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WO1999048845A1 - Systeme de reacteur d'alkylation a l'acide sulfurique - Google Patents

Systeme de reacteur d'alkylation a l'acide sulfurique Download PDF

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Publication number
WO1999048845A1
WO1999048845A1 PCT/US1999/005712 US9905712W WO9948845A1 WO 1999048845 A1 WO1999048845 A1 WO 1999048845A1 US 9905712 W US9905712 W US 9905712W WO 9948845 A1 WO9948845 A1 WO 9948845A1
Authority
WO
WIPO (PCT)
Prior art keywords
isoparaffin
reactor vessel
olefin
hydrocarbon
sulfuric acid
Prior art date
Application number
PCT/US1999/005712
Other languages
English (en)
Inventor
Brian A. Cunningham
Saverio G. Greco
Original Assignee
Mobil Oil Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mobil Oil Corporation filed Critical Mobil Oil Corporation
Priority to AU34516/99A priority Critical patent/AU3451699A/en
Publication of WO1999048845A1 publication Critical patent/WO1999048845A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/56—Addition to acyclic hydrocarbons
    • C07C2/58—Catalytic processes
    • C07C2/62—Catalytic processes with acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
    • C07C2527/054—Sulfuric acid or other acids with the formula H2Sn03n+1

Definitions

  • the present invention reduces the possibility of leaks in the reactor system, by reducing the number of moving parts entering or exiting the reactor, which must be sealed against acid and hydrocarbon leakage.
  • a class of petroleum-derived compounds known to have particularly high octane ratings are branched paraffins, having from 6 to 12 carbon atoms.
  • Unfortunately, the amount of naturally occuring C ⁇ - ⁇ 2 branched paraffins in crude petroleum is limited and is insufficient to meet the increasing demand for high octane blend stocks. Accordingly, the petroleum industry has developed methods for synthesizing branched paraffins from existing materials to supplement the naturally existing supply of such high-octane materials.
  • alkylates One important method of obtaining branched C ⁇ -i2 paraffins, termed “alkylates", is by acid catalyzed alkylation of short-chain isoparaffins with short-chain olefins, derived from various refinery processes.
  • alkylates two commercially successful acid catalyzed alkylation systems are being utilized: A sulfiiric acid catalyzed system and a hydrofluoric acid (HF) catalyzed system.
  • the sulfiiric acid catalyzed system is conducted at low-temperatures, from 2° to 7°C, while the HF catalyzed system is conducted at ambient to elevated temperatures from 20° to 40°C. Therefore, the sulfiiric acid catalyzed system is relatively more complex and energy intensive, requiring some source of refrigeration of the reactants and/or the reactor to work effectively.
  • sulfiiric acid reactor systems Two major designs of sulfiiric acid reactor systems are currently in use, both of which were developed in the 1940's and have received few major improvements in the ensuing years.
  • Both major systems the horizontal contactor (Fig. 4), commonly known as the effluent refrigeration system, and the cascade reactor (Fig. 5), commonly known as the Cascade Auto Refrigeration system, employ stirrers or impellers 30 with externally mounted motors and rotating shafts running into the reactor vessel, which must be sealed against leakage to the ambient environment.
  • the stirrers are used to create and maintain an emulsion within the system, assuring maximum reactive surface area and intimate contact between the reactants and the catalyst, so as to maximize the reaction efficiency.
  • a first object of the present invention is to provide a sulfiiric acid alkylation reactor system having few or no moving parts entering the reactor which must be sealed against leaks to the ambient environment.
  • a second object of the present invention is to provide a safer sulfiiric acid alkylation reactor system in which, in the event of a leak to ambient, the system can be easily and rapidly shut-down, so as to minimize the volume of the leak.
  • a third object of the present invention is to provide a sulfiiric acid alkylation reactor which is less expensive to build and maintain, relative to existing reactor systems, and also has a lower operating cost.
  • a fourth object of the present invention is to provide a sulfiiric acid alkylation reactor system in which some degree of phase separation is achieved between the sulfiiric acid and hydrocarbon phases of the reaction products, so as to increase the efficiency of the phase separation step, and thereby the overall efficiency of the system.
  • a sulfiiric acid-catalyzed alkylation reactor system for alkylating isoparaffins with olefins, to produce hydrocarbon alkylates.
  • the reactor vessel has a vertical cylindrical wall, a top, an inverted conical bottom portion and internal perforated baffles, and communicates with a settling vessel for separating the sulfiiric acid from the alkylate through a transfer pipe having a vertical portion suspended within the central portion of the reactor vessel and a horizontal portion sealably extending through the cylindrical wall of the reactor vessel.
  • the transfer pipe has a first end near the conical bottom portion of the reactor vessel and a second end at a top portion of the settling vessel.
  • the present invention is directed to a process for alkylating at least one isoparaffin with at least one olefin, in the presence of sulfiiric acid catalyst, to produce a hydrocarbon alkylate.
  • a first liquid stream comprising the isoparaffin(s) is combined with a second liquid stream comprising sulfiiric acid and the combined streams are passed through at least one static mixer to form an isoparaffin/ sulfiiric acid emulsion stream.
  • a third liquid stream comprising the olefin(s) is combined with the isoparaffin/sulfuric acid emulsion stream and the further combined streams are passed through at least one static mixer 4 to form an olefin/isoparaffin/sulfuric acid emulsion stream.
  • the olefin/isoparaffin/sulfuric acid emulsion stream is injected into a reactor vessel having a vertical cylindrical wall, in a direction tangential to the cylindrical wall and with sufficient force to impart a circular motion to the olefin/isoparaffin/sulfuric acid emulsion within the reactor vessel, wherein the olefin is reacted with the isoparaffin to form a hydrocarbon alkylate/isoparaffin/sulfuric acid mixture.
  • Fig. 1 is a cross-sectional diagram of the sulfiiric acid alkylation system of the present invention.
  • Fig. 2 is an enlargement of the cross-section of the reactor vessel of the present invention.
  • Fig. 3 is a horizontal section along line A-A of Fig. 2, which illustrates the internal arrangement of the elements in the reactor vessel of the present invention.
  • Fig. 4 is a cross-sectional diagram of the prior art horizontal contactor sulfiiric acid alkylation reactor system.
  • Fig. 5 is a cross-sectional diagram of the prior art cascade sulfiiric acid alkylation reactor system.
  • the following detailed description of the invention is provided to aid those skilled in the art in practicing the present invention. Even so, the following detailed description of the invention should not be construed to unduly limit the present invention, as modifications and variations in the embodiments herein discussed may be made by those of ordinary skill in the art without departing from the spirit or scope of the present inventive discovery.
  • the reactor system of the present invention is illustrated in Fig.
  • a vertical, cylindrical reactor vessel 10 with an inverted conical bottom portion 10a, having disposed centrally therein a vertical portion of a U-shaped transfer pipe 25, with a first end disposed toward the inverted conical bottom portion 10a, for transfer of reacted materials and catalyst to a separator vessel 20.
  • the vertical portion of the transfer pipe is disposed coaxially with the axis of the cylindrical reactor vessel.
  • the horizontal run of the transfer pipe extends through the vertical wall of the reactor vessel, and is sealed against leakage at its contact points with the vertical wall.
  • the other vertical portion of the tranfer pipe 25 empties into the phase separation vessel 20, wherein the mixed emulsion of sulfiiric acid catalyst and hydrocarbon reaction products, including the desired alkylate, are left to settle and separate, based upon the differences in specific gravities between the two phases.
  • the reactants for the system are derived from separate sources within a typical refinery, which are conventional and not depicted.
  • the incoming isoparaffin, typically isobutane passes from the isoparaffin source, not shown, through line 16, and combines with a sulfiiric acid-rich emulsion exiting the inverted conical bottom portion of the reactor.
  • the combined isoparaffin/sulfiiric acid stream passes through emulsion pump 17, which partially emulsifies the stream by the action of the pump impeller, and is further combined with the relatively pure sulfiiric acid stream recycled from the bottom of the separator tank 20, and pumped through the acid pump 21, which effects further emulsification.
  • the combined isoparaffin/sulfiiric acid stream then passes through the injection inlet pipe 11, which splits into multiple injection inlet ports near the reactor vessel 10.
  • Each of the injection inlet pipes has disposed therein at least two static mixers 12 in series, more clearly illustrated in Figs. 2 and 3.
  • the combined isoparaffin/sulfuric acid stream passes through at least one, but preferably multiple static mixers, so as to maximize the emulsification of the isoparaffin and sulfiiric acid.
  • the olefin inlet line(s) 18 injects the olefin, typically butene, into the isoparaffin/sulfuric acid emulsion through a nozzle which disperses the olefin into small droplets.
  • the thus-combined stream is passed through at least one more static mixer, to form an olefin/isoparaffin/sulfuric acid emulsion.
  • the total number of static mixers in each injection inlet line may vary, but is preferably four: One or three before and one or three after the olefin inlet line connection.
  • the injection inlet pipes are arranged tangentially around the cylindrical reactor vessel, and the emulsified reactant stream enters the reactor vessel with sufficient force and velocity to impart a circular motion to the emulsion within the reactor vessel.
  • a suitable reactant stream velocity is 13 ft/sec.
  • Within the reactor vessel are a number of perforated baffles 15, extending radially inward from the reactor vessel wall, or radially outward from the central transfer pipe, or preferably both radially inward from the reactor vessel wall and radially outward from the central transfer pipe.
  • the perforated baffles act to further increase shear and mixing so as to maintain the reactants in the emulsified state within the reactor vessel, as the circulating emulsion contacts and passes through the baffle perforations.
  • At least one isoparaffin is alkylated with at least one olefin, in the presence of sulfiiric acid catalyst, to produce hydrocarbon alkylates.
  • a first liquid stream comprising the isoparaffin(s) is combined with a second liquid stream comprising sulfiiric acid and the combined streams are passed through at least one static mixer to form an isoparaffin/sulfiiric acid emulsion stream.
  • a third liquid stream comprising the olefin(s) is combined with the isoparaffin/sulfuric acid emulsion stream and the further combined streams are passed through at least one static mixer to form an olefin/isoparaffin/sulfuric acid emulsion stream, which is injected into a reactor vessel having a vertical cylindrical wall, in a direction tangential to the cylindrical wall and with sufficient force to impart a circular motion to the olefin/isoparaffin/sulfuric acid emulsion within the reactor vessel, wherein the olefin(s) is reacted with an excess of the isoparaffin(s) to form a hydrocarbon alkylate/isoparaffin/sulfuric acid mixture. It is believed that a majority, if not all, of the olefin is reacted within the last static mixer, although the inventors do not wish to be held to this theory.
  • the olefin feed is derived from one or more existing refinery processors, such as the fluidized catalytic cracker (FCC), a thermal cracking reactor or the coker.
  • FCC fluidized catalytic cracker
  • Any short chain olefin selected from C 2 . 5 olefins, such as ethene, propene, 1-butene, 2-butene, pentenes or mixtures thereof are suitable as the olefin reactant feed stream, although the butenes are preferred.
  • the isoparaffin feed is derived from naturally occuring isoparaffins isolated in the refining of crude petroleum, such as isobutane, or is derived from various refinery processors, such as the FCC, coker, hydrocracker or the reformer. While isobutane is a preferred isoparaffin, the liquid fuel value of which is limited by its vapor pressure, other isoparaffins may be used, either alone or in combination with isobutane.
  • the nature of the olefin and isoparaffin feeds is in theory limited only by the fact that the desired alkylate products should have boiling points within the gasoline fraction boiling range, from 40° to 200°C.
  • Reaction parameters of the present invention are essentially the same as in the existing sulfiiric acid alkylation systems. Acid to hydrocarbon ratio is 1:1, while it is preferred that a large excess of isoparaffins relative to olefins be present, to maximize olefin conversion to alkylates.
  • the isoparaffin: olefin ratio should be from 4:1 to 10:1, preferably 8:1 or greater.
  • Reaction temperatures are subambient, ranging between 2° to 10°C, with cooling provided by evaporation of the isoparaffin from the surface of the reaction emulsion within the reactor vessel. Preferably, all cooling is provided by evaporation of the isoparaffin from the surface of the reaction emulsion.
  • the evaporate is withdrawn from the top of the vessel, fed to a compressor, condensed and recycled into the system.
  • the olefin, the isoparaffin and the sulfiiric acid enter the reactor vessel of the present invention as an emulsion, rather than being mixed in the reactor vessel in the first instance.
  • the emulsion of the present invention circulates within the reactor vessel, it is maintained in the emulsion state by passing through the perforated baffles in the reactor to complete the alkylation reaction. That is, the static mixers and baffles, in combination with the emulsion and acid pumps, provide the mixing energy for forming the reactant emulsion, thus minimizing moving parts in the present system. In fact, moving parts are eliminated within the reactor vessel itself.
  • the circular motion of the emulsion within the reactor vessel acts to partially phase-separate the sulfiiric acid and hydrocarbon phases of the emulsion toward the bottom of the vessel due to the centrifugal force imparted to the emulsion and the greater specific gravity of the sulfiiric acid phase. That is, upon moving into the bottom of the reactor vessel, where the perforated baffles are absent, increased residence time is provided so that the heavier sulfiiric acid phase tends to concentrate toward the bottom portion of the vessel. This effect is enhanced by the inverted conical shape of the bottom of the reactor vessel, wherein the angular velocity and therefore the centrifugal force on the circulating acid-rich emulsion is increased.
  • the hydrocarbon/sulfuric acid mixture passing into the transfer tube or pipe 25 from the bottom of the reactor vessel is already enriched in the hydrocarbon phase, requiring less settling time in the settling tank 20 and/or a smaller settling tank.
  • Phase separation is completed in the settling tank, with the less dense alkylate-containing hydrocarbon phase floating to the top and being collected through line 22. Any unreacted isoparaffin may be removed by flash-off or distillation, to recover the alkylate.
  • level control within the system is optionally maintained by a level controller LC, the output of which is fed to control valve 23 (Fig. 1).
  • the sulfiiric acid alkylation reactor of the present invention satisfies the stated objects of the present invention by eliminating moving parts which penetrate the reactor vessel, and the sealing surfaces therefor, by statically mixing the reactants and catalyst prior to their entry into the reactor vessel, and maintaining the emulsion within the vessel by static mixing through the perforated baffles.
  • the reactor system of the present invention is less expensive to build, run and maintain than previous reactor systems.
  • the only moving parts which are likely to leak are the seals associated with the emulsion and acid pumps, leakage can be readily stopped by shutting down the pumps and isolating them by conventional automatic shut-off valving, thus minimizing leakage volume.
  • the two prior art systems will continue to leak until the entire system is depressurized.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un système de réacteur d'alkylation catalysé à l'acide sulfurique pour l'alkylation d'isoparaffines avec des oléfines, de sorte que des alkylats hydrocarburés soient produits. La cuve de réacteur présente une paroi cylindrique verticale, un sommet, une partie inférieure conique inversée, des chicanes internes perforées et de multiples tuyaux d'entrée d'injection d'émulsion, placés tangentiellement par rapport à l'intérieur de la cuve de réacteur et en communication avec celle-ci. Les tuyaux d'entrée d'injection contiennent des mélangeurs statiques intégrés et l'injection tangentielle de l'émulsion imprime un mouvement circulaire au contenu de la cuve de réacteur, ce qui induit une séparation de phase partielle des produits ayant réagi. La cuve de réacteur communique avec une cuve de clarification par l'intermédiaire d'un tuyau de transfert doté d'une partie verticale suspendue dans la partie centrale de la cuve de réacteur, et d'une partie horizontale s'étendant de manière étanche à travers la paroi cylindrique de la cuve de réacteur. Le tuyau de transfert présente une première extrémité proche de la partie inférieure conique de la cuve de réacteur et une seconde extrémité au sommet de la cuve de clarification. Le système de réacteur permet une réaction catalysée à l'acide sulfurique des oléfines avec les isoparaffines, par mélange statique des réactants, et la réduction au minimum des fuites de réactants dans l'environnement.
PCT/US1999/005712 1998-03-20 1999-03-16 Systeme de reacteur d'alkylation a l'acide sulfurique WO1999048845A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU34516/99A AU3451699A (en) 1998-03-20 1999-03-16 Sulfuric acid alkylation reactor system with static mixers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US4492098A 1998-03-20 1998-03-20
US09/044,920 1998-03-20

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001094283A1 (fr) * 2000-06-06 2001-12-13 Orgral International Technologies Corporation Procede et dispositif de production d'alkylates
WO2009139848A1 (fr) * 2008-05-16 2009-11-19 Exxonmobil Research And Engineering Company Réacteur pour l'alkylation d'oléfines par des isoparaffines
WO2019046558A1 (fr) * 2017-08-31 2019-03-07 E. I. Du Pont De Nemours And Company Système de réacteur d'alkylation à l'acide sulfurique et conversion d'une unité d'alkylation au fluorure d'hydrogène en une unité d'alkylation à l'acide sulfurique
CN114432976A (zh) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 一种烷基化汽油的生产装置和方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2347195A (en) * 1942-05-25 1944-04-25 Universal Oil Prod Co Means of contacting fluid reactants
US4236036A (en) * 1979-04-05 1980-11-25 Phillips Petroleum Company Catalytic alkylation of hydrocarbons
US4383977A (en) * 1979-10-02 1983-05-17 Phillips Petroleum Company Catalytic alkylation apparatus with hydrocarbon recycle

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2347195A (en) * 1942-05-25 1944-04-25 Universal Oil Prod Co Means of contacting fluid reactants
US4236036A (en) * 1979-04-05 1980-11-25 Phillips Petroleum Company Catalytic alkylation of hydrocarbons
US4383977A (en) * 1979-10-02 1983-05-17 Phillips Petroleum Company Catalytic alkylation apparatus with hydrocarbon recycle

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001094283A1 (fr) * 2000-06-06 2001-12-13 Orgral International Technologies Corporation Procede et dispositif de production d'alkylates
US7435864B2 (en) 2000-06-06 2008-10-14 Orgral International Technologies Corporation Method and device for the production of alkylates
WO2009139848A1 (fr) * 2008-05-16 2009-11-19 Exxonmobil Research And Engineering Company Réacteur pour l'alkylation d'oléfines par des isoparaffines
US8119084B2 (en) 2008-05-16 2012-02-21 Exxonmobil Research & Engineering Company Reactor for isoparaffin olefin alkylation
US8383874B2 (en) 2008-05-16 2013-02-26 Exxonmobil Research And Engineering Company Process for isoparaffin olefin alkylation
WO2019046558A1 (fr) * 2017-08-31 2019-03-07 E. I. Du Pont De Nemours And Company Système de réacteur d'alkylation à l'acide sulfurique et conversion d'une unité d'alkylation au fluorure d'hydrogène en une unité d'alkylation à l'acide sulfurique
CN111344250A (zh) * 2017-08-31 2020-06-26 杜邦工业生物科学美国有限责任公司 硫酸烷基化反应器系统和氟化氢烷基化单元向硫酸烷基化单元的转换
US11148115B2 (en) 2017-08-31 2021-10-19 Refining Technology Solutions, Llc Sulfuric acid alkylation reactor system and conversion of a hydrogen fluoride alkylation unit to a sulfuric acid alkylation unit
CN111344250B (zh) * 2017-08-31 2023-09-22 精炼技术解决方案有限责任公司 硫酸烷基化反应器系统和氟化氢烷基化单元向硫酸烷基化单元的转换
CN114432976A (zh) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 一种烷基化汽油的生产装置和方法
CN114432976B (zh) * 2020-10-31 2023-11-07 中国石油化工股份有限公司 一种烷基化汽油的生产装置和方法

Also Published As

Publication number Publication date
AU3451699A (en) 1999-10-18

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