Verbiest et al. Air Liquide, S.A. pour /'Etude et /'Exploitation des Procedes Georges Claude Eur. Pat. Appl. 327,734, Aug. 16, 1989; Appl. Feb. 11, 1988 At least 1 gas is separated from a mixture containing _> 2 gases by contacting with a pore-containing modified zeolite for selectivity adsorbing _> 1 component of the mixture in the pores of the zeolite, thereafter separating the zeolite from the non-adsorbed compo- nent(s) and optionally desorbing the adsorbed component(s). The zeolite is modified with a modifying agent containing ~ 1 weak acid, a salt of a weak acid, or a derivative of a weak acid of -> 1 Group Ilia to VA elements. The modifying agent can be H3BO3, NaH2POz, Na4PzO7.10H20, K3PO4, (NH4)zHPOz, borax, or Si(OH)4. The zeolite is a mordenite; zeolite X, A, and Y; clinoptilolite; etc. in the H and/or cation form. The gas mixture can be air or a gas mixture containing -> 1 noble gas, -> 1 lower hydrocarbon, or -> 1 oxide from N and/or C.

Manufacture of methane-rich fuel gas T. Nojima; M. Shiraishi Kansai Coke and Chemicals Co. Ltd. Jpn Kokai Tokkyo Koho 89,29,326, Jan. 31, 1989; Appl. July 25, 1987 A method for manufacturing CH4-rich fuel gas, especially town gas, comprises passing the feedstock mainly containing CH4 through a pressure-swing adsorption (PSA) tower packed with zeolite adsor- bent (av. pore diam. -> 5A °) to selectively remove CO2; desorbing the CH4 from the zeolite bed under reduced pressure; withdrawing the CH4-rich stream and recycling to the PSA tower.

Zeolites as selective adsorbents for dimethylnaph- thalene isomer separations J.P. Verduijn; M.J.G. Janssen; C.B. De Gruitjer et al. Exxon Chemical Patents Inc. Eur. Pat. Appl. 323,893, July 12, 1989; U.K. Appl. Jan. 4, 1988 L-type zeolites, useful as selective adsorbents for the separation of 1,5-, 2,6-, and 2,7-dimethylnaphthalenes, are prepared by heating an alkaline reaction mixture containing an alkali metal (M) source, a source of AI or Ga, and a Si source. The reaction mixture has the molar ratio parameters: MzO/SiO2 = 0.42-0.48, HzO/MzO = 15-30, and SIO2/(AI203 or GazO3) = 5-11.

Purification of hydrogen S. Kajiyama; H. Nakamura; T. Matsuzawa et al. Mitsubishi Gas Chemical Co. Inc. Jpn Kokai Tokkyo Koho 88,315,503, Dec. 23, 1988; Appl. June 18, 1987 Hydrogen gas containing impurities is purified by adsorption chro- matography comprising two-step purification processes: a coarse purification process and a final purification process. In both proces- ses, > 2 adsorption columns are used, and adsorption, depressuriz- ing, purging, and pressurizing operations are carried out alternately. Crystalline zeolites are used as the adsorbents.

Si lcon tetrafluoride refining with hydrophobic crysta l - l ine zeo l i tes H. Momotake; I. Harada; N. Koto Mitsui Toatsu Chemicals Inc. Jpn Kokai Tokkyo Koho 89,51,314; 89,51,315, Feb. 27, 1989; Appls. Aug. 21, 1987 Raw SiF4 is contacted with zeolites which are previously modified for hydrophobicity, to refine the SiF4, CO2, HzS, and SO2 in SiF4 are rem6ved at high efficiency by feeding SiF4 gas through the modified zeolites. For example, zeolite 4A was modified by fluorination with CF3CI prior to use.

Patent report

Selective adsorption of 2,6-diisopropylnaphthalene from its isomeric mixtures Y. Shirato; K. Shimokawa; J. Kaita et al. Chiyoda Chemical Engineering and Construction Co. Ltd. Jpn Kokai TokkyoKoho 88,243,040; 88,243,042; 88,243,044, Oct. 7, 1988; Appls. Mar. 30, 1987 2,6-Diisopropylnaphthalene (2,6-1), useful as a polyester material, is selectively recovered from 2,6- and 2,7-1 isomeric mixtures by passing the mixtures through a pseudo-moving bed packed with a zeolite, e.g., Ba-exchanged NaY, for selective adsorption-desorption.

Selective adsorption/separation of diiodonaphthalenes on zeo l i tes M. Rule; H.L. Browning Eastman Kodak Co. U.S. 4,814,526, Mar. 21, 1989; Appl. July 28, 1987 iodonaphthalene mixtures (from iodination of naphthalene) contain- ing 2-iodonaphthalene and 2,6- and 2,7-diiodonaphthalenes are separated by selective adsorption on a non-acid zeolite, e.g., K-X zeolite, with elution of the adsorbed component by an aromatic hydrocarbon.

Purification of hexafluoropropylene K. Hayashi; H. Adachi Asahi Chemical Industry Co. Ltd. Jpn Kokai Tokkyo Koho 89,40,436, Feb. 10, 1989; Appl. Aug. 6, 1987 Hexafluoropropylene (I), useful as a monomer for fluoropolymers, was purified by removal of perfiuoro-2-butyne (11) from II-containing I by contacting and adsorbing with zeolite 5A.

DETERGENTS

Bleaching agents for cellulose pulp A. Von Raven; J. Weigl; F. Ruf et al. S(Jd-Chemie A.-G. Ger. Often. 3,739,655, June 1, 1989; Appl. Nov. 23, 1987 Bleaching agents for pulp, wastepaper, etc., which minimize the consumption of alkalies, silicates, and complexing agents contain H202 and a zeolite modified with alkali metal (bi) carbonates.

Bleaching compositions for detergents K. Takyama; A. Sato; M. Kusakabe et al. Nippon Peroxide Co Ltd; Nippon Gosei Senzai K.K. Jpn Kokai Tokkyo Koho 89,95,198, Apr. 13, 1989; Appl. Oct. 7, 1987 Bleaching compositions for detergents comprise Na percarbonate, a synthetic crystalline zeolite (known to destabilize the percarbonate) and -> 1 stabilize from Mg salts of aromatic hydrocarbonsulphonic acids, Mg salts of alkyl-substituted aromatic hydroxyhydrocarbon- ethylene oxide adduct sulphate esters, Mg salts of aliphatic higher alcohol sulphate esters, and Mg salts of aliphatic higher alcohol- ethylene oxide adduct sulphate esters.

Laundry detergents with high bulk density K. Takyama; A. Sato; S. Naito Nippon Gosei Senzai K.K. Jpn Kokai Tokkyo Koho 89,121,400, May 15, 1989; Appl. Nov. 4, 1987 ABS are neutralized with -> 1 equivalent of NazCO3 and zeolites to form NaHCO3 without generation of CO2, giving detergents with high bulk density and good flow and solubility.

Pumpable aqueous suspensions of Na a luminos i l i ca tes s tab i l i zed by cat ion ic sur factants M.J. Garvey; I.C. Griffiths Unilever PIc; Unilever N.V. Eur. Pat. Appl. 318,219, May 31, 1989; U.K. Appl. Nov. 24, 1987 The title suspensions, containing 0.001-0.5% cationic surfactant

ZEOLITES, 1990, Vol 10, September/October 711

Patent report

having 1 saturated C12-1s alkyl group, had good stability (i.e., are redispersible after standing) and are useful in the manufacture of detergent compositions. A 46% aqueous zeolite 4A suspension was stabilized by cetyltrimethylammonium bromide.

Aluminosilicate-built detergent bleach compositions for laundering at low temperature W.D. Emery; S.G. Barnes; P.S. Sims Unilever P/c; Unilever N.V. Eur. Pat. Appl. 319,054, June 7, 1989; U.K. Appl. Dec. 4, 1987 The title compositions contain -> 1 surfactant 5-40, a water insoluble zeolite NaA builder 15-40, a polyphosphonate R2N(CH2CH2NR)mR (R = CH2PO3H2, optionally in water-soluble salt form; m = 0-2) 0.5-3, an inorganic peroxide 5-35, and a peroxybenzoic acid precursor XCsH4CO2(;sH4Y (X = H, NO2, C1-4 alkyl, CI, Br; Y = H CO2M, SO3M, OSO3M, NO2, CI, Br; M = solubilizing cation) 1-10% and give good cleaning and stain removal at -< 40°C.

Storage-stable bleaching laundry detergent composi- tions K. Isobe; Y. Yoneyama; H. Kanao Lion Corp. Jpn Kokai Tokkyo Koho 89,06,098, Jan. 10, 1989; Appl. June 29, 1987 The title powdered compositions are prepared by mixing 77-98.5 parts spray-dried globular detergents containing crystalline alumi- nosilicate zeolites, e.g., zeolite 4A, 1-15 parts per carbonate salts (A), and 0.5-8 parts tetra-N-acetylethylenediamine (I) at A/I ratio 1:1- 10:1.

Zeolites in liquid detergent compositions J.N.P.M. Dekker; T.J. Osinga Unilever N. V.; Unilever PIc. Eur. Pat. Appl. 315,282, May 10, 1989; U.K. Appl. Nov. 4, 1987 A finely divided 4A- and/or Pl-type zeolite, 50% of which has particle diam. 0.1-1.0 microns is used in a liquid detergent composition. The zeolite gives rapid sequestering of hardness ions upon addition to water and is resistant to sedimentation during storage.

MISCELLANEOUS APPLICATIONS

Zeolite-containing coating material for medical care K. Maeda Eur. Pat. Appl. 298,726, Jan. 11, 1989; Appl. July 9, 1987 A coating material, applicable to wounds and burns, is made of silicone coated with zeolite, or Ag-, Cu-, or Zn-exchanged zeolite. The coating material controls Pseudomonas aeruginosa, Staphylococ- cus aureus, Escherichia coil and fungi. It is resistant to body heat.

Composition releasing active oxygen slowly T. Maruoka; S. Maeda; M. Matsushita Shikoku Chemicals Corp. Jpn Kokai Tokkyo Koho 89,87,503, Mar. 31, 1989; Appl. Sept. 28, 1987

The title composition contains crystalline zeolite (SIO2/AI203 mol ratio -> 25:1) and H202 adduct of an inorganic compound. The composition is used as a freshness-retaining agent for food includ- ing fruits, deodorizer, and bactericide.

Stabilized chlorine dioxide-generating agent w i t h im- p roved storage s tab i l i t y S. Ogata; K. Hara; T. Ikeda Osaka Soda Co. Ltd. Jpn Kokai Tokkyo Koho 89,99,559, Apr. 18, 1989; Appl. Oct. 12, 1987 The title agent, useful as deodorant and disinfectant, is prepared by impregnating sepiolite with an alkali and stabilized CIO2 and/or an alkali chlorite. The agent has excellent storage stability and gener- ates CIO2 when it is heated or mixed with an acid or oxidizing agent.

Exhaust gas treatment catalyst T. Tanaka; S. Matsumoto; S. Tateishi et al. Toyota Motor Corp.; Toyota Central Research and Development Laboratories Inc. Jpn Kokai Tokkyo Koho 89,135,541, May 29, 1989; Appl. Nov. 19, 1987 The title catalyst comprises zeolite ion-exchanged with -> 1 of Pt, Pd, Rh, Ir, or Ru. The catalyst maintains high efficiency for NOx removal in O2-rich conditions.

Method for treating wounds with dehydrated zeolite t o stop the f low of blood F.X. Hursey; F.J. Dechene U.S. 4,822,349, Apr. 18, 1989; Appl. Apr. 25, 1984 A dehydrated zeolite is provided in a suitable binder and in sterilized form such that it can be applied directly to an open wound. The wound or opening to be treated is completely covered in order to achieve the best results. Blood from the wound is absorbed in the interstices present in the zeolite with the result that increased coagulation is achieved since the blood is demoisturized as it passes through the layer of zeolite applied to the wound. In addition, heat is generated as a result of the exothermic action when the zeolite absorbs the moisture from the blood and this heat, although not excessive, is sufficient to cauterize the wound in addition to the improved coagulation effect.

Pervaporation membranes for liquid or gas separation F. Abe; Y. Fujita NGK Insulators Ltd. Jpn Kokai Tokkyo Koho 88,287,504, Nov. 24, 1988; Appl. May 19, 1987 Alcohol-water solutions are concentrated by pervaporation through a hydrophobic inorganic membrane loaded on a porous ceramic support. The hydrophobic membrane is preferably of zeolites (SiO2/ AI=O3 ratio ~> 5:1 ) and has an average pore diam. of ~< 20A °. Thus, a 5 wt.% EtOH-water solution was permeated through a synthetic zeolite membrane (av. pore diam. 15A °, thickness approx. 10 mic- rons); the separation factor was 150, vs. 5 for a conventional membrane.

PATENTS RECEIVED BUT NOT ABSTRACTED

Preparation of a lubricating base oil by catalytic dewaxing with a zeolite catalyst J. Lucien; G. Dutot Shell Internationale Research Maatschappij B.V. Eur. Pat. Appl. 324,528, July 19, 1989; Appl. Jan. 14, 1988 Hydroprocassing with a zeolite Y catalyst containing non- hydrolyzable halogen E.L. Moorehead Union Oil Co. of California U.S. 4,844,791, July 4, 1989; Appl. Aug. 7, 1984

Composite zeolite/CaClz adsorbents for air dehumidification H. Uchikawa; H. Hagiwara; Y. Mihara et al. Onoda Cement Co. Ltd. Jpn Kokai Tokkyo Koho 89,04,218, Jan. 9, 1989; Appl. Feb. 19, 1987

Zeolite catalyst for synthesis of gasoline from olefins Y. Dai Nanjing Petroleum Refinery Chinese 87,103,258, Nov. 23, 1988; Appl. May 4, 1987

Method of ZSM-5-type crystalline zeolite production for catalysts D. Mravec; A. Simkova; J. Ilavsky et al. Czech. 255,394, Nov. 15, 1988; Appl. July 22, 1986

712 ZEOLITES, 1990, Vol 10, September /October

Patent report

Grebenshchikov, 1. V., Institute of Silicate Chemistry USSR 1,498,708, Aug. 7, 1989; Appt. July 7, 1987

Process for the production of gasoline from fuel gas and catalytic reformate in a turbulent reactor with a fluidized bed of zeoliie catalyst J.H. Beech; M.N. Harandi; J.D. Kushnerick et a/. Mobil Oil Corp. PCT Int. Appl. 89,07,586, Aug. 24, 1989; U.S. Appl. Feb. 19, 1988

Alkanes and alkenes conversion to high-octane gasoline in a 2 stage process catalyzed by a crystalline shape selective zeolite M.N. Harandi; H. Owen Mobil Oil Corp. U.S. 4,851,602, July 25, 1989; Appl. Apr. 11, 1988

Catalyst for exhaust gas purification consists of a refractory support carrying zeoliie ion-exchanged with transition metal T. Tanaka; S. Matsumoto; H. Muraki et al. Toyota Motor Corp.; Toyota Central Research and Development Laboratories Inc. Jpn Kokai Tokkyo Koho 89,130,735, May 23, 1989; Appl. Nov. 18, 1987

Exhaust gas treatment with a reducing catalyst comprising zeolite ion-exchanged with transition metal and an oxidizing catalyst comprising Alloy loaded with catalyst component H. Ito; S. Matshumoto; H. Matsuki et a/. Toyota Motor Corp.; Toyota Central Research and Development Laboratories Inc. Jpn Kokai Tokkyo Koho 89,139,144; 89,139,145, May31,1989; Appls. Nov. 25, 1987

Removal of nutrients from industrial wastewater by using zeoliies and water-granulated slag Y. Yoshino Jpn Kokai Tokkyo Koho 89,18,490, Jan. 23, 1989; Appl. July 11, 1987

Method for preparing hydroxysilanes by reacting an alkoxysilane with water in a solvent in the presence of zeoliie Y as catalyst S. Uchimura; H. Sato Hitachi Chemical Co. Ltd. Eur. Pat. Appl. 313,095, Apr. 26, 1989; Jpn.‘Appl. Oct. 23, 1987

NaA-type zeolite treated to give Fe ion-substituted powder reduced in H to give a Fe-dispersed magnetic powder N. Tokina; T. Ishikawa; T. Kawabe et al. Lion Corp. Jpn Kokai Tokkyo Koho 89,140,603, June 1, 1989; Appl. Nov. 26, 1987

Food containers made from cellular styrene containing a dehy- drogenase adsorbed on a zeoliie I. Sunaba; M. Hirano Origin Co. Ltd.; Chubu Srirol Co. Ltd. Jpn Kokai Tokkyo Koho 88,294,372, Dec. 1,1988; Appl. May 25.1987

Ethylene adsorbents containing Ag-ZSM-5 reolite for fruits, vege- tables, and flowers T. Maruoka; S. Maeda; M. Matsushita Shikoku Chemicals Corp. Jpn Kokai Tokkyo Koho 89.148.341, June 9.1989; Appl. Dec. 2.1987

Separation of flavors from fermentation products by adsorption with zeolites and desorption with ethanol A. Furuta; M. Masuda; K. Fujita JGC Corp. Jpn Kokai Tokkyo Koho 89,153,058, June 15,198s; Appl. Dec. 9,1987

Process for 0-methylation of phenols over zeolite catalysts E. Fischer; 0. Steiner Wilhelm-Pieck-Universitst Restock E. Ger. 267,034, Apr. 19, 1989; Appl. Nov. 19, 1987 Process for the preparation of phenylacetaldehydes using borosili- cate zeoliie catalysts H. Smuda; W. Hoelderich; N. Goetr et al. BASF A.-G. Eur. Pat. Appl. 317, 911, May 31, 1989; Ger. Appl. Nov. 27. 1987

Method for the preparation of dihydrofurans and alpha. beta- unsaturated aldehydes and ketones using B-substituted xeoliie catalysts W. Hoelderich; M. Schwarzmann

Purification of acetylene by two-step adsorption of impurities on zeolites and activated carbon G. Saito; T. Nakamura Toho Acetylene Co. Ltd. Jpn Kokai Tokkyo Koho 89,132,535, May 25, 1989; Appl. Nov. 19, 1987

Process for the separation of dihydroxybenrene isomers using a Y type reolite, cation-exchanged with K, Ca. Ba, or Li H.A. Zinnen UOP Inc. U.S. 4,827,049, May 2, 1989; Appl. Mar. 28, 1988

Manufacture of pyrroles from dialkoxytetrahydrofurans and amines in the presence of acidic borosilicate zeolite catalyst W. Hoelderich; M. Hesse; H. Siegel BASF A.-G. Eur. Pat. Appl. 303,206, Feb. 15, 1989; Ger. Appl. Aug. 14, 1987

Mordenite- and titanium-containing isomerization catalysts for nor- mal paraffins C. Travers; J.P. Franck lnstitut Francais du P&role Ger. Offen. 3,837,225, May 18, 1989; Fr. Appl. Nov. 3, 1987

Separating gases using zeolite-containing composite membranes A. Rojey; A. Deschamps; A. Grehier et a/. lnstitut Franqais du P&o/e Eur. Pat. Appl. 324,675, July 19, 1989; Fr. Appl. Jan. 11, 1988

Zeoliie absorbents for the purification of chlorofluorocarbons W.H. Goodman Allied-Signal Inc. U.S. 4,849,558, July 18, 1989; Appl. June 30, 1988

Modified rare-earth Y reolite catalysts for cracking of heavy hyro- carbon feedstocks containing metal poisons P. Chu; G.W. Kirker; A. Huss Mobil Oil Corp. Eur. Pat. Appl. 323,735, July 12, 1989; U.S. Appl. Dec. 28, 1987

Method for stabilization of zinc on zeolite-containing aromatization catalysts S.B. McCullen; P.G. Rodewald Mobil Oil Corp. Eur. Pat. Appl. 325,859, Aug. 2, 1989; U.S. Appl. Dec. 31, 1987

Deodorant paper coated with Y-type zeolite and Fe oxide H. Fujita Mitsubishi Heavy Industries Ltd. Jpn Kokai Tokkyo Koho 89,111,099, Apr. 27,198s; Appl. Oct. 26,1987

Alkylation of aromatic compounds with para-position preference using an acidic mordenite zeolite having SiOz/A1203 mol ratio 2 15:l G.S.J. Lee; J.J. Maj; S.C. Rocke eta/. Dow Chemical Co. Eur. Pat. Appl. 317,907, May 31, 1989; U.S. Appl. Nov. 23, 1987

Process for the catalytic hydration of olefins in the presence of zeolite beta W.K. Bell; T.J. Huang; W.O. Haag eta/. Mobil Oil Corp. Eur. Pat. Appl. 323,270, July 5, 1989; U.S. Appl. Dec. 30, 1987

Noble metal-containing titanosilicates having the structure of zeolite beta and their use as aromatization catalysts N.Y. Chen; S.E. McCullen Mobil Oil Corp. Eur. Pat. Appl. 325,053, July 26, 1989; U.S. Appl. Dec. 29, 1987

Removal of 1,4-dioxane from aqueous alkyl ether sulphate solution by silicalite G. Hiller; D. Schmidt Rewo Chemische Werke GmbH Ger. Offen. 3,740,695, June 15, 1989; Appl. Dec. 1, 1987 Manufacture of zeolites from diatomite and/or AI~OJ sludges K. Yamakawa Yamakawa Sangyo K.K. Jpn Kokai Tokkyo Koho 89.115.814, May 9,198s; Appl. Oct. 28,1987

Manufacture of zeoliie NaX S.P. Zhdanov; N.N. Feoktistova; L.M. Vtyurina

ZEOLITES, 1990, Vol IO, September/October 713

Patent reporl

BASF A.-G. Eur. Pat. Appl. 309,906, Apr. 5, 1989; Appl. Sept. 30, 1987

Fire-resistant elastic resins from modified sepiolite and monomers M. Kato; K. Matsuia Takeda Chemical Industries Ltd. Jpn Kokai Tokkyo Koho 89,09,810, Jan. 13, 1989; Appl. July 2, 1987

Treatment of clay compositions with zeolites for improved paper coatings P.A.C. Gane; G.P. O’Neill ECC International Ltd. U.S. 4,854,971, Aug. 8, 1989; U.K. Appl. Dec. 2, 1986

Regeneration of Y zeolite catalysts H. Saito Tosoh Corp. Jpn Kokai Tokkyo Koho 89,80,433, Mar. 27,1989; Appl. May 21,1987

Manufadture of oxygen-enriched gas from nitrogen-oxygen mix- tures by pressure-swing-adsorption using zeolite adsorbents K. Haruna; K. Ueda; M. lnoue et a/. Seitetsu Kagaku Co. Ltd. Eur. Pat. Appl. 334,495, Sept. 27. 1989; Jpn. Appl. Mar. 17, 1988

Bound, shaped zeolite Y P. Schroeder IBS Engineering and Consulting lngenieurbuero Schroeder GmbH Ger. Offen. 3.738.916, May 24, 1989; Appt. Nov. 17, 1987

Large-pored crystalline titanium zeolites S.M. Kuznicki Engelhard Corp. U.S. 4,853,202, Aug. 1, 1989; Appl. Sept. 8, 1987

Crystalline silicon-rich [metallo] silicates of the sodalite type J.J. Keijsper; M. Mackay Shell lnternationale Research Maatschappij B.V. Eur. Pat. Appl. 333,283, Sept. 20, 1989; U.K. Appl. Mar. 15, 1988

Alkali-free preparation of large crystals of pentasil as shell or solid catalysts A. Danner; U. Mueller; K.P. Unger et a/. BASF A.-G. Eur. Pat. Apl. 304,852, Mar. 1, 1989; Ger. Appl. Aug. 26, 1987

Preparation of Coxa aldehydes by isomerization of 1,3-dioxanes using zeolite catalysts W. Hoelderich; F. Merger BASF A.-G. Ger. Offen. 3,715,755, Nov. 24, 1988; Appl. May 12, 1987

Zeolite-containing prepreg laminates with good antibacterial prop- ertV M. Aoki Toshiba Chemical Corp. Jpn Kokai Tokkyo Koho 89,48,838, Feb. 23,1989; Appl. Aug. 17,1987

Concentration of oxygen by pressure-swing adsorption using crys- talline zeoliie adsorbent M. Tomomura; J. Tomuro; T. Haga et a/. Hitachi L rd. Jpn Kokai Tokkyo Koho 88,315,504, Dec. 23, 1988; Appl. June 16, 1987

Upgrading naphtha with matched catalyst[sl including metal- containing ZSM-5 zeoliie catalyst A.L. Salusinszky Royal Melbourne Institute of Technology ltd. U.S. 4.806.230, Feb. 21, 1989; Australian Appl. Nov. 29, 1985

Process for removal of polynuclear aromatics from a hydrocarbon in an endothermic reformer reaction system using crystalline zeolite adsorbents D.Y. Ngan Shell Oil Co. U.S. 4,804,457, Feb. 14, 1989; Appl. July 22, 1987

lsomeriration process with recycle of mono-methyl-branched paraf- fins and normal paraffins using double separatory sieves [Ca-5A/H ferrierite) W.E. Evans; S.C. Stem She// Oil Co. U.S. 4.804.802, Feb. 14, 1989; Appl. Jan. 25, 1988

Silica-rich zeoliie adsorbents for wastewater treatment J. Jurkschat; K.H. Bergk; W. Schwieger et a/. Martin-Luther-Universitgt Ha//e-Wittenberg E. Ger. 264,207, Jan. 25, 1989; Appl. Sept. 16, 1987

Synthetic resins containing crystalline reolites in fruit preservatives S. Goto; K. Kira Showa benko K.K. Jpn Kokai Tokkyo Koho 88,309,136; 88,309,137, Dec. 16,198s; Appls. June 12, 1987

Reducing heat stress in animals with teolite A in the diet S.M. Laurent; R.N. Sanders Ethyl Corp. U.S. 4,759,932, July 26, 1988; Appl. Mar. 14, 1983

Method for producing m-benzyltoluene by reaction of toluene with diphenylmethane over ZSM-5 zeolite catalysts S. Kawakami; K. Endo; H. Dohi et a/. Nippon Petrochemicals Co. Ltd. Eur. Pat. ADDI. 306.961. Mar. 15. 1989; Jpn. Appl. Sept. 9, 1987 . Process for the production of acylated imidazoles and pyrazoles in the presence of [pentasil-type or faujasite-type] zeolite catalysts H. Lermer; W. Hoelderich; T. Dockner et a/. BASF A.-G. Eur. Pat. Appl. 300,324, Jan. 25, 1989; Ger. Appl. July 21, 1987

Process and ZSM-5 zeolite catalysts for aldehyde manufacture by primary alcohol dehydrogenation I. Tschistowskaia; F. Janowski: W. Schwieger et a/. Martin-Luther-l.%versitit Ha//e-Wiftenberg E. Ger. 264,209, Jan. 25, 1989; Appl. Aug. 31, 1987

Synthetic zeolite-13X-containing packaging films for fruits and vegetables K. Yamaguchi: M. Takase; K. Miyoshi Asahi Chemical Industry Co. Ltd. Jpn Kokai Tokkyo Koho 89,43,543, Feb. l&1989; Appl. Aug. 11,1987 Sepiolite-containing rubber joint sheets for gaskets K. Mimura; H. Kobiyama Nippon Valqua Industries Ltd. Jpn Kokai Tokkyo Koho 88,305,183, Dec. 13,198s; Appl. June 8,1987

Process and borosilicate zeolite catalysts for the manufacture of 1,2-dialkoxyethenes from trialkoxyethanes W. Hoelderich; D. Koeffer; W. Bertleff BASF A.-G. Eur. Pat. Appl. 302,486, Feb. 8, 1989; Ger. Appl. Aug. 6, 1987

Process and ZSM-5 zeolite-based catalys+s for the manufacture of aromatic hydrocarbons from ethane B. Kulbe; H. Siegel; 0. Baeder-Bederski et a/. VEB Chemieanlagenbaukombinat Leipzig-Grimma E. Ger. 262,020, Nov. 16, 1988; Appl. July 13, 1987

Method for selectivity control of n-heptane conversion on zeolite catalysts K.H. Steinberg; F. Roessner; U. Mroczek et a/. Karl-Marx-Universitat Leipzig E. Ger. 261,358, Oct. 26, 1988; Appl. May 12, 1987

Pentasil-type aluminosilicate reoliies with high catalytic activity Y. Magaya; K. Iwayama; T. lnoue Toray Industries Inc. Jpn Kokai Tokkyo Koho 89,03,007, Jan. 6, 1989; Appl. Jan. 16, 1987

Hydrocracking naphthas using mildly steamed, noble metal- containing zeolite beta K.J. Hickey; R.A. Morrison Mobil Oil Corp. U.S. 4.812.223, Mar. 14, 1989; Appl. May 1, 1987 Removal of nitrogen oxides from waste gases conraining sulphur oxides by reduction using iron silicate teolites of the pentasil-type as catalysts W. Hoelderich; 0. Scheidsteger; R. Drews et a/. BASF A.-G. Ger. Offen. 3,723,072, Jan. 19, 1989; Appl. July 11, 1987

Manufacture of aluminum-free pentasil zeolites as cation exchan- gers for use in water purification M. Buelow; J. Caro; D. Freude et a/. Karl-Marx lJniversit& Leipzig E. Ger. 261,747, Nov. 9, 1988; Appl. July 3, 1987

714 ZEOLITES, 7990, Vol 70, September/October

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Union Oil Co. of California U.S. 4,816,538, Mar. 28, 1989; Appl. July 16, 1987

Preparing a noble metal-containing zeolite catalyst T.Y.P. Tsao Mobil Oil Corp. Eur. Pat. Appl. 306,237, Mar. 8, 1989; U.S. Appl. Sept. 2, 1987

Nitrogen resistant paraffin hydroisomerization catalysts comprising ZSM-22,ZSM-23,ZSM-35 and their mixtures in combination with a Group VIII metal N.Y. Chen; W.E. Gatwood; S.B. McCullen Mobil Oil Corp. U.S. 4.814.543, Mar. 21, 1989; Appl. Dec. 28, 1987

Preparation of alcohols by olefin hydration in the presence of H-type ZSM-5 zeolite catalyst T. Shirafuji; K. Sakai Sumitomo Chemical Co. ltd. Jpn Kokai Tokkyo Koho 89,13,044, Jan. 17.1989; Appl. July 6,1987

Regeneration of methanol/methyl ether crystalline zeolite conver- sion catalysts for light olefin manufacture N.P. Forbus; M.M.S. Wu Mobil Oil Corp. U.S. 4,777,156, Oct. 11, 1988; Appl. Dec. 30, 1981 Cont.-in-part of U.S. 4,423,272

Electrically insulating phenolic resins containing zeolites for electric

pa* T. Hanawa; N. Katayanagi Hitachi Chemical Co. Ltd. Jpn Kokai Tokkyo Koho 89,79,252, Mar. 24, 1989; Appl. Sept. 21, 1987

Process and zeolite catalysts for the removal of ethylbenzene in separation and isomerization of Cs aromatic hydrocarbon mixtures K. Tada; E. Minomiya; M. Watanabe Toray Industries Inc. Eur. Pat. Appl. 307,113, Mar. 15, 1989; Jpn. Appl. Aug. 25, 1987

Zeoliie catalysts for transalkylation of polyalkylated aromatic hyd- rocarbons by benzene Y.F. Chu; D.O. Marler; J.P. McWilliams Mobil Oil Corp. Eur. Pat. Appl. 308.097, Mar. 22, 1989; U.S. Appl. Sept. 2, 1987

Improving the selectivity of zeolite-supported catalysts for syn- thesis gas conversion to lower aliphatic alcohols by treatment with nitrogen bases A.K. Bhattacharya; M.S. Bolmer; G. Prada-Silva Texaco Inc. U.S. 4,822,825, Apr. 18, 1989; Appl. Apr. 25, 1988

Antibiotic zeoliie-containing films for pharmaceutical use and food applications R. Niira; T. Yamamoto; M. Uchida Shinagawa Fuel Co. Ltd.; Shinanen New Ceramic K.K. Eur. Pat. Appl. 297,538, Jan. 4. 1989; Jpn. Appl. June 30, 1987

Preparation of lower olefins by zeolites-catalyzed conversion of methanol and/or dimethylether Y. Kiyozumi; K. Suzuki; S. Shin et al. Agency of Industrial Sciences and Technology Jon Kokai Tokkyo Koho 89,31,733, Feb. 2, 1989; Appl. July 27, 1987

Olefin oligomerization using deactivated ZSM-23 zeoliie catalyst D.A. Blain; N.M. Page; L.B. Young Mobil Oil Corp. Eur. Pat. Appl. 311,310, Apr. 12, 1989; U.S. Appl. Oct. 7, 1987

Production of amines by amination of olefins using dealuminated zeolite catalysts M. Deeba Air Products and Chemicals Inc. Eur. Pat. Appl. 305,564, Mar. 8, 1989; Appl. Sept. 1, 1987

Shape selective crystalline CoINi aluminosilicate catalysts for CU alkanol amination M. Deeba Air Products and Chemicals inc. Eur. Pat. Appl. 311,900, Apr. 19, 1989; U.S. Appl. Oct. 13, 1987

Regeneration of a platinum-containing zeoliie catalyst M.J. Cohn; D.W. Robinson; R.J. Lawson UOP Inc.

.U.S. 4,810,683, Mar. 7, 1989; Appl. Jan. 25, 1988

Method for producing stabilized zeolite catalysts T.D. Trowbridge: SC. Fung; T.H. Vanderspurt Exxon Research and Engineering Co. Eur. Pat. Appl. 309,139, Mar. 29, 1989; U.S. Appl. Sept. 21, 1987

Hydrogen reactivation of zeolite cracking and conversion catalysts H. Owen Mobil Oil Corp. Eur. Pat. Appl. 309,219, Mar. 29, 1989; U.S. Appl. Sept. 75, 1987

Fluid catalytic cracking process and apparatus for more effective regeneration of zeoliie catalyst J.A. Herbst; H. Owen; P.H. Schipper Mobit Oil Corp. U.S. 4,814,068, Mar. 21, 1989; Appl. Sept. 3, 1986

Ni-containing Y zeolite hydrocracking catalyst S.F. Abdo

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