WO1989010190A1 - Catalyseur de transformation d'olefines et de paraffines - Google Patents

Catalyseur de transformation d'olefines et de paraffines Download PDF

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Publication number
WO1989010190A1
WO1989010190A1 PCT/AU1989/000173 AU8900173W WO8910190A1 WO 1989010190 A1 WO1989010190 A1 WO 1989010190A1 AU 8900173 W AU8900173 W AU 8900173W WO 8910190 A1 WO8910190 A1 WO 8910190A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
energy content
silica
catalyst according
gas
Prior art date
Application number
PCT/AU1989/000173
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English (en)
Inventor
Duncan Seddon
Original Assignee
Duncan Seddon
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 Duncan Seddon filed Critical Duncan Seddon
Publication of WO1989010190A1 publication Critical patent/WO1989010190A1/fr
Priority to NO90904652A priority Critical patent/NO904652L/no

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C01B39/082—Gallosilicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates

Definitions

  • Simple aromatic molecules such as benzene, toluene and xylene are key components and building blocks in many facets of modem industrialised societies. They find use as building blocks and intermediates in synthetic fibre manufacture such as polyesters and nylon, and intermediates in bulk commodity plastics such as polystyrene. They also find use as components of special hydrocarbon solvents. The supply of these aromatic molecules to modern industry is thus of crucial importance.
  • paraffins are available from a wide range of sources. For example, in the recovery of natural -gas large quantities of paraffins, usually known as condensate, and paraffinic gases, referred to as LPG, are often co:— produced: with the gas. Paraffins, together with small olefins are also produced in large quantities from refinery operations such as catalytic cracking and hydrocracking.
  • the purpose of the present invention is to produce small aromatic molecules from paraffins, boiling -from ethane upwards, and olefins from ethylene upwards, using catalysts and process plants which are cheaper than catalytic reforming.
  • the invention concerns the conversion of paraffins and olefins into aromatics by zeolite catalysts.
  • the conversion of paraffins and olefins into aromatics has been described in Australian Patent 509285 (to British Petroleum pic), this patent describes the preparation and use of gallium impregnated and ion - exchanged ZSM -5 zeolite catalysts.
  • Australian Patents 479875 and 484974 both to Mobil Oil Corp.) describe the use of zinc exchanged zeolite to effect paraffin onversion into an aromatic rich product.
  • the above processes utilise a conventionally synthesised ZSM -5 zeolite which is subsequently impregnated or exchanged with the promoting metal either gallium or zinc.
  • the conventionally synthesised ZSM -5 zeolite contains aluminium in the crystal lattice.
  • Zeolites with gallium in the lattice have been known for a long time (see "Zeolite Molecular Sieves" by D.W.Breck published in 1974). Zeolite catalysts with gallium in the lattice have been described in Australian Patent 558232 (to Shell International Research Maatschappij B.V.) This patent describes gallium compositions made from gels with a silica/gallia mole ratio of 25 - 100. As well as aromatic rich liquids these catalysts gave a high selectivity to hydrogen gas. Such byproduct hydrogen is useful in developed centres where there is a growing demand for molecular hydrogen.
  • an improved: catalyst can be made from a zeolite synthesised from a silicate gel containing a source of gallium and containing substantially no aluminium.
  • the said zeolite can be beneficially used for the conversion of paraffins and olefins from ethane and ethylene upwards into aromatics or aromatic rich blendstock and a high energy content (in volume terms) hydrocarbon gas, without further ion -exchange or impregnation with gallinrrp ox zinc.
  • the said silicate gel preferably has a silica/gallia mole ratio ⁇ *1 and siKca/alumina mole ratio > 100, the alumina coming from common impurities in the starting materials.
  • the conversion of the paraffins and olefins occurs at temperatures preferably from 300°C upwards, and at low pressure in the absence of added hydrogen.
  • Zeolite catalysts are a crucial feature of the invention. Zeolites and zeolite like materials are described in "Zeolite Molecular Sieves" by D.W.Breck published in 1974. Of particular interest are zeolites of the ZSM-5 family some of which are described in Australian Patents 424568, 446123, 450820 and 458708 (all to Mobil Oil Corp.).
  • the zeolites of the invention are characterised by an open pored structure which will allow the entry of paraffinic molecules, and more importantly the egress of the small aromatic molecules of interest.
  • the zeolite structures of interest can be characterised by vacuum microbalance sorption using simply branched paraffins such as 3 -methylpentane as sorbent.
  • the zeolites of interest will, in the hydrogen or acid form of the zeolite, sorb more than 2% by weight of
  • Zeolites are usually regarded as crystalline alu ino - silicates although it is now recognised that combinations of many other elements can give open pore structures similar to the alumino - silicate zeolites.
  • a distinguishing feature of the zeolite materials of this invention is that they are formed in a gallo - silicate form, i.e. gallium is substituted for aluminium in the synthesis of the zeolite and the zeolite structure is essentially free of aluminium. It will be recognised that aluminium is a common impurity in gallium and silica source materials and small quantities of aluminium may be present.
  • the zeolite catalysts of the invention will have a silica/alumina mole ratio of at least 100.
  • a particular feature of the gallo - silicates of the invention is that gallium is added at the time of synthesis.
  • Methods of adding gallium include as oxide or as a soluble salt such as gallium nitrate, which is added to the synthesis gel before the zeolite is crystallised. The -preference is for a sihca/gaHia ⁇ m ⁇ le ratio of at least 10, although lower ratios may be used.
  • the zeolite will be capable of being transformed into a solid Bronsted acid.
  • the method by which this is achieved is dependent upon the particular zeolite used. Many methods are described in the literature. Some zeolites are incapable of being transformed and structure collapse will occur reducing the zeolites ability to sorb pertinent simply branched paraffins.
  • the zeolite will be fabricated into a solid particle, chip- or pellet This fabrication may or may not require the assistance of " a binder or inert diluent material. The choice of binder and size of particle will be determined by the engineering requirements of the equipment in which the catalyst is to be used.
  • alumina or clays e.g. bentonite:- JQr
  • the binder may not be totally inert but may provide a co- catalytic role by, for example, bringing additional acid sites or dehydrogenation function to the final catalyst composite.
  • the catalyst of the invention is used to convert paraffinic or olefinic hydrocarbons by contact with the feedstock in the gaseous phase.
  • the paraffinic feedstock may range from LPG to heavy naphthas, be individual components such as propane, or wide ranging mixtures.
  • Present with the paraffin may be naphthenic materials, c clo -paraffins, olefins such as ethylene or propylene or aromatics.
  • the paraffins may be branched or linear or any mixture.
  • the feedstock may be very rich in olefins. In a likewise manner the olefin feedstock may be very rich in paraffins, be linear or branched or any mixture, or contain aromatics.
  • the olefins of interest may be ethylene, produced by pyrolysis of higher hydrocarbons else as the product of oxidative coupling of methane or the high temperature catalytic pyrolysis of methane.
  • Olefins such as propylene are produced as byproduct in the catalytic cracking of hydrocarbons.
  • the olefin feed will contain significant quantities of paraffin from methane onwards in molecular weight.
  • the conversion conditions used will depend upon the nature of the feedstock. At one extreme are products from oxidative coupling of methane in which ethylene and ethane might be diluted with a large excess of methane.
  • the efficient conversion of the paraffins and olefins in such a feedstock might be best brought about at high temperatures e.g 600-700°C and relatively low space velocity e.g. O.lhr -1 . For the most part however conversion conditions will be much less severe.
  • conversion is brought about by contacting the feedstock at a temperature from 350 to 600°C preferably 400 to 550°C and at a weight hourly space velocity ranging from 0.1 to 20hr ⁇ 1 , preferably 0.5 to 5hr ⁇ ⁇
  • conversion can be brought about at lower temperature e.g. 300°C.
  • a distinguishing feature of the catalysts and the process of the invention is that no additional hydrogen need be added to the feedstock; this contrasts with catalytic reforming which is usually conducted in the pressence of a substantial hydrogen partial pressure.
  • Another distinguishing feature is the energy content in volume terms, of the byproduct gas.
  • the main light byproducts are hydrogen, methane, ethane, ethylene, propane and propylene. After separation of the liquid product some of these light gaseous products may be recycled so as to increase the overall yield of aromatics (principally by converting all of the olefins and more of the propane).
  • methane and ethane would not be converted and would have to be prurged from the system together with some residual olifin and propane.
  • the catalyst of the invention will give a light gaseous byproduct containing methane, ethane and propane, with an energy content greater than 900BTU/ft 3 .
  • the catalyst of the. invention will give a light gaseous product containing methane and ethane, with an energy content greater than 800BTU/ft 3 .
  • This example illustrates the synthesis of the zeolite of the invention.
  • a gel was made up by mixing together sodium hydroxide (7.4g) dissolved in water (50.0g), a dispersion of silica (made from Cab-O-SilTM (133.4g), water (800g) and gallium nitrate solution (230ml, 0.179M)), and a soluton of tetra-n-propylammonium bromide (73.9g) in water (200g). After mixing, sodium chloride (250g) was stirred in. The pH of the gel was adjusted to 113 by the addition of a further portion of sodium hydroxide solution (45ml of 10% wt/wt). The zeolite gel had a silica/gallia mole ratio of 107.
  • the zeolite was crystallised in a stirred autoclave at 170°C over 16hr.
  • the as -made product was transformed to the acid form by ion -exchange with ammonium nitrate solution, followed by calcination to 500°C. The ion -exchange and the calcination steps were repeated.
  • the product zeolite was shown to be of the ZSM-5 structure by powder x-ray diffraction. Vacuum microbalance studies gave 11.4% n-hexane and 7.6% 3 -methylpentane sorption at 2kPa.
  • the zeolite was fabricated into 3mm tablets using CatapelTM, a pseudo-boehmite aliimina phase, as binder,(l:4 wt/wt).
  • This example illustrates the use of a catalyst prepared in the above manner.
  • the catalyst (lOg) was charged to a stainless steel reactor of conventional downflow geometry. Liquid feedstock was vapourised in a preheater and aromatic rich product collected using a condenser placed immediately after the reactor, before use the catalyst was dried on a stream of nitrogen for 3hr at 400°C. The following results were obtained at 500°C and a WHSV of lhr - 1 . Analysis was performed by gas -chromatography. Because of the small scale of this test these results merely illustrate the types of feedstock that can be processed.
  • the catalyst of the invention is capable of converting a wide range of paraffinic feedstock, from propane upwards into aromatics.
  • the conversion of olefins such as propene and butenes into aromatic rich products is also illustrated.
  • This example compares the catalyst of the invention with the prior -art catalyst prepared in accordance with Australian Patent 509285 by impregnation of a ZSM-5 zeolite with a silica/alumina ratio of 70 with gallium nitrate solution.
  • the samples were obtained by the incipient wetness using IM gallium nitrate - alternative - 1 - and 2M gallium nitrate - alternative -2.
  • the equipment used was as in Example 2.
  • n-Pentane was fed over the catalysts at 500°C, a WHSV of lhr " 1 and at 1 atm. pressure.
  • the example shows the higher concentration of aromatics that can be obtained using the catalyst of the invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

On a mis au point un catalyseur permettant de transformer des paraffines, des oléfines ou des mélanges des deux en un produit hydrocarbure riche en aromatiques et un gaz à haute teneur énergétique. Le catalyseur comprend un gallium-silicate cristallin de la famille ZSM-5 et est préparé à partir d'un gel de gallo-silicate. Ledit gel a un rapport molaire dioxyde de silicium/dioxyde de gallium situé dans la plage comprise entre 80 et 115, et un rapport molaire dioxyde de silicium/oxyde d'aluminium supérieur à 100. Le gaz à haute teneur énergétique est un hydrocarbure gazeux ayant une haute teneur énergétique par volume unitaire.
PCT/AU1989/000173 1988-04-28 1989-04-20 Catalyseur de transformation d'olefines et de paraffines WO1989010190A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
NO90904652A NO904652L (no) 1988-04-28 1990-10-26 Katalysatorer for olefin- og parafinomdanning.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPI794088 1988-04-28
AUPI7940 1988-04-28

Publications (1)

Publication Number Publication Date
WO1989010190A1 true WO1989010190A1 (fr) 1989-11-02

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EP (1) EP0423134A1 (fr)
WO (1) WO1989010190A1 (fr)
ZA (1) ZA893173B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0472462A1 (fr) * 1990-08-24 1992-02-26 Institut Francais Du Petrole Utilisation d'un catalysateur de type galloalumino-silicate en aromatisation des hydrocarbures contenant 5 à 7 atomes de carbone par molécule
GB2367292A (en) * 2000-09-27 2002-04-03 Daicel Chem Crystalline Gallium Silicate Catalysts and their use in the preparation of Est ers
US10619109B2 (en) 2016-05-16 2020-04-14 Suncor Energy Inc. Direct olefin reduction of thermally cracked hydrocarbon streams

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU1863483A (en) * 1982-09-04 1984-03-08 British Petroleum Company Plc, The Preparation of gallosilicates and use as catalysts
EP0107875A2 (fr) * 1982-10-28 1984-05-09 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'un mélange d'hydrocarbures aromatiques
EP0107876A2 (fr) * 1982-10-28 1984-05-09 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'un mélange d'hydrocarbures aromatiques
AU2615684A (en) * 1983-03-29 1984-10-04 British Petroleum Company Plc, The Crystalline galloaluminosilicate and conversion of aliphatics to aromatics
AU4181185A (en) * 1984-05-02 1985-11-07 Shell Internationale Research Maatschappij B.V. Process for the preparation of an aromatic hydrocarbon mixture
AU4219785A (en) * 1984-04-24 1985-11-15 British Petroleum Company Plc, The Process for the production of hydrocarbons from hetero- substituted methanes
US4582949A (en) * 1984-05-18 1986-04-15 Shell Oil Company Process for the preparation of an aromatic hydrocarbon mixture
EP0223345A1 (fr) * 1985-09-17 1987-05-27 Mobil Oil Corporation Procédé pour la conversion d'oléfines légères en hydrocarbures plus lourds
EP0230356A1 (fr) * 1986-01-09 1987-07-29 Research Association For Utilization Of Light Oil Production d'une réserve de mélange pour essence à indice d'octane élevé
US4704494A (en) * 1984-08-15 1987-11-03 Showa Shell Sekiyu Kabushiki Kaisha Conversion process of aromatic hydrocarbon from low molecular paraffin hydrocarbon
EP0252742A2 (fr) * 1986-07-11 1988-01-13 Mobil Oil Corporation Procédé pour la conversion de composés aliphatiques inférieurs contenant de l'oxygène en des composés oléfiniques et aromatiques au moyen d'un catalyseur ZSM-5 contenant du gallium
EP0299392A1 (fr) * 1987-07-15 1989-01-18 Research Association For Utilization Of Light Oil Procédé pour préparer un silicate gallo-alumineux cristallin et procédé pour préparer des hydrocarbures aromatiques
AU2831189A (en) * 1988-01-07 1989-07-13 Mobil Oil Corporation Zsm-5 catalysts having predominantly framework gallium, methods of their preparation and use

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU1863483A (en) * 1982-09-04 1984-03-08 British Petroleum Company Plc, The Preparation of gallosilicates and use as catalysts
EP0107875A2 (fr) * 1982-10-28 1984-05-09 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'un mélange d'hydrocarbures aromatiques
EP0107876A2 (fr) * 1982-10-28 1984-05-09 Shell Internationale Researchmaatschappij B.V. Procédé de préparation d'un mélange d'hydrocarbures aromatiques
AU2615684A (en) * 1983-03-29 1984-10-04 British Petroleum Company Plc, The Crystalline galloaluminosilicate and conversion of aliphatics to aromatics
AU4219785A (en) * 1984-04-24 1985-11-15 British Petroleum Company Plc, The Process for the production of hydrocarbons from hetero- substituted methanes
AU4181185A (en) * 1984-05-02 1985-11-07 Shell Internationale Research Maatschappij B.V. Process for the preparation of an aromatic hydrocarbon mixture
US4582949A (en) * 1984-05-18 1986-04-15 Shell Oil Company Process for the preparation of an aromatic hydrocarbon mixture
US4704494A (en) * 1984-08-15 1987-11-03 Showa Shell Sekiyu Kabushiki Kaisha Conversion process of aromatic hydrocarbon from low molecular paraffin hydrocarbon
EP0223345A1 (fr) * 1985-09-17 1987-05-27 Mobil Oil Corporation Procédé pour la conversion d'oléfines légères en hydrocarbures plus lourds
EP0230356A1 (fr) * 1986-01-09 1987-07-29 Research Association For Utilization Of Light Oil Production d'une réserve de mélange pour essence à indice d'octane élevé
EP0252742A2 (fr) * 1986-07-11 1988-01-13 Mobil Oil Corporation Procédé pour la conversion de composés aliphatiques inférieurs contenant de l'oxygène en des composés oléfiniques et aromatiques au moyen d'un catalyseur ZSM-5 contenant du gallium
EP0299392A1 (fr) * 1987-07-15 1989-01-18 Research Association For Utilization Of Light Oil Procédé pour préparer un silicate gallo-alumineux cristallin et procédé pour préparer des hydrocarbures aromatiques
AU2831189A (en) * 1988-01-07 1989-07-13 Mobil Oil Corporation Zsm-5 catalysts having predominantly framework gallium, methods of their preparation and use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0423134A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0472462A1 (fr) * 1990-08-24 1992-02-26 Institut Francais Du Petrole Utilisation d'un catalysateur de type galloalumino-silicate en aromatisation des hydrocarbures contenant 5 à 7 atomes de carbone par molécule
FR2666085A1 (fr) * 1990-08-24 1992-02-28 Inst Francais Du Petrole Utilisation d'un catalyseur de type galloaluminosilicate en aromatisation des hydrocarbures contenant 5 a 7 atomes de carbone par molecule.
GB2367292A (en) * 2000-09-27 2002-04-03 Daicel Chem Crystalline Gallium Silicate Catalysts and their use in the preparation of Est ers
US10619109B2 (en) 2016-05-16 2020-04-14 Suncor Energy Inc. Direct olefin reduction of thermally cracked hydrocarbon streams

Also Published As

Publication number Publication date
EP0423134A1 (fr) 1991-04-24
ZA893173B (en) 1989-12-27
EP0423134A4 (fr) 1991-03-01

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