EP1856009A2 - Production d'essence par polymerisation d'olefine - Google Patents

Production d'essence par polymerisation d'olefine

Info

Publication number
EP1856009A2
EP1856009A2 EP06736479A EP06736479A EP1856009A2 EP 1856009 A2 EP1856009 A2 EP 1856009A2 EP 06736479 A EP06736479 A EP 06736479A EP 06736479 A EP06736479 A EP 06736479A EP 1856009 A2 EP1856009 A2 EP 1856009A2
Authority
EP
European Patent Office
Prior art keywords
catalyst
olefin
product
feed
spa
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP06736479A
Other languages
German (de)
English (en)
Other versions
EP1856009A4 (fr
Inventor
Stephen H. Brown
George M. K. Mathys
Jane Chi-Ya Cheng
Jeffrey Thomas Elks
Ajit Bhaskar Dandekar
Benjamin Santiago Umansky
Michael Christopher Clark
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
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
Priority claimed from US11/362,257 external-priority patent/US20060194999A1/en
Application filed by ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of EP1856009A2 publication Critical patent/EP1856009A2/fr
Publication of EP1856009A4 publication Critical patent/EP1856009A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • 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
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1081—Alkanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • C10G2300/1092—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • C10G2300/802—Diluents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • This invention relates to light olefin polymerization for the production of gasoline boiling range motor fuel.
  • the first catalytic polymerization process used a sulfuric acid catalyst to polymerize isobutene selectively to dimers which could then be hydrogenated to produce a branched chain octane for blending into aviation fuels.
  • Other processes polymerized isobutylene with normal butylene to form a co-dimer which again results in a high octane, branched chain product.
  • An alternative process uses phosphoric acid as the catalyst, on a solid support and this process can be operated to convert all the C 3 and C 4 olefins into high octane rating, branched chain polymers.
  • This process may also operate with a C 4 olefin feed so as to selectively convert only isobutene or both n-butene and isobutene.
  • This process has the advantage over the sulfuric acid process in that propylene may be polymerized as well as the butenes and at the present time, the solid phosphoric acid [SPA] polymerization process remains the most important refinery polymerization process for the production of motor gasoline.
  • feeds are pretreated to remove hydrogen sulfide and mercaptans which would otherwise enter the product and be unacceptable, both from the view point of the effect on octane and upon the ability of the product to conform to environmental regulations.
  • a feed is washed with caustic to remove hydrogen sulfide and mercaptans, after which it is washed with water to remove organic bases and any caustic carryover. Because oxygen promotes the deposition of tarry materials on the catalyst, both the feed and wash water are maintained at a low oxygen level. Additional pre- treatments may also be used, depending upon the presence of various contaminants in the feeds.
  • the unit may be classified as having chamber reactors or tubular reactors.
  • the chamber reactor contains a series of catalyst beds with bed volume increasing from the inlet to the outlet of the reactor, with the most common commercial design having five beds.
  • the catalyst load distribution is designed to control the heat of conversion.
  • Chamber reactors usually operate with high recycle rates.
  • the recycle stream depleted in olefin content following polymerization, is used to dilute the olefin at the inlet of the reactor and to quench the inlets of the following beds.
  • Chamber reactors usually operate at pressure of approximately 3500-5500 kPag (about 500-800 psig) and temperature between 180° to 200 0 C (about 350° - 400 0 F).
  • the conversion, per pass of the unit is determined by the olefin specification in the LPG product stream.
  • Fresh feed LHSV is usually low, approximately 0.4 to 0.8 hr "1 .
  • the cycle length for chamber reactors is typically between 2 to 4 months.
  • the tubular reactor is basically a shell-and-tube heat exchanger in which the polymerization reactions take place in a number of parallel tubes immersed in a cooling medium and filled with the SPA catalyst.
  • Reactor temperature is controlled with the cooling medium, invariably water in commercial units, that is fed on the shell side of the reactor. The heat released from the reactions taking place inside the tubes evaporates the water on the shell side.
  • Temperature profile in a tubular reactor is close to isothermal.
  • Reactor temperature is primarily controlled by means of the shell side water pressure (controls temperature of evaporation) and secondly by the reactor feed temperature.
  • Tubular reactors usually operate at pressure between 5500 and 7500 kPag (800-1100 psig) and temperature of around 200 0 C (about 400 0 F). Conversion per pass is usually high, around 90 to 93% and the overall conversion is around 95 to 97%.
  • the space velocity in tubular reactors is typically high, e.g., 2 to 3.5 hr "1 LHSV. Cycle length in tubular reactors is normally between 2 to 8 weeks.
  • butene and lighter olefins are employed as feeds to polymerization processes as heavier olefins up to about C 10 or C 11 can be directly incorporated into the gasoline.
  • propylene and butylene are satisfactory feedstocks and ethylene may also be included, to produce a copolymer product in the gasoline boiling range.
  • Limited amounts of butadiene may be permissible although this diolefin is undesirable because of its tendency to produce higher molecular weight polymers and to accelerate deposition of coke on the catalyst.
  • the process generally operates under relatively mild conditions, typically between 150° and 200 0 C, usually at the lower end of this range between 150° and 180 0 C, when all butenes are polymerized.
  • the olefin feed together with paraffinic diluent is fed to the reactor after being preheated by exchange with the reaction effluent.
  • the solid phosphoric acid catalyst used is non-corrosive, which permits extensive use of carbon steel throughout the unit.
  • the highest octane product is obtained by using a butene feed, with a product octane rating of [R+Mj/2 of 89 to 91 being typical.
  • product octane is typically about 91 and with propylene as the primary feed component, product octane drops to typically 87.
  • the Mobil Olefins-to-Gasoline [MOG] process employs a proprietary shape selective zeolite catalyst in a fluidized bed reactor to produce high octane motor gasoline by the conversion of reactive olefins such as ethylene and propylene in FCC off-gas; butenes as well as higher olefins may also be included and converted to form a high octane, branched chain gasoline product.
  • the feed is converted over the catalyst into C 5 + components by mechanisms including oligomerization, carbon number redistribution hydrogen transfer, aromatizaiion, alkylation and isomerization.
  • MOG Based on olefins converted, MOG yields 60 to 75 weight percent of high-octane gasoline blend stock with specific qualities of the product depending of the processing severity selected and the character of the feed olefins. Typically, the octane rating for the product is in the range of 88 to 91 [R+M]/2.
  • the zeolite catalyst used in the process is environmentally safe and its attrition rate is low, and as an alternative to disposal, the spent catalyst can be reused in the FCC unit to increase octane quality.
  • the MOG process has, however, the economic disadvantage relative to the SPA process in that new capital investment may be required for the fluidized bed reactor and regenerator used to operate the process. If an existing SPA unit is available in the refinery, it may be difficult to justify replacement of the equipment in spite of the drawbacks of the SPA process, especially in view of current margins on fuel products. Thus, although the MOG process is technically superior, with the fluidized bed operation resolving heat problems and the catalyst presenting no environmental problems, displacement of existing SPA polymerization units has frequently been economically unattractive. What is required, therefore, is an economically attractive alternative to the SPA process for the condensation of light olefins to form motor fuels.
  • the process should be capable of operation in existing refinery equipment, especially as a "drop in” type replacement for the solid phosphoric acid catalyst used in the SPA process so that existing SPA polymerization units can be directly used with the new catalyst.
  • the catalyst should present fewer handling, operational and disposal problems than solid phosphoric acid and, for integration into existing refineries, the product volumes and distributions should be comparable to those of the SPA process.
  • the catalyst used in the present process is a solid, particulate catalyst which is non-corrosive, which is stable in fixed bed operation, which exhibits the capability of cycle durations before regeneration is necessary and which can be readily handled and which can be finally disposed of simply and economically without encountering significant environmental problems. Accordingly, the catalyst used in the present process commends itself as a "drop in" replacement for the solid phosphoric acid catalyst used in the SPA catalytic condensation process for the production of motor fuels.
  • a light olefin stream such as ethylene, propylene, optionally with butylene and possibly other light olefins
  • a catalyst which comprises a member of the MWW family of zeolites, a family which includes zeolites PSH 3, MCM-22, MCM-49, MCM-56, SSZ 25, ERB-I and ITQ-I.
  • polymerized is used here consistent with the petroleum refinery usage although, in fact, the process is one of oligomerization (which term will be used in this specification interchangeably with the conventional term) in which a low molecular weight polymer is the desired product.
  • the process is carried out in a fixed bed of the catalyst with feed dilution, normally a hydrocarbon diluent, or added quench to control the heat release which takes place.
  • feed dilution normally a hydrocarbon diluent
  • the solid catalysts used in the present process exhibit better activity and selectivity than solid phosphoric acid; compared to SPA, MCM-22 itself is three to seven times more active and significantly more stable for the production of motor gasoline by the polymerization of light olefin feeds.
  • the catalytic performance of regenerated MCM-22 catalyst is comparable to that of the fresh MCM-22 catalyst, demonstrating that the catalyst is amenable to conventional oxidative regeneration techniques.
  • the conversion of an SPA process unit to operation with the present molecular sieve based catalysts therefore comprises, in principle, withdrawing the solid phosphoric acid [SPA] catalyst from the unit and loading an olefin condensation catalyst comprising an MWW zeolite material into the reactor of the process unit.
  • the unit may be used for production of the gasoline and, if desired, other liquid hydrocarbon fuels by polymerization of the refinery olefins using the appropriate conditions as described below.
  • Figure 1 shows a process schematic for the olefin polymerization unit for converting light refinery olefins to motor gasoline by the present process.
  • the present process is for the condensation of light cracking olefins to produce motor gasoline and other motor fuels, for example, road diesel blend stock and is intended to provide a replacement for the SPA polymerization process. It provides a catalyst which can be used as a direct replacement for SPA and so enables existing SPA units to be used directly with the new catalyst, so allowing the advantages of the new catalyst and process to be utilized while retaining the economic benefit of existing refinery equipment.
  • the process units used for the operation of the SPA process for the catalytic condensation of light olefins to produce motor fuels are well known. These units typically comprise a feed surge drum to which the olefins and any diluent are supplied, followed by a heat exchanger in which the feed is preheated by exchange with the reactor effluent, after which it is charged to the reactor where the polymerization (condensation) takes place. Control of the heat release in the reactor is accomplished both by feed dilution and by the injection of recycled quench between catalyst beds in the reactor. The reactor effluent, cooled in exchange with the feed, is directed to a flash drum where the flash vapor is condensed and the condensate cooled.
  • Flash drum liquid flows to a stabilizer where the polymer gasoline product at the desired Reid Vapor Pressure [RVP] and light ends are separated.
  • the light ends may be sent to a C 3 -C 4 splitter depending on the refinery needs.
  • SPA units of this kind can be directly converted to use the catalysts of the present process without significant changes since the present catalysts are a straight forward "drop in” replacement for the solid phosphoric acid [SPA] catalyst used in the conventional process technology.
  • the molecular sieve catalysts used in the present process are non-corrosive but possess significant advantages with respect to SPA, in that they are more stable, less subject to break down and are largely unaffected by the amount of water in the feed.
  • the present catalysts are readily regenerable using conventional hydrogen stripping or oxidative regeneration, after which complete catalytic activity is substantially restored. Cycle times before regeneration or reactivation is required may be six months, one year, or even longer, representing a significant improvement over SPA. Since conventional SPA condensation units necessarily include facilities for the discharge and reloading of catalysts as a result of the short life of a catalyst, these units may readily accommodate the present molecular sieve catalysts.
  • the SPA units do not, however, include facilities for in-situ regeneration since the SPA catalyst is used on a once-through basis before it requires disposal.
  • the molecular sieve catalysts used in the present process are fully regenerable and for this purpose, will need to be withdrawn from the reactors for ex-situ regeneration. This will typically be a simple matter to arrange using the spent catalyst discharge equipment of the SPA unit.
  • the SPA charging equipment lends itself directly to the charging of the zeolite catalysts into the reactors.
  • a schematic for a converted olefin condensation unit made by the conversion of an existing SPA unit is shown in simplified from in Figure 1.
  • a light olefin feed typically C 2 , C 3 or C 4 olefins or mixtures of these olefins from an FCC gas plant, is led into the unit through line 10 and combined with recycled hydrocarbon as diluent before passing through heat exchanger 12 in which it picks up heat from the reactor effluent before being brought to reaction temperature in heater 13.
  • the olefin charge plus diluent passes through a guard bed reactor 14a to remove contaminants such as organic nitrogen and sulfur- containing impurities.
  • the guard bed may be operated on the swing cycle with two beds, 14a, 14b, one bed being used on stream for contaminant removal and the other on regeneration in the conventional manner.
  • a three-bed guard bed system may be used with the two beds used in series for contaminant removal and the third bed on regeneration. With a three guard system used to achieve low contaminant levels by the two-stage series sorption, the beds will pass sequentially through a three-step cycle of: regeneration, second bed sorption, first bed sorption.
  • the olefins in the charge stream are polymerized or condensed in reactor 15 to form the desired olefin polymer product during its passage over a sequence of catalyst beds in the reactor. Additional diluent is injected as quench from line 16 between the beds in order to control the exotherm. Effluent passes out of the reactor through heat exchanger 12 and then to flash drum 20 in which the diluent is separated from the olefin polymer product.
  • the diluent which is suitably a light paraffin such as propane, butane and a portion of the polymerization product, is passed to recycle drum 21 and from there by way of recycle pump 23 and line 24 to feed line 10 for feed dilution and to recycle line 16 for injection as interbed quench in reactor 15.
  • the olefin polymer product passes out of flash drum 20 through line 22 to the fractionator 25 to provide the final stabilized gasoline blend component in line 26 with reboil loop 28 providing column heat; light ends including unreacted olefins pass out through line 27 from reflux loop 29.
  • the catalysts used in the present process contain, as their essential catalytic component, a molecular sieve of the MWW type.
  • the MWW family of zeolite materials has achieved recognition as having a characteristic framework structure which presents unique and interesting catalytic properties.
  • the MWW topology consists of two independent pore systems: a sinusoidal ten-member ring [10 MR] two dimensional channel separated from each other by a second, two dimensional pore system comprised of 12 MR super cages connected to each other through 10 MR windows.
  • the crystal system of the MWW framework is hexagonal and the molecules diffuse along the [100] directions in the zeolite, i.e., there is no communication along the c direction between the pores.
  • the crystals are formed of relatively small number of units along the c direction as a result of which, much of the catalytic activity is due to active sites located on the external surface of the crystals in the form of the cup-shaped cavities.
  • the cup-shaped cavities combine together to form a supercage.
  • the MCM-22 family of zeolites has attracted significant scientific attention since its initial announcement by Leonovicz et al.
  • MCM-22 The relationship between the various members of the MCM-22 family have been described in a number of publications.
  • MCM-22 When initially synthesized from a mixture including sources of silica, alumina, sodium, and hexamethylene imine as an organic template, the initial product will be MCM-22 precursor or MCM-56, depending upon the silica: alumina ratio of the initial synthesis mixture.
  • silica:alumina ratios greater than 20 MCM-22 precursor comprising H-bonded vertically aligned layers is produced whereas randomly oriented, non-bonded layers of MC-56 are produced at lower silica: alumina ratios.
  • Both these materials may be converted to a swollen material by the use of a pillaring agent and on calcination, this leads to the laminar, pillared structure of MCM-36.
  • the as-synthesized MCM-22 precursor can be converted directly by calcination to MCM-22 which is identical to calcined MCM-49, an intermediate product obtained by the crystallization of the randomly oriented, as-synthesized MCM-56.
  • the layers are covalently bonded with an interlaminar spacing slightly greater than that found in the calcined MCM- 22/MCM 49 materials.
  • the unsynthesized MCM-56 may be calcined itself to form calcined MCM 56 which is distinct from calcined MCM-22/MCM-49 in having a randomly oriented rather than a laminar structure.
  • MCM-22 is described in U.S. Patent No. 4,954,325 as well as in U.S. 5,250,777; 5,284,643 and 5,382,742.
  • MCM-49 is described in U.S. 5,236,575; MCM-36 in U.S. 5,229,341 and MCM-56 in U.S. 5,362,697.
  • the preferred zeolitic material for use in the catalyst of the present process is MCM-22 although zeolite MCM-49 may be found to have certain advantages relative to MCM-22. It has been found that the MCM-22 may be either used fresh, that is, not having been previously used as a catalyst or alternatively, regenerated MCM-22 may be used. Regenerated MCM-22 may be used after it has been used in any of the catalytic processes for which it is suitable, including the present process in which the catalyst has shown itself remain active after even multiple regenerations.
  • MCM-22 catalyst which has previously been used for the production of aromatics such as ethyl- benzene or cumene, normally using reactions such as alkyaltion and transalkyla- tion.
  • the cumene production (alkylation) process is described in U.S. Patent No. 4,992,606 (Kushnerick et al).
  • Ethylbenzene production processes are described in U.S. Pat. Nos. 3,751,504 (Keown); 4,547,605 (Kresge); and 4,016,218 (Haag); U.S. Pat. Nos.
  • MCM-22 catalysts may be regenerated after catalytic use in these processes and other aromatics production processes by conventional air oxidation techniques similar to those used with other zeolite catalysts. Conventional air oxidation techniques are also suitable when regenerating the catalysts after use in the present process.
  • the catalysts for use in the present process will often contain a matrix material or binder in order to give adequate strength to the catalyst as well as to provide the desired porosity characteristics in the catalyst.
  • High activity catalysts may, however, be formulated in the binder-free form by the use of suitable extrusion techniques, for example, as described in U.S. 4,908,120.
  • matrix materials suitably include alumina, silica, silica alumina, titania, zirconia, and other inorganic oxide materials commonly used in the formulation of molecular sieve catalysts.
  • the level of MCM-22 in a finished matrixed catalyst will be typically from 20 to 70% by weight, and in most cases from 25 to 65% by weight.
  • the active ingredient will typically be mulled with the matrix material using an aqueous suspension of the catalyst and matrix, after which the active component and the matrix are extruded into the desired shape, for example, cylinders, hollow cylinders, trilobe, quadlobe, etc.
  • a binder material such as clay may be added during the mulling in order to facilitate extrusion, increase the strength of the final catalytic material and to confer other desirable solid state properties. The amount of clay will not normally exceed 10% by weight of the total finished catalyst.
  • Self-bound catalysts (alternatively referred to as unbound or binder- free catalysts), that is, catalysts which do not contain a separately added matrix or binder material, are useful and may be produced by the extrusion method described in U.S. Pat. No. 4,582,815, to which reference is made for a description of the method and of the extruded products obtained by its use.
  • the method described there enables extrudates having high constraining strength to be produced on conventional extrusion equipment and accordingly, the method is eminently suitable for producing the high activity self-bound catalysts.
  • the catalysts are produced by mulling the zeolite, as described in U.S. Pat. No.
  • the self-bound catalysts can be characterized as particulate catalysts in the form, for instance, of extrudates or pellets, containing at least 90 wt. pet., usually at least 95 wt. pet., of the active zeolite component with no separately added binder material e.g. alumina, silica- alumina, silica, titania, zirconia etc.
  • Extrudates may be in the conventional shapes such as cylinders, hollow cylinders, trilobe, quadlobe, flat platelets etc.
  • the catalyst used in the guard bed will normally be the same catalyst used in the alkylation reactor as a matter of operating convenience but this is not required: if desired another catalyst or sorbent to remove contaminants from the feed may used, typically a cheaper guard bed sorbent, e.g a used catalyst from another process or alumina.
  • the objective of the guard bed is to remove the contaminants from the feed before the feed comes to the reaction catalyst and provided that this is achieved, there is wide variety of choice as to guard bed catalysts and conditions useful to this end.
  • the volume of the guard bed will normally not exceed about 20% of the total catalyst bed volume of the unit.
  • the light olefins used as the feed for the present process are normally obtained by the catalytic cracking of petroleum feedstocks to produce gasoline as the major product.
  • the catalytic cracking process usually in the form of fluid catalytic cracking (FCC) is well established and, as is well known, produces large quantities of light olefins as well as olefinic gasolines and by-products such as cycle oil which are themselves subject to further refining operations.
  • FCC fluid catalytic cracking
  • the olefins which are primarily useful in the present process are the lighter olefins from ethylene up to butene; although the heavier olefins may also be included in the processing, they can generally be incorporated directly into the gasoline product where they provide a valuable contribution to octane.
  • the present process is highly advantageous in that it will operate readily not only with butene and propylene but also with ethylene and thus provides a valuable route for the conversion of this cracking by-product to the desired gasoline product. For this reason as well as their ready availability in large quantities in a refinery, mixed olefin streams such a FCC Off-Gas streams (typically containing ethylene, propylene and butenes) may be used.
  • Conversion of the C 3 and C 4 olefin fractions from the cracking process provides a direct route to the branch chain C 6 , C 7 and C ⁇ products which are so highly desirable in gasoline from the view point of boiling point and octane.
  • the mixed olefin streams may be obtained from other process units including cokers, visbreakers and thermal crackers.
  • the presence of diolefins which may be found in some of these streams is not disadvantageous since catalysis on the MWW family of zeolites takes place on surface sites rather than in the interior pore structure as with more conventional zeolites so that plugging of the pores is less problematic catalytically.
  • the catalysts used in the present process are robust they do have sensitivity to certain contaminants (the conventional zeolite deactivators), especially organic compounds with basic nitrogen as well as sulfur-containing organics. It is therefore preferred to remove these materials prior to entering the unit if extended catalyst life is to be expected. Scrubbing with contaminant removal washes such as caustic, MEA or other amines or aqueous wash liquids will normally reduce the sulfur level to an acceptable level of about 10-20 ppmw and the nitrogen to trace levels at which it can be readily tolerated.
  • One attractive feature about the present process is that although activity benefits are achieved by the use of low or very low water levels in.
  • the zeolite catalyst does not require the presence of water in order to maintain activity and therefore the feed may be dried before entering the unit, for example, to below 200 ppmw water or lower, e.g. below 50 or even 20 ppmw.
  • the water content typically needs to be held between 300 to 500 ppmw at conventional operating temperatures for adequate activity while, at the same time, retaining catalyst integrity.
  • the present zeolite catalysts may readily tolerate higher levels of water up to about 1,000 ppmw water although levels above about 800 ppmw may reduce activity, depending on temperature.
  • the olefin feed may contain from 300 or 500 to 1,000 ppmw water, although 300-800 ppmw should be regarded as a workable range for activity with existing feed treatment equipment. As noted, however, activity benefits are secured with markedly lower feed water levels and these benefits may justify feed pre-treatment to operate at lower water contents.
  • the use of the guard bed is particularly desirable in the operation of the present process since the refinery feeds customarily routed to polymerization units (as distinct from petrochemical unit feeds which are invariably high purity feeds for which no guard bed is required) may have a contaminant content, especially of polar catalyst poisons, such as the polar organic nitrogen and organic sulfur compounds, which is too high for extended catalyst life.
  • polar catalyst poisons such as the polar organic nitrogen and organic sulfur compounds
  • the present process is notable for its capability of being operated at low temperatures and under moderate pressures.
  • the temperature will be from about 120° to 250 0 C (about 250° to 480 0 F) and in most cases between 150° and 250 0 C (about 300°-480°C).
  • Temperatures of 170° to 205°C (about 340° to 400 0 F) will normally be found optimum for feeds comprising butene while higher temperatures will normally be appropriate for feeds with significant amounts of propene.
  • Pressures may be those appropriate to the type of unit from which the conversion was made, so that pressures up to about 7500 kPag (about 1100 psig) will be typical but normally lower pressures will be sufficient, for example, below about 7,000 Kpag (about 1,000 psig) and lower pressure operation may be readily utilized, e.g. up to 3500 kPag (about 500 psig).
  • Ethylene again, will require higher temperature operation to ensure that the products remain in the gasoline boiling range.
  • Space velocity may be quite high, for example, up to 50 WHSV (hr "1 ) but more usually in the range of 5 to 30 WHSV.
  • a high quality product is obtained from the polymerization step, suitable for direct blending into the refinery gasoline pool after fractionation as described above. With clean feeds, the product is correspondingly low in contaminants.
  • the product is high in octane rating with RON values of 95 being regularly obtained and values of over 97 being typical; MON is normally over 80 and typically over 82 so that (RON+MON)/2 values of at least 89 or 90 are achievable with mixed propylene/butene feeds.
  • RON+MON RON+MON
  • the linear octenes are routinely lower than with the SPA product, typically being below 0.06 wt. pet. of all octenes except at the highest conversions and even then, the linears are no higher than those resulting from SPA catalyst.
  • the higher octane di-branched octenes are noteworthy in consistently being above 90 wt. pet. of all octenes, again except at the highest conversions but in all cases, higher than those from SPA; usually, the di-branched octenes will be at least 92 wt. pet of all octenes and in favorable cases at least 93 wt. pet.
  • the levels of tri-branched octenes are typically lower than those resulting from the SPA process especially at high conversions, with less than 4 wt. pet being typically except at the highest conversions when 5 or 6 wt. pet. of all octenes may be achieved, approximately half that resulting from SPA processing.
  • high levels of di-branched C8 hydrocarbons may be found, with at least 85 weight percent of the octene components being di- branched C8 hydrocarbons, e.g. 88 to 96 weight percent di-branched C8 hydrocarbons.
  • the isoparaffin-olefin alkylation reaction is not significant but at higher conversions above about 75% (olefin conversion), e.g. at conversion levels of 80% or more (olefin conversion), particularly at 90% or higher, this reaction will increase markedly with the production of high octane gasoline components.
  • Example 1 2-Butene Oligomerization with Solid Phosphoric Acid
  • SPA solid phosphoric acid
  • a commercial solid phosphoric acid (SPA) catalyst was sized to 14-24 mesh in a glove box. In a glove bag, one gram of this sized catalyst was diluted with sand to 3 cc and charged to an isothermal, down-flow, 9 mm (outside diameter) fixed-bed reactor. The catalyst was dried at 150 0 C and atmospheric pressure with 100 cc/min flowing N 2 for 2 hours. The N 2 was turned off and reactor pressure was set to 5270 kPaa (750 psig) by a Grove loader.
  • SPA solid phosphoric acid
  • a 2-butene feed (containing 57.1% cis-butene, 37.8% trans-butene, 2.5% n-butane, 0.8% isobutene and 1-butene, 1.8% others) was introduced into the reactor at 60 cc/hr until desire reactor pressure of 5270 kPaa (750 psig) was reached.
  • the reactor temperature was then ramped at 2°C per minute to 170 0 C. During the temperature ramp, the feed flow was reduced to a desired level and kept at this level for 12 hours before data collection. Liquid products were collected at 50%, 70%, then 90% conversion (not necessary in this order) in a cold-trap and analyzed off-line.
  • Product carbon number distribution was determined with a HP-5890 GC equipped with a 60 meter DB-I column (0.25 mm id and 1000 nm film thickness).
  • Product branching was determined with an H 2 -GC using a HP-5890 GC equipped with (a) a 100 meter DB-I column (0.25 mm id and 500 nm film thickness); (b) hydrogen as the carrier gas; and (c) 0.1 g of 0.5% Pt/alumina catalyst in the GC insert for in-situ hydrogenation.
  • Both GCs use the same temperature program: 2 min at -20 0 C, 8°C/min to 275°C, hold at 275°C for 35 min.
  • the catalyst was a binder-free, 1.6 mm quadralobe extrudate containing 100% MCM-22. A 0.10 gram sample of this catalyst, chopped to 3mm length, was tested for 2-butene oligomerization using the same procedure described in Example 1. Representative data are shown in Tables 3-5.
  • the catalyst was a 1.6 mm cylindrical extrudate containing 65% MCM- 22 and 35% alumina binder. A 0.20 gram of this catalyst, chopped to 1.6mm length, was tested for 2-butene oligomerization using the same procedure described in Example 1. Representative data are shown in Tables 3-5.
  • the sample was treated in flowing air at 700 v/v/minute, 455C (85O 0 F) and 60 torr partial pressure of water for 1 hour. The treatment was repeated 4 additional times on the same sample, with the intention of simulating 5 additional regenerations of the already commercially regenerated MCM-22. A 0.20 gram of this multiple regenerated catalyst, chopped to 1.6 mm length, was evaluated for 2-butene oligomerization using the same procedure described in Example 1. Representative data are shown in Tables 3-5.
  • Tables 3-5 compare catalyst performance at 50%, 70%, and 90% conversion of 2-butene.
  • Table 4 further compares catalysts activity and deactivation rate. Relative activity of each catalyst is determined by measuring the first- order rate constant for 2-butene oligomerization at 170 0 C relative to that of SPA catalyst. Deactivation rate is given as conversion drop observed per day per WHSV.
  • a C4 feed comprising isomeric butenes and isobutane was reacted over a regenerated MCM-22 catalyst in a laboratory scale reactor unit at 3790 kPag (550 psig) at temperatures from 124° to 236°C (256 to 456 0 F), using one, two or three reactors in sequence under isothermal (I) or adiabatic (A) conditions.
  • the feed composition was as shown in Table 8 below.
  • the three reactors contained, respectively, 4.84 g, 17.74 g. and 27.42 g of the catalyst.
  • Example 10 Comparison with SPA Polymerization Product
  • a refinery FCC gas stream containing olefins up to C 4 was polymerized over an SPA catalyst to produce a gasoline boiling range product which was then hydrotreated at 65°C (150 0 F) and 93°C (200 0 F) over a Pt/Pd hydrotreating catalyst at 2410 kPag (3560 psig), 2 hr "1 WHSV, 5:1 hydrogen/liquid ratio, to saturate olefins.
  • the hydrotreated product was then analyzed for composition and the octane ratings (RON, MON) were determined by engine test.
  • the same olefinic stream was also polymerized over an MCM-22 catalyst in a unit of the same configuration and the same determinations made.
  • the simulated distillation data (ASTM D 2887) are given in Table 10 below for the polymerized products and the hydrotreated (93°C) products.
  • the results of the octane testing are shown in Table 11 below.
  • the hydrotreating technique was used to demonstrate more clearly the extent of branching in the two polymerization products: hydrotreatment saturates the olefins so that their contribution to product octane is eliminated with the differences remaining then being attributable to the branching of the paraffin chains, the product being essentially free of aromatics.
  • a feed containing iso-butane and mixed butene isomers was passed into a three-reactor unit which could be operated under isothermal or adiabatic conditions containing a supported MCM-22 zeolite catalyst.
  • the feed composition is given in Table 12 below.
  • Reaction temperatures first reactor inlet
  • the product compositions are given in Table 13 below together with the conditions for present in the unit.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne la transformation d'unités de traitement d'oligomérisation d'oléfine utilisant de l'acide phosphorique solide afin que celles-ci puissent être utilisées avec un catalyseur solide plus favorable pour l'environnement. Lesdites unités, dans lesquelles une charge d'oléfine légère est oligomérisée pour former un produit d'hydrocarbure à limites d'ébullition d'essence, sont transformées afin de pouvoir fonctionner avec un catalyseur d'oligomérisation d'oléfine à tamis moléculaire comprenant une matière de zéolithe MWW. Les zéolithes, outre qu'elles sont à l'utilisation plus favorables pour l'environnement, offrent des avantages quant à la durée de vie du catalyseur, la sélectivité et la qualité du produit. Après chargement du catalyseur, on actionne l'unité transformée comme une unité à lit fixe en transférant la charge oléfinique en C2-C4 vers un lit fixe du catalyseur de condensation à zéolithe MWW, généralement à une température comprise entre 150 et 250 °C, à une pression ne dépassant pas 7000 kPag, habituellement inférieure à 4000 kPag, et à une vitesse spatiale pouvant atteindre 30 WHSV. Le produit à limites d'ébullition d'essence est caractérisé par un taux élevé d'octènes à chaîne ramifiée, qui assure une qualité d'octane supérieure.
EP06736479A 2005-02-28 2006-02-28 Production d'essence par polymerisation d'olefine Withdrawn EP1856009A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US65695405P 2005-02-28 2005-02-28
US11/362,257 US20060194999A1 (en) 2005-02-28 2006-02-27 Gasoline production by olefin polymerization
PCT/US2006/007168 WO2006094006A2 (fr) 2005-02-28 2006-02-28 Production d'essence par polymerisation d'olefine

Publications (2)

Publication Number Publication Date
EP1856009A2 true EP1856009A2 (fr) 2007-11-21
EP1856009A4 EP1856009A4 (fr) 2012-01-04

Family

ID=36941751

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06736479A Withdrawn EP1856009A4 (fr) 2005-02-28 2006-02-28 Production d'essence par polymerisation d'olefine

Country Status (6)

Country Link
EP (1) EP1856009A4 (fr)
JP (1) JP2008531818A (fr)
BR (1) BRPI0609156A2 (fr)
CA (1) CA2599492A1 (fr)
RU (1) RU2007134098A (fr)
WO (1) WO2006094006A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0713674A2 (pt) 2006-07-28 2012-10-23 Exxonmobil Chem Patents Inc formulações farmarcêuticas e composições de um antagonista seletivo cxcr2 ou cxcr1 e métodos para o uso do mesmo visando o tratamento de distúrbios inflamatórios
BRPI0714316B1 (pt) * 2006-07-28 2018-05-15 Exxonmobil Chemical Patents Inc Composição de peneira molecular da família de mcm-22, seu método de preparação, e uso para conversões de hidrocarboneto
US7959899B2 (en) 2006-07-28 2011-06-14 Exxonmobil Chemical Patents Inc. Molecular sieve composition (EMM-10-P), its method of making, and use for hydrocarbon conversions
EP2098498A1 (fr) * 2008-03-04 2009-09-09 ExxonMobil Chemical Patents Inc. Oligomérisation sélective d'isobutylène

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960978A (en) * 1974-09-05 1976-06-01 Mobil Oil Corporation Converting low molecular weight olefins over zeolites
EP0159848A1 (fr) * 1984-04-09 1985-10-30 Mobil Oil Corporation Procédé pour la fabrication d'hydrocarbures lubrifiants à partir d'oléfines inférieures
US4919896A (en) * 1987-12-28 1990-04-24 Mobil Oil Corporation Multistage catalytic reactor system for production of heavy hydrocarbons
WO1995022516A1 (fr) * 1994-02-22 1995-08-24 Exxon Chemical Patents Inc. Oligomerisation et catalyseurs utilises a cette fin
WO2005118512A1 (fr) * 2004-06-01 2005-12-15 Exxonmobil Chemical Patents Inc. Procede d'oligomerisation d'olefines

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4956514A (en) * 1988-10-06 1990-09-11 Mobil Oil Corp. Process for converting olefins to higher hydrocarbons
DE69312268T2 (de) * 1992-01-30 1997-12-18 Exxon Chemical Patents Inc Alkenoligomerisierung
US6399843B1 (en) * 2000-10-12 2002-06-04 Uop Llc Upflow oligomerization reaction process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960978A (en) * 1974-09-05 1976-06-01 Mobil Oil Corporation Converting low molecular weight olefins over zeolites
EP0159848A1 (fr) * 1984-04-09 1985-10-30 Mobil Oil Corporation Procédé pour la fabrication d'hydrocarbures lubrifiants à partir d'oléfines inférieures
US4919896A (en) * 1987-12-28 1990-04-24 Mobil Oil Corporation Multistage catalytic reactor system for production of heavy hydrocarbons
WO1995022516A1 (fr) * 1994-02-22 1995-08-24 Exxon Chemical Patents Inc. Oligomerisation et catalyseurs utilises a cette fin
WO2005118512A1 (fr) * 2004-06-01 2005-12-15 Exxonmobil Chemical Patents Inc. Procede d'oligomerisation d'olefines

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2006094006A2 *

Also Published As

Publication number Publication date
EP1856009A4 (fr) 2012-01-04
WO2006094006A2 (fr) 2006-09-08
JP2008531818A (ja) 2008-08-14
WO2006094006A3 (fr) 2006-12-21
RU2007134098A (ru) 2009-04-10
BRPI0609156A2 (pt) 2016-08-23
CA2599492A1 (fr) 2006-09-08

Similar Documents

Publication Publication Date Title
US20060194999A1 (en) Gasoline production by olefin polymerization
US7525002B2 (en) Gasoline production by olefin polymerization with aromatics alkylation
CA2599347C (fr) Procede d'alkylation d'aromatiques en phase liquide
RU2515525C2 (ru) Способ получения высокооктанового бензина с пониженным содержанием бензола путем алкилирования бензола при высокой конверсии бензола
US20060194998A1 (en) Process for making high octane gasoline with reduced benzene content
US20080029437A1 (en) Olefin upgrading process with guard bed regeneration
CA2599351C (fr) Fabrication d'essence par polymerisation d'olefine au moyen d'alkylation d'hydrocarbures aromatiques
EP2673245B1 (fr) Procédé de réduction de la teneur en benzène de l'essence par alkylation du benzène à l'aide d'une oléfine inférieure en présence d'un diluant paraffinique
WO2006094006A2 (fr) Production d'essence par polymerisation d'olefine
CA2599503C (fr) Procede d'alkylation d'hydrocarbures aromatiques en phase vapeur
US20070185359A1 (en) Gasoline production by olefin polymerization
US20080029435A1 (en) Rejuvenation process for olefin polymerization and alkylation catalyst
US7498474B2 (en) Vapor phase aromatics alkylation process

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070913

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE FR GB IT NL

RIN1 Information on inventor provided before grant (corrected)

Inventor name: CHENG, JANE, CHI-YA

Inventor name: DANDEKAR, AJIT, BHASKAR

Inventor name: CLARK, MICHAEL, CHRISTOPHER

Inventor name: MATHYS, GEORGE, M., K.

Inventor name: BROWN, STEPHEN, H.

Inventor name: ELKS, JEFFREY, THOMAS

Inventor name: UMANSKY, BENJAMIN, SANTIAGO

DAX Request for extension of the european patent (deleted)
RBV Designated contracting states (corrected)

Designated state(s): BE DE FR GB IT NL

A4 Supplementary search report drawn up and despatched

Effective date: 20111205

RIC1 Information provided on ipc code assigned before grant

Ipc: C07C 2/02 20060101AFI20111129BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20120703