Chemplex Company

National Petro Chemicals Corporation

Norchem, Inc.

Enron Chemical Corporation

William Kirch

Robert A Dombro

Jerome H Krekeler

Henri A Aboutboul

Paul A Thompson

R Sven Solvik

Wayne L Carrick

A method of preparing a high pore volume, high surface area zirconia-titania-silica tergel useful as an olefin polymerization or copolymerization catalyst support comprises the steps of coprecipitating hydrous zirconia, hydrous titania and hydrous silica, aging and washing the resulting hydrotergel, removing water from the washed hydrotergel and optionally calcining the resulting xerotergel. Resins with predetermined properties such as high melt index, broad molecular weight distribution, high weight swell, etc. can be produced from catalysts of the chromium or Ziegler type based on these supports.

Zirconia-titania-silica tergels and their use as catalyst supports

A method of polymerizing olefins comprising contacting an olefin or mixture of olefins with a catalyst prepared with large pore volume zirconia-silica catalyst supports. The supports are prepared by reacting a zirconium compound of the formula M.sub.4 Zr(C.sub.2 O.sub.4).sub.4.nH.sub.2 O, where M is an alkali metal or ammonium ion and n equals 0 to 10, with a silicon compound of the type A.sub.2 SiO.sub.3, where A is an alkali metal, in an aqueous solution at a pH equal to at least 11, then adding an acidic solution to a pH of about 5-9 to produce a hydrocogel. The hydrocogel is then aged and washed free of soluble by-products with an aqueous washing agent. Water is removed from the washed hydrocogel by azeotropic distillation or by washing with a water miscible solvent and then calcining the resulting xerocogel.

Method of polymerizing olefins

Ethylene is copolymerized with one or more 1-olefins under conditions of high temperature and pressure in the presence of an inert gaseous ratio modifier. As a result, liquid condensation which contributes to equipment damage and unsafe operation is avoided, and copolymer product density is readily controllable.

Copolymerization of ethylene

A process and apparatus for the polymerization of an olefin in a particle form process to form solid particles of polyolefin in a liquid slurry in a polymerization zone and the solid polymer particles are separated from the liquid diluent and any unreacted monomer, in which a portion of the slurry is diverted in the polymerization zone through a liquid cyclone separator. This separator has a separating portion thereof in heat exchange relationship with the zone liquid. After the separation in the liquid cyclone, the clarified separated liquid is returned continuously to the polymerization zone and the resulting concentrated slurry is directed to a place of separation of the polymer particles.

Method of making and recovering olefin polymer particles

A method of preparing large pore volume zirconia-silica catalyst supports, the resulting supports and a method of polymerizing olefins comprising contacting an olefin or mixture of olefins with a catalyst prepared with these supports. The supports are prepared by reacting a zirconium compound of the formula M.sub.4 Zr(C.sub.2 O.sub.4).sub.4.nH.sub.2 O, where M is an alkali metal or ammonium ion and n equals 0 to 10, with a silicon compound of the type A.sub.2 SiO.sub.3, where A is an alkali metal, in an aqueous solution at a pH equal to at least 11, then adding an acidic solution to a pH of about 5-9 to produce a hydrocogel. The hydrocogel is then aged and washed free of soluble by-products first with water, then with aqueous ammonium nitrate and again with water. The water is removed from the washed hydrocogel by azeotropic distillation or by washing with a water miscible solvent and then calcining the resulting xerocogel.

Method of preparing zirconia-silica xerogels, the xerogels, and xerogel

A catalyst for polymerizing one or more 1-olefins and prepared by the process of (1) forming an initial mixture of a finely divided support such as silica and a chromium.sup.+3 compound of either of the formulas ##STR1## or Cr(OOCR).sub.3 or a mixture in an amount to provide about 0.1-30 weight percent of chromium in the finished catalyst and in which each R is individually selected from hydrogen or a hydrocarbyl group of 1-20 carbon atoms and the necessary hydrogen atoms, followed by (2) heating the mixture of (1) in a stream of dry, inert, and non-oxidizing gas and heating to a temperature of about 230.degree.-540.degree. C., and then (3) forming a second combination by adding a titanium compound to the product of (2) at a temperature ranging from 95.degree.-370.degree. C., and then (4) activating the mixture of (3) by heating in a dry, oxidizing atmosphere such as dry air to a temperature of about 370.degree.-1100.degree. C. The disclosure also includes a method of preparing such a catalyst and the method of polymerizing at least one 1-olefin with said catalyst.

Polymerization process

Apparatus for the polymerization of an olefin in a particle form process to form solid particles of polyolefin in a liquid slurry in a polymerization zone and the solid polymer particles are separated from the liquid diluent and any unreacted monomer, in which a portion of the slurry is diverted in the polymerization zone through a liquid cyclone separator. This separator has a separating portion thereof in heat exchange relationship with the zone liquid. After the separation in the liquid cyclone the clarified separated liquid is returned continuously to the polymerization zone and the resulting concentrated slurry is directed to a place of separation of the polymer particles.

Manufacture and recovery of olefin polymer particles

Catalyst and process of preparing the catalyst

Silica xerogels having pore volumes greater than about 2.0 cc/g., the major portion of which volumes are provided by pores having pore diameters ranging from 300 to 600 A, and surface areas ranging from 200 to 500 m.sup.2 /g. Xerogels having such cumulative pore volume, pore diameter distribution, and surface area characteristics are useful as supports for stereospecific catalysts for particle form olefin polymerization reactions effecting the production of low molecular weight, high melt index polyolefins.

Silica xerogels

An olefin polymerization catalyst comprising a silica xerogel support having a pore volume greater than about 2.0 cc/g, the major portion of which volume is provided by pores having pore diameters ranging from 300 to 600 A and a surface area ranging from 200 to 500 m.sup.2 /g, and having deposited thereon a metal-containing catalytic material, such as chromium oxide, or other metal oxide. Further, a polymerization process utilizing such a catalyst for the preparation of polyolefins having relatively low molecular weights and high melt indexes without loss of catalyst activity, especially a process for the preparation of polymers and copolymers of 1-olefins having a maximum of 8 carbon atoms in the chain and having no branching nearer the double bond than the 4-position, e.g., ethylene polymers.

Catalyst useful for olefin polymerization process

An olefin polymerization process for the preparation of polyolefins having relatively low molecular weights and high melt indexes without loss of catalyst activity, utilizing a catalyst comprising a silica xerogel support having a pore volume greater than about 2.0 cc/g, the major portion of which volume is provided by pores having pore diameters ranging from 300 to 600 A and a surface area ranging from 200 to 500 m.sup.2 /g, and having deposited thereon a metal-containing catalytic material, such as chromium oxide, or other metal oxide. The process is designed for the preparation of polymers and copolymers of 1-olefins having a maximum of 8 carbon atoms in the chain and having no branching nearer the double bond than the 4-position, e.g., ethylene polymers.

Growing community of inventors

Clinton, IA, United States of America

William Kirch