Phillips Petroleum Company

Joe Van Pool

Paul D Hann

Charles C Chapman

Stone P Washer

Mack F Potts

R Neil Jackson

A continuous process for alkylating an alkylatable hydrocarbon in the presence of a acid-type catalyst. The reaction product is separated in a first separation zone into an alkylate product phase, located in the upper portion and a catalyst phase located in the lower portion. The catalyst phase is separated into a first portion and second portion, the first portion is cooled and recycled for use in the alkylation reaction zone, and the second portion is passed into a second separation zone, wherein the second portion catalyst phase is further separated into a hot rerun catalyst stream and an acid soluble oil stream. The rerun catalyst stream is passed into the alkylate product phase of the first separation zone. In order to prevent excessive pressure in the first separation zone as a result of the hot rerun catalyst stream, two liquid hydrocarbon drawoffs from the first separation zone are employed. The hotter upper drawoff of the first separation zone is charged as feed to a depropanizer and stripper zone and the cooler lower drawoff of the first separation zone is charged as reflux feed to an isostripper zone. The pressure in the upper portion of the first separation zone is determined. As the determined pressure increases, the flow rate of the cooler lower drawoff is decreased and the flow rate of the hotter upper drawoff is increased such that an increased amount of hot hydrocarbon is shifted to the isostripper zone so as to lower the heat in the first separation zone.

Catalytic alkylation process

MTBE is recovered from an ether containing effluent by fractionation. When driers are not used on the hydrocarbon feed to MTBE manufacture, a separate water-methanol phase occurs in the fractionation overhead which is separately processed in a methanol fractionator and the water recovered is used to water wash the separated hydrocarbon phase from the overhead while methanol is recycled to MTBE and when driers are used on the hydrocarbon feed a separate methanol phase occurs in the fractionation overhead which can be recycled to MTBE manufacture and the hydrocarbon phase is directly passed to a drier preceding alkylation.

Ether recovery

A method for removing organic fluorides from HF alkylation propane in which a stream of relatively pure liquid HF obtained by settling liquid HF from the liquefied hydrocarbon passed to the overhead accumulator common for both the depropanizing column and a hydrogen fluoride stripping column is intimately contacted with a stream of liquid hydrocarbon containing organic fluorides derived from condensing the mixed overhead vapor from a depropanizing column and overhead vapor from an HF stripping column in the process of separating products from a hydrogen fluoride alkylation. In preferred embodiments, the contacting takes place in the static mixer.

Removal of organic fluorides from HF alkylation products

Introduction of undesirable materials through liquid containing vessels of an ether forming unit into an alkylation unit is prevented by pressurizing one or more of these liquid containing vessels of the ether forming unit with a gas which is compatible with both the ether forming reaction and the alkylation reaction and which has a boiling point to keep it in essentially the gas phase in the pressurized vessel and to keep it in the liquid or dissolved form in the overhead accumulator associated with the fractionator of the alkylation unit (if said gas is present in the accumulator at all).

Combined ether and alkylate production

Hydrocarbon vapors containing HF, as from an HF alkylation refrigerated vent gas yield, the reactor settler, and the like are charged to a liquid knock-out drum to remove entrained liquid therefrom, the recovered liquid being pumped to storage in response to liquid level control on the knock-out drum. Recovered vapors are charged to a circulating aqueous caustic treater to yield HF-free vapors, as to a flare. The circulating caustic solution is indirectly heated in response to a preselected caustic solution temperature to prevent freezing. A high pressure rupture disc, upstream from the knock-out drum, affords a vapor relief safety by-pass of the treater. Dry gas, such as nitrogen or sweet, natural gas, continuously sweeps the relief line to maintain this line open and operable.

Relief system

In an HF alkylation process the HF phase leaving the reaction zone is introduced into a separate resaturation zone wherein this HF phase is contacted with isobutane to resaturate the HF with isobutane. In the main hydrocarbon fractionator only a very small quantity of isobutane has to be evaporated and this isobutane can be withdrawn as a side stream and recycled.

HF Alkylation process and apparatus

An alkylation process comprising fractionating the hydrocarbon phase separated from the alkylation effluent into an overhead condensate comprising at least three portions wherein one portion is subjected to depropanization, another portion is used as reflux for the fractionating, and another portion is recycled to the alkylation.

Alkylation process

In a cracking process wherein used catalyst is regenerated, contacted with reducing gas to counter effects of contaminating metals, and recycled to the cracking zone, the improvement comprising using a gas seal to assure that a major portion of the unconsumed reducing gas is also passed into the cracking zone.

Catalytic cracking process

The tail gas from a sulfur process is added directly to the fuel gas supplied to an incinerator burner. The H.sub.2 S in the tail gas is converted by the burner to SO.sub.2 to enable the sulfur process to meet environmental air pollution requirements.

Apparatus for incineration of sulfur plant tail gas

HF is removed from hydrocarbon streams, e.g., a propane liquid stream from HF alkylation by water washing, the wash stream being contacted with solid caustic to remove moisture therefrom. The used wash water containing HF is combines with aqueous caustic obtained from said contacting and the admixture is used to contact HF acid soluble oil to remove HF therefrom. The thus, used aqueous stream separated from this last contacting is reacted with a calcium compound to form insoluble calcium fluoride and a supernatant aqueous liquid containing regenerated caustic. The regenerated caustic is used to remove the sulfur compounds from the alkylation hydrocarbons feed.

Treatment of sulfur-containing HF-alkylation feed, hydrocarbon product,

Incineration of sulfur plant tail gas

In the removal of HF from hydrocarbon streams by chemical reaction with solid potassium hydroxide, runaway temperatures and subsequent explosions can occur when excess HF is present in the hydrocarbon charged to the KOH treater. According to the invention, a control system and method are provided which regulate the flow of hydrocarbon charged to the KOH treater responsive to temperature changes within the system indicative of excessive amounts of HF in the hydrocarbon stream, thereby preventing the treater temperature from exceeding a preselected maximum allowable value. Several embodiments are provided whereby temperature changes in the KOH treater or a differential temperature across an HF stripper are used as temperature sensing points to control flow of hydrocarbon to the KOH treater.

Hydrocarbon purification apparatus

Catalyst regeneration process and apparatus wherein air introduced to a midsection of a downwardly-moving mass of catalyst particles is taken off at the top and at the bottom of said bed through provided outlets and a third outlet is provided at the bottom portion of the said bed adapted to be controlled responsive to change in the flows through the top outlet and first mentioned bottom outlet to maintain substantially constant the total upward and downward flows through said bed. In an embodiment in which coke laydown on a hydrocarbon treated catalyst is burned off flue gases flow upwardly and out from the bed, e.g., through a carbon monoxide or flue gas burning boiler while downwardly flowing flue gas is taken off through a pressure control outlet or opening on which suction is taken by a blower passing flue gases to a boiler, a third outlet also flow controlled is operated responsive to change in the desired upward and downward flows of the flue gases. The third outlet, in operation of the regeneration system, can be normally closed or partly opened so that a condition of no flow or some flow, respectively, can exist.

Catalyst combustion regeneration process in downwardly moving bed with

In the removal of HF from hydrocarbon streams by chemical reaction with solid potassium hydroxide, runaway temperatures and subsequent explosions can occur when excess HF is present in the hydrocarbon charged to the KOH treater. According to the invention, a control system and method are provided which regulate the flow of hydrocarbon charged to the KOH treater responsive to temperature changes within the system indicative of excessive amount of HF in the hydrocarbon stream, thereby preventing the treater temperature from exceeding a preselected maximum allowable value. Several embodiments are provided whereby temperature changes in the KOH treater or a differential temperature across an HF stripper are used as temperature sensing points to control flow of hydrocarbon to the KOH treater.

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Bartlesville, OK, United States of America

Joe Van Pool