WO1993014048A1 - Procede de transformation d'olefines - Google Patents

Procede de transformation d'olefines Download PDF

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Publication number
WO1993014048A1
WO1993014048A1 PCT/US1992/000370 US9200370W WO9314048A1 WO 1993014048 A1 WO1993014048 A1 WO 1993014048A1 US 9200370 W US9200370 W US 9200370W WO 9314048 A1 WO9314048 A1 WO 9314048A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
mcm
olefin
silica
conversion
Prior art date
Application number
PCT/US1992/000370
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English (en)
Inventor
Kathleen Marie Keville
Albin Huss, Jr.
Altaf Husain
Kenneth Joseph Del Rossi
Robert Glenn Bundens
Cynthia Ting-Wah Chu
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 AU12643/92A priority Critical patent/AU1264392A/en
Priority to PCT/US1992/000370 priority patent/WO1993014048A1/fr
Publication of WO1993014048A1 publication Critical patent/WO1993014048A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. 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

Definitions

  • This invention relates to a process for converting olefins, e.g., C_-C 16 linear mono-alkenes to isoalkene hydrocarbon products, especially C . -C-. tertiary alkenes.
  • olefins e.g., C_-C 16 linear mono-alkenes
  • isoalkene hydrocarbon products especially C . -C-. tertiary alkenes.
  • shape selective zeolites such as ZSM-5 to convert propylene to C. + C 5 olefins has been recognized previously, see for example EP-A-26041.
  • MCM-22 a recently discovered zeolite, designated MCM-22, is an effective catalyst for converting lower olefins to isoalkenes at high selectivity.
  • the invention resides in a process for converting a lower olefin feedstock to an iso-alkene rich product by contacting the feedstock with a catalyst comprising a synthetic porous crystalline zeolite which, in its calcined form, has an x-ray diffraction pattern including the values listed in Table I below.
  • the conversion is olefin or double bond isomerization, in which a double bond possessed by a olefinic molecule is moved from an alpha position to an internal position within the molecule.
  • the feed preferably contains n-butene and conversion is preferably effected at a temperature of 0 to 650°C, more preferably 150 to 250°C, a pressure of 100 to 14000 kPa (1 to 2000psia) and a weight hourly space velocity of 0.1 to 500.
  • the conversion involves olefin interconversion or restructuring in which a C---C.,--, preferably a C -C,, olefin feed is converted to a product containing at least 6 wt% tertiary C and C 5 olefins.
  • This process involves a combination of operations including cracking, polymerization or dimerization and isomerization so as to provide a product rich in tertiary olefins having a carbon number less than twice that of the starting olefin.
  • Interconversion conditions preferably include a temperature of 250 to 700°c, preferably 300 to 450°C, a pressure of 100 to 1500 kpa, preferably 150 to 500 kpa and an LHSV of 0.1 to 100, preferably 0.2 to 20.
  • the zeolite catalyst (described in detail below) has an acid activity (alpha value) of 1 to 150, more preferably less than 50, and most preferably less than 10.
  • acid activity alpha value
  • Many olefins are suitable for use as the feedstock in the interconversion process of the second embodiment r especially linear monoalkenes having 3 to 16 carbon atoms.
  • Suitable olefinic feedstocks can be obtained from a variety of sources including fossil fuel processing streams such as gas separation units, the cracking of C_ hydrocarbons, coal by-products, and various synthetic fuel processing streams. The cracking of ethane and the conversion of the effluent is disclosed in U.S. Patent No.
  • MCM-22 has an X-ray diffraction pattern in its calcined form including the lines listed in Table II below:
  • the calcined form of MCM-22 may have an X-ray diffraction pattern including the lines listed in Table III below:
  • MCM-22 has in its calcined form by an X-ray diffraction pattern including the lines listed in Table IV below:
  • zeolite MCM-22 has a formula, on an anhydrous basis and in terms of moles of oxides per n moles of Y0- > ., as follows:
  • Zeolite MCM-22 is thermally stable and exhibits
  • MCM-22 is synthesized nearly free of Na cations. It can, therefore, be used as an olefin conversion catalyst with acid activity without an exchange step.
  • the original sodium cations of the as-synthesized material can be replaced in accordance with techniques well known in the art, at least in part, by ion exchange with other cations.
  • Preferred replacing cations include metal ions, hydrogen ions, hydrogen precursor, e.g., ammonium, ions and mixtures thereof.
  • Particularly preferred cations are those which tailor the activity of the catalyst for olefin interconversion. These include hydrogen, rare earth metals and metals of Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the Periodic Table of the Elements.
  • the zeolite MCM-22 olefin conversion catalyst herein can also be used in intimate combination with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed.
  • a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed.
  • a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed.
  • Such component can be introduced in the catalyst composition by way of cocrystall
  • Such component can be impregnated in, or on, the zeolite such as, for example, by, in the case of platinum, treating the zeolite with a solution containing a platinum metal-containing ion.
  • suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex.
  • Zeolite MCM-22 can be prepared from a reaction mixture containing sources of alkali or alkaline earth metal (M) , e.g., sodium or potassium, cation, an oxide of trivalent element X, e.g, aluminum, an oxide of tetravalent element Y, e.g. , silicon, an organic (R) directing agent, preferably hexamethylene i ine, and water, said reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges:
  • M alkali or alkaline earth metal
  • R organic
  • the YO- reactant contains a substantial amount of solid Y0 2 , e.g., at least about 30 wt.% solid YO..
  • Y0 2 is silica
  • the use of a silica source containing at least about 30 wt.% solid silica e.g., Ultrasil (a precipitated, spray dried silica containing about 90 wt.% silica) or HiSil (a precipitated hydrated SiO_ containing about 87 wt.% silica, about 6 wt.% free H-0 and about 4.5 wt.% bound H O of hydration and having a particle size of about 0.02 micron) favors crystal formation from the above mixture.
  • the Y0 2 e.g., silica
  • the Y0 2 contains at least about 30 wt.% solid Y0_, e.g., silica, and more preferably at least about 40 wt.% solid YO,, e.g., silica.
  • Crystallization of the MCM-22 crystalline material can be carried out at either static or stirred conditions in a suitable reactor vessel such as, e.g., polypropylene jars or teflon-lined or stainless steel autoclaves. Crystallization is preferably effected at a temperature of 80 ⁇ C to 225 ⁇ C for a time of 25 hours to 60 days. Thereafter, the crystals are separated from the liquid and recovered.
  • a suitable reactor vessel such as, e.g., polypropylene jars or teflon-lined or stainless steel autoclaves. Crystallization is preferably effected at a temperature of 80 ⁇ C to 225 ⁇ C for a time of 25 hours to 60 days. Thereafter, the crystals are separated from the liquid and recovered.
  • Synthesis of the MCM-22 crystals is facilitated by the presence of at least about 0.01 percent, preferably about 0.10 percent and still more preferably about 1 percent, seed crystals (based on total weight) of the crystalline product.
  • MCM-22 crystalline material may be desirable to incorporate with another material which is resistant to the temperatures and other conditions employed in the olefin conversion process of this invention.
  • Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • Use of a material in conjunction with zeolite MCM-22, i.e., combined therewith or present during its synthesis, which itself is catalytically active may change the conversion and/or selectivity of the catalyst.
  • Inactive materials suitably serve as diluents to control the amount of conversion so that the higher value olefin products can be obtained economically without employing other means for controlling the rate of reaction.
  • These materials may be incorporated into naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the catalyst.
  • Said materials, i.e., clays, oxides, etc. function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in commercial use, it is desirable to prevent the catalyst from breaking down into powder-like materials.
  • These clay binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
  • Naturally occurring clays which can be composited with MCM-22 crystals include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite. dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Binders useful for compositing with zeolite MCM-22 also include inorganic oxides, notably alumina.
  • the MCM-22 crystals can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia.
  • a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia.
  • the relative proportions of finely divided crystalline material and inorganic oxide matrix vary widely, with the crystal content ranging from 1 to 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range 2 to 80 weight percent of the composite.
  • the stability of the catalyst of this invention may be increased by steaming.
  • 4,663,492; 4,594,146; 4,522,929; and 4,429,176 describe conditions for the steam stabilization of zeolite catalysts which can be utilized to steam-stabilize the catalyst for use herein.
  • the steam stabilization conditions include contacting the catalyst with, e.g.,
  • the catalyst can be made to undergo steaming with 75-100% steam at 315°-500°C and atmospheric pressure for 2-25 hours.
  • Figures 1 and 2 are graphs comparing the butene-2 yield and C g + yield respectively for MCM-22 and a conventional silica-alumina catalyst in the isomerization of butene-1;
  • Figures 3 to 6 are graphs comparing the properties of MCM-22 and [B]MCM-22 in the interconversion of propylene.
  • a weighed sample of the calcined absorbent was contacted with the desired pure absorbate vapor in an adsorption chamber, evacuated to less than 1 mm Hg and contacted with 12 Torr of water vapor or 40 Torr of n-hexane or 40 Torr of cyclohexane vapor, pressures less than the vapor-liquid equilibrium pressure of the respective adsorbate at 90°C.
  • the pressure was kept constant (within about ⁇ 0.5 mm Hg) by addition of adsorbate vapor controlled by a manostat during the adsorption period, which did not exceed about 8 hours.
  • the decrease in pressure caused the manostat to open a valve which admitted more adsorbate vapor to the chamber to restore the above control pressures. Sorption was complete when the pressure change was not sufficient to activate the manostat.
  • the increase in weight was calculated as the adsorption capacity of the sample in g/100 g of calcined adsorbant.
  • the Alpha Test is described in U.S. Patent
  • the chemical composition of the uncalcined material was determined to be as follows: Component wt.%
  • H-MCM-22 prepared according to the method outlined in Example 1 was compared with a commercial silica-alumina catalyst, Sorbead W (Kali-Chemie) , for olefin isomerization.
  • Sorbead W Kali-Chemie
  • the catalyst was sized to 14/24 mesh and 10 cc were loaded into a 1/2" stainless steel fixed bed micro-unit.
  • the catalyst bed was heated to 430 ⁇ C (800°F) with 100 cc/min of dry nitrogen flowing through the unit.
  • the catalyst bed was held at 430°C (800°F) for one hour before cooling to 320°C (600°F).
  • the unit was pressurized to 450 kPa (50 psig) , and a pure 1-butene feed (Matheson) was admitted at 1 gram/gram catalyst/hr.
  • the nitrogen flow was adjusted to give l/l mol/mol N-/HC.
  • the temperature of the reactor was lowered from 320°C (600°F), initially, to a final temperature of 150°C (300°F) in 55°C (100°F) increments.
  • the total effluent from the reactor at each temperature was anlyzed with an on-line gas chromatograph equipped with a 30 meter megabore DB-1 column.
  • H-MCM-22 can give near-equilibrium amounts of isomerized product from olefinic feeds, and can be more selective than a commercial silica-alumina catalyst, Sorbead W, for olefin isomerization (less C-.+ product) .
  • Another zeolite MCM-22 sample was prepared by adding 4.49 parts quantity of hexamethyleneimine to a mixture containing 1.00 part sodium aluminate, 1.00 part 50% NaOH, 8.54 parts Ultrasil VN3 and 44.19 parts deionized H-,0.
  • the reaction mixture was heated to 143°C (290°F) and stirred in an autoclave at that temperature for crystallization. After full crystallinity was achieved, the majority of the hexamethyleneimine was removed from the autoclave by controlled distillation and the zeolite crystals separated from the remaining liquid by filtration, washed with deionized H.,0 and dried.
  • the zeolite was then calcined in nitrogen at 540°C, exchanged with an aqueous solution of ammonium nitrate and calcined in air at 540°C.
  • the zeolite was tabletted, crushed and sized to 30/40 mesh.
  • the MCM-22 catalyst had the following properties: Surface Area (BET) , m 2 /g 503 Si0 2 / l 2 0 3 (molar) Na, ppm Alpha
  • EXAMPLE 4 This example illustrates the conversion of propylene to an isoalkene-rich product containing isobutene, isoamylenes, and C6+ gasoline employing zeolite MCM-22 prepared in Example 3 as catalyst, and compared with prior art amorphous silica alumina and ZSM-5 catalysts.
  • the conditions of the MCM-22 conversion reaction were 400-410°C, 210 kPa and an WHSV of 10 hr " ( based on active catalyst solids) .
  • the experiments were carried out in small tubular fixed bed reactor using chemically pure propene (propylene, C ⁇ ) feed. In the standard procedure, the catalyst was charged to the reactor and the reactor heated to 230°c (450 ⁇ F) in a nitrogen stream. Nitrogen was slowly replaced by propylene at 10 WHSV and 210 kPa.
  • MCM-22 gives excellent propylene conversion and good selectivity to the desirable isobutylene and isoamylenes.
  • Table VII the performance of MCM-22 is compared with ZSM-5 and alumina-bound amorphous silica/alumina catalyst.
  • MCM-22 is far superior to the amorphous catalyst, both in terms of activity and isobutylene and isoamylene yields. Its performance is comparable with that of ZSM-5, though it ages more rapidly than the latter. However, the effects of catalyst aging may be minimized if the process is run in a fluidized bed mode with continuous regeneration.
  • This example illustrates preparation of the zeolite MCM-22 in which X of the general formula, supra. is boron. Boric acid, 2.2 parts, was added to a solution of 1 part of 50% NaOH solution and 73.9 parts H 2 0. To this solution was added 15.3 parts of HiSil silica followed by 6.7 parts of hexamethyleneimine. The reaction mixture was crystallized in a stainless steel reactor, with agitation, at 150°C (300°F) for 72 hours. The crystalline product was filtered, washed with water and dried at 120°C.
  • the as-synthesized material had a Si0 2 /Al 2 0 ratio of 400 and a Si0 2 /B 2 0 3 ratio of 32.4.
  • the as-synthesized material was precalcined for six hours in N 2 at 480°C (900°F) .
  • the final material had an alpha value acid activity of 2, a surface area of 370 m 2/g, and contained 220 ppm

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Procédé de transformation d'oléfines légères en produits hydrocarbures riches en isoalkène tels que de l'isobutène et des isoamylènes, selon lequel on utilise un catalyseur zéolithique appelé MCM-22.
PCT/US1992/000370 1992-01-16 1992-01-16 Procede de transformation d'olefines WO1993014048A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU12643/92A AU1264392A (en) 1992-01-16 1992-01-16 Olefin conversion process
PCT/US1992/000370 WO1993014048A1 (fr) 1992-01-16 1992-01-16 Procede de transformation d'olefines

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PCT/US1992/000370 WO1993014048A1 (fr) 1992-01-16 1992-01-16 Procede de transformation d'olefines

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WO1993014048A1 true WO1993014048A1 (fr) 1993-07-22

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Citations (1)

* 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

Patent Citations (1)

* 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

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