Phillips Petroleum Company

Donald J Makovec

Thomas Hutson, Jr

Donald M Haskell

Alden E Beckworth

Paul D Hann

Gary R Patton

Robert O Dunn

Martyn E Pfile

Larry E Lew

A novel integrated olefin processing scheme is provided where olefins and paraffins are processed to produce high octane gasoline blending components. The integrated process involves the dehydrogenation of paraffin compounds to olefin compounds and the processing of olefins by hydroisomerization to produce hydroisomerate streams which are subsequently etherified. Those olefin compounds which are not etherified pass to an alkylation process where they are alkylated with branched chain paraffin compounds to produce an alkylate product.

Integrated olefin processing

A apparatus for the catalytic alkylation of an isoparaffin with one or more olefins. Reactant hydrocarbons are passed in contact with a liquid catalyst such as hydrofluoric acid in a reaction zone. The hydrocarbon phase is allowed to separate from the catalyst phase in a settling zone, and a portion of the hydrocarbon phase is cooled and reintroduced to the reaction zone in a separate stream from that of the feed hydrocarbons. The alkylation apparatus by which the process is carried out includes a vertical reaction vessel, which in a preferred embodiment is 2 to 6 feet in height, a settling vessel, means for fluid flow from the reaction vessel to the settling vessel, a conduit for fluid flow between the upper part of the settling vessel and the reaction zone, and means for cooling fluid in this conduit.

Catalytic alkylation apparatus with hydrocarbon recycle

Dialkyl ether is produced by passing isoolefin, alkanol and diluent through a series of catalyst zones, cooling the effluent between zones and adding isoolefin and/or alkanol between zones.

Dialkyl ether production

A continuous process for the alkylation of an alkylatable hydrocarbon with an alkylating agent in the presence of an acid-type catalyst, including; contacting an alkylatable hydrocarbon with an alkylating agent in the presence of an acid-type catalyst at a temperature and pressure and for a time sufficient to alkylate the alkylatable hydrocarbon; separating the reaction effluent stream into an alkylate product phase and a catalyst phase containing catalyst-soluble oil; cooling the catalyst phase to a temperature essentially equal to the alkylation reaction temperature; recycling the cooled catalyst phase to the alkylation reaction; contacting a diolefinic hydrocarbon with an acid-type catalyst at a temperature and pressure sufficient to form additional catalyst-soluble oil and combining the additional catalyst-soluble oil with the circulating catalyst phase. In accordance with another aspect of the invention, a quantity selected from the amount of catalyst-soluble oil, water and/or the total of the amount of catalyst-soluble oil and water in the catalyst phase is controlled, within specific limits. A start-up procedure and apparatus for carrying out the process are also included.

Catalytic alkylation of hydrocarbons

Control of the temperature rise across a reactor where a portion of the product stream flowing from the reactor is recycled and mixed with the feed flowing to the reactor is accomplished by controlling the flow rate of the recycle stream to thus control the concentration of the reactants flowing to the reactor in such a manner that a desired temperature differential across the reactor is obtained. The inlet temperature to the reactor is controlled by manipulating the temperature of the recycle stream to thus maintain the inlet temperature to the reactor at some desired temperature. Ratio control is utilized to maintain a desired ratio of reactants flowing to the reactor if more than one reactant is flowing to the reactor.

Temperature control for a reactor

A process and apparatus for the catalytic alkylation of an isoparaffin with one or more olefins. Reactant hydrocarbons are passed in contact with a liquid catalyst such as hydrofluoric acid in a reaction zone. The hydrocarbon phase is allowed to separate from the catalyst phase in a settling zone, and a portion of the hydrocarbon phase is cooled and reintroduced to the reaction zone in a separate stream from that of the feed hydrocarbons. The alkylation apparatus by which the process is carried out includes a vertical reaction vessel, which in a preferred embodiment is 2 to 6 feet in height, a settling vessel, means for fluid flow from the reaction vessel to the settling vessel, a conduit for fluid flow between the upper part of the settling vessel and the reaction zone, and means for cooling fluid in this conduit.

Catalytic alkylation method and apparatus with hydrocarbon recycle

A cyclic system for the alkylation of an isoparaffin, e.g., isobutane, wherein a first olefinic reactant, e.g., butylene, is used to alkylate the isoparaffin for a first period of time in an alkylation reactor and then a second olefinic reactant, e.g., propylene, is used to alkylate the isoparaffin for a second period of time in the same alkylation reactor. During the period that the isoparaffin is alkylated with the first olefinic reactant, the reactor effluent stream is continuously separated into a liquid hydrocarbon phase comprising alkylation products and unreacted isoparaffin and a liquid acid alkylation catalyst phase. The acid catalyst is continuously recycled to the reactor and the hydrocarbon phase is passed to a first surge zone or holding tank. During the second period of time, the isoparaffin-rich hydrocarbon phase from the first surge zone and the second olefinic reactant, along with continuously recycled catalyst, are charged to the same alkylation reactor so that, preferably, feed to the reactor is continuously effected. The reactor effluent is continuously separated into a liquid hydrocarbon phase containing unreacted isoparaffin and a liquid catalyst phase. The hydrocarbon phase is charged in part to fractionation and in part to a second surge zone. During the first period of time, hydrocarbon from the second surge zone is charged to this fractionation so the fractionation is continuously in operation. Isoparaffin is continuously removed from the fractionation to a third surge zone. Isoparaffin can be charged from the third surge zone to the alkylation reactor.

Alkylation process utilizing plural olefinic reactants

A continuous process for the alkylation of an alkylatable hydrocarbon with an alkylating agent in the presence of an acid-type catalyst, including; contacting an alkylatable hydrocarbon with an alkylating agent in the presence of an acid-type catalyst at a temperature and pressure and for a time sufficient to alkylate the alkylatable hydrocarbon; separating the reaction effluent stream into an alkylate product phase and a catalyst phase containing catalyst-soluble oil; cooling the catalyst phase to a temperature essentially equal to the alkylation reaction temperature; recycling the cooled catalyst phase to the alkylation reaction; contacting a diolefinic hydrocabon with an acid-type catalyst at a temperature and pressure sufficient to form additional catalyst-soluble oil and combining the additional catalyst-soluble oil with the circulating catalyst phase. In accordance with another aspect of the invention, a quantity selected from the amount of catalyst-soluble oil, water and/or the total of the amount of catalyst-soluble oil and water in the catalyst phase is controlled, within specific limits. A start-up procedure and apparatus for carrying out the process are also included.

Acid type hydrocarbon alkylation with acid-soluble oil addition

A method of alkylating an alkylatable hydrocarbon with different alkylating agents, at different reaction temperatures and in a single reaction zone, in which an alkylatable hydrocarbon is contacted with an acid-type catalyst and at different points in an elongated reaction zone, the reaction zone effluent is separated into a hydrocarbon phase and a catalyst recycle phase and the reaction temperatures of the various alkylating agents are maintained at different temperatures by splitting the recycle catalyst phase into an equal number of streams and adjusting the reaction temperatures by adjusting the temperatures of the recycle catalyst phase streams, the relative proportions of the recycle catalyst phase streams or both. A method of starting-up the process and apparatus for conducting the process are also disclosed.

Acid-type hydrocarbon alkylation with acid recycle streams at spaced

In a conventional reactor into which at one end portion there are fed olefin, isoparaffin and HF acid, or other catalysts, and from which an alkylate containing product is passed to a phase separator or settling zone, there is added to the reactor to a downstream portion therein, beyond the original point of entry of the first olefin feed a second portion of olefin feed together with hydrocarbon phase recycled from the phase separator or settling zone.

Olefin feed in HF alkylation of isoparaffin with olefin

An improved HF alkylation process comprising, in series, HF and isoparaffin flow and parallel injection of at least two different olefins into a vertically extended reaction zone coupled with recycle of some of the alkylation hydrocarbon effluent to each point of olefin introduction into the alkylation zone. The improved alkylation system allows minimum sized fractionation and extremely high isoparaffin/olefin ratios with temperature control of the reaction at each olefin injection.

HF alkylation introducing separate olefins in vertically extended reactor

The time for effecting separation of HF acid-hydrocarbon emulsions is substantially decreased by adding a finite amount of up to about 700 ppm of a tetraalkylammonium iodide coalescing promoter to the emulsion. The rapid separation of HF acid-hydrocarbon emulsions comprising reaction effluent obtained from alkylation processes is facilitated by the addition of a tetraalkylammonium iodide to the reaction effluent prior to phase separation.

Growing community of inventors

Bartlesville, OK, United States of America

Donald J Makovec