WO1991017827A1 - Procede et catalyseur de craquage - Google Patents

Procede et catalyseur de craquage Download PDF

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Publication number
WO1991017827A1
WO1991017827A1 PCT/GB1991/000757 GB9100757W WO9117827A1 WO 1991017827 A1 WO1991017827 A1 WO 1991017827A1 GB 9100757 W GB9100757 W GB 9100757W WO 9117827 A1 WO9117827 A1 WO 9117827A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
zsm
gallium
zeolite
weight
Prior art date
Application number
PCT/GB1991/000757
Other languages
English (en)
Inventor
David William Aitchison
Michael Robert Gelsthorpe
Christopher Sharp
Simon Anthony Weeks
Original Assignee
The British Petroleum Company Plc
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 The British Petroleum Company Plc filed Critical The British Petroleum Company Plc
Publication of WO1991017827A1 publication Critical patent/WO1991017827A1/fr

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Classifications

    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming

Definitions

  • the present invention relates to fluid catalytic cracking of hydrocarbons, and to a catalyst suitable for use in such a process.
  • Fluid catalytic cracking is a well-known process for the conversion of higher boiling hydrocarbons into more valuable lower 5 boiling fractions, in particular gasoline.
  • Various catalysts have been used for this process including catalysts based on various types of zeolite.
  • the conventional cracking catalysts give relatively good yields of the desirable gasoline fraction.
  • the quality of the 10 gasoline as measured by its octane number tends to be poor.
  • EP 259 155A proposes to improve the quality of gasoline produced by fluid catalytic cracking by using two catalysts.
  • a conventional cracking catalyst based for example on zeolite X or Y is used together with a relatively smaller amount of an additive catalyst which is based on a zeolite, e.g. ZSM-5, differing from 25 that used in the conventional catalyst.
  • the presence of such an additive improves the quality of the gasoline.
  • the gasoline yield i.e. the proportion of the cracked product in the gasoline boiling range is decreased.
  • EP 259 155A contains a brief reference, without supporting experimental evidence, to the possibility of introducing certain elements, including gallium, on to the additive catalyst so as to increase more feed to aromatics so as to improve the quality of the gasoline.
  • a process for making a catalyst suitable for use as an additive catalyst for _he fluid catalytic cracking of hydrocarbons comprises depositing on zeolite ZSM-5, which zeolite is in the (alkyl)ammonium form, a quantity of gallium in the range 0.1% to 2% by weight based on the weight of ZSM-5, from a solution with a pH in the range 1.5 to 3.5.
  • a process for cracking a hydrocarbon feed to give gasoline in the presence of a fluidized bed of a catalyst based on ZSM-5 zeolite is characterised in that gallium has been deposited on the ZSM-5 zeolite, which zeolite is in (alkyl)ammonium form, from a solution of gallium ions with a pH in the range 1.5 to 3.5 in an amount in the range 0.1 to 2% by weight based on the weight of ZSM-5.
  • the present invention is particularly suitable for use in a catalytic cracking process using two zeolite catalysts with a major amount of a first (or main) catalyst based on a zeolite and a minor amount of a second (or additive) catalyst based on ZSM-5 catalyst.
  • the additive catalyst is present in an amount which is 0.5 to 20% by weight of the total catalyst.
  • zeolite-based catalysts for fluid catalytic cracking usually only forms part of the total catalyst partic --. which contains an amorphous matrix, e.g. alumina, and clay binders in addition to the zeolite.
  • the ZSM-5 zeolite may for example form from 5 to 60% by weight of the catalyst particle.
  • the production of zeolite-based catalysts for use in fluid catalytic cracking is carried out on a large scale commercially. It is not therefore necessary to give detailed information on catalyst preparation techniques or desired particle sizes.
  • ZSM-5 is usually supplied in the hydrogen form. Before deposition of the gallium the ZSM-5 zeolite is converted to the (alkyl)ammonium form.
  • (alkyl) mmonium it is meant throughout this specification to be the ammonium ion itself and derivatives of the ammonium ion resulting from the substitution of hydrogen atoms by alkyl groups.
  • the ZSM-5 zeolite may be converted to the (alkyl)ammonium form by heating in an aqueous solution containing (alkyl)ammonium ions.
  • the ZSM-5 may be refluxed with an aqueous solution of an ammonium salt, e.g. ammonium nitrate.
  • the solution is preferably a relatively concentrated one containing a 1.5 to 2M solution of the ammonium salt (assuming that the salt has sufficient solubility). It may be desirable to adjust the pH to provide an alkaline solution by the addition of an (alkyl)ammonium hydroxide.
  • the (alkyl)ammonium exchanged ZSM-5 is preferably washed with large quantities of water to remove unexchanged material, and then dried, for example at temperatures in the range 100-150°C.
  • Suitable techniques for introducing the gallium are doping or impregnation from an aqueous or organic gallium solution. However it is undesirable to deposit the gallium from excessively acid solutions and thus the solution used must have a pH in the range 1.5 to 3.5, preferably not below 2.
  • the quantity of gallium introduced on to the ZSM-5 is in the range 0.1 to 2.0% based on the weight of ZSM-5, preferably 0.3 to 1.0%.
  • Aqueous solutions of gallium nitrate may be used to deposit the gallium.
  • Such solutions have an acid pH, e.g. about 2.3.
  • the resulting product is dried, for example at temperatures in the range 100-150*C.
  • Octane values were obtained from a GC octane correlation developed following the method of Anderson Sharkey and Walsh (J Inst pet vol March 1972) specifically for catalytically cracked gasoline. Examples 1-4
  • Zeolite ZSM-5 in the hydrogen form (500g) was refluxed for 2 hours in aqueous 2M ammonium nitrate solution (5 litres) whose pH had been adjusted to pH 9.0 with cone, aqueous ammonia. The resulting ammonium-exchanged zeolite was then filtered off and washed with distilled water (20 litres) and dried at 120*C.
  • a gallium nitrate stock solution with a gallium concentration of 0.05g/ml was prepared by dissolving gallium nitrate in distilled water. This solution had a pH of 2.3.
  • a solution for impregnating the ZSM-5 zeolite was prepared by diluting the stock solution with distilled water. The ZSM-5 zeolite (250 mg) was impregnated with the diluted solution (200 ml). The degree of dilution is selected to give the desired amount of gallium on the zeolite (as indicated in Table 1). The resulting paste was dried at 120*C for 17 hours. The ZSM-5 was then bound into catalyst particles by a commercially established procedure.
  • the ZSM-5 catalyst particles were mixed with a commercial catalytic cracking base catalyst to give 5% by weight of the ZSM-5 catalyst in the total catalyst.
  • the resulting mixtures were tested using the steam deactivators and performance evaluator procedures described earlier. The results are shown in Table 1.
  • DG dry gas (methane, C )
  • LPG liquefied petroleum gases (propane, butane)
  • CCS cracked catalytic spirit (gasoline)
  • LCO light cycle oil
  • HCO heavy cycle oil.
  • a comparison of the results for Tests A and B shows the l eduction in gasoline yield and increase in quality obtained using ar. additive catalysts.
  • a comparison of the results for Test B and those shown in Table 1 for Examples 1-4 shows the increased gasoline yield obtained when the additive catalyst contains gallium, while still remaining an improved gasoline quality.
  • a comparison of the results for Test B and Test A shows that the use of a gallium-containing additive catalyst not prepared in accordance with the invention gives no increase in gasoline yield compared with an additive catalyst which does not contain gallittm. The presence of gallium is not in itself sufficient to give good results.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

Catalyseur convenant en tant que catalyseur adjuvant pour craquage catalytique à lit fluide obtenu en déposant 0,1 % à 2 % de Ga sur de la zéolite ZSM-5 sous forme d'ammonium(alkyle), à partir d'une solution dont le pH se situe entre 1,5 et 3,5.
PCT/GB1991/000757 1990-05-17 1991-05-14 Procede et catalyseur de craquage WO1991017827A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9011106.3 1990-05-17
GB909011106A GB9011106D0 (en) 1990-05-17 1990-05-17 Catalyst

Publications (1)

Publication Number Publication Date
WO1991017827A1 true WO1991017827A1 (fr) 1991-11-28

Family

ID=10676169

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1991/000757 WO1991017827A1 (fr) 1990-05-17 1991-05-14 Procede et catalyseur de craquage

Country Status (4)

Country Link
EP (1) EP0483325A1 (fr)
AU (1) AU637238B2 (fr)
GB (1) GB9011106D0 (fr)
WO (1) WO1991017827A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4426319A1 (de) * 1993-07-23 1995-02-09 Melnikov Vjaceslav Boris Katalysator für die Verbesserung der Qualität von Benzinen und Verfahren zur Herstellung desselben
EP1179581A1 (fr) * 2000-08-10 2002-02-13 China Petro-Chemical Corporation Promoteurs catalytiques pour le craquage catalytique d'hydrocarbures
ES2343937A1 (es) * 2009-01-29 2010-08-12 Uop Llc Catalizador fcc para produccion de olefinas ligeras.

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4377504A (en) * 1981-05-01 1983-03-22 Phillips Petroleum Company Cracking catalyst improvement with gallium compounds
EP0259155A1 (fr) * 1986-09-03 1988-03-09 Mobil Oil Corporation Procédé pour le stripping d'un catalyseur d'un zone de réaction pour le craquage catalytique
EP0309089A1 (fr) * 1987-08-25 1989-03-29 Mobil Oil Corporation Procédé pour la conversion d'aliphatiques en aromatiques sur une zéolite activée par du gallium
US4882039A (en) * 1986-12-04 1989-11-21 Mobil Oil Corporation Catalytic cracking of hydrocarbons with oxygen promoted alkali metal zeolite cracking catalyst
US5006497A (en) * 1988-12-30 1991-04-09 Mobil Oil Corporation Multi component catalyst and a process for catalytic cracking of heavy hydrocarbon feed to lighter products

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1561590A (en) * 1976-12-20 1980-02-27 British Petroleum Co Zeolites containing gallium
FR2634140B1 (fr) * 1988-07-12 1990-09-14 Inst Francais Du Petrole Catalyseur du type aluminosilicate contenant du gallium et son utilisation en aromatisation des gaz legers c2-c4

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4377504A (en) * 1981-05-01 1983-03-22 Phillips Petroleum Company Cracking catalyst improvement with gallium compounds
EP0259155A1 (fr) * 1986-09-03 1988-03-09 Mobil Oil Corporation Procédé pour le stripping d'un catalyseur d'un zone de réaction pour le craquage catalytique
US4882039A (en) * 1986-12-04 1989-11-21 Mobil Oil Corporation Catalytic cracking of hydrocarbons with oxygen promoted alkali metal zeolite cracking catalyst
EP0309089A1 (fr) * 1987-08-25 1989-03-29 Mobil Oil Corporation Procédé pour la conversion d'aliphatiques en aromatiques sur une zéolite activée par du gallium
US5006497A (en) * 1988-12-30 1991-04-09 Mobil Oil Corporation Multi component catalyst and a process for catalytic cracking of heavy hydrocarbon feed to lighter products

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPIL, Abstract Nr. 91-124897[17], Derwent Publications Ltd, London, GB; & US,A,5 006 497 (MOBIL OIL CORP), 9 April 1991. *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4426319A1 (de) * 1993-07-23 1995-02-09 Melnikov Vjaceslav Boris Katalysator für die Verbesserung der Qualität von Benzinen und Verfahren zur Herstellung desselben
DE4426319C2 (de) * 1993-07-23 1998-08-13 V & M Metallhandelsgesellschaf Katalysator für die Verbesserung der Qualität von Benzinen und Verfahren zur Herstellung desselben
EP1179581A1 (fr) * 2000-08-10 2002-02-13 China Petro-Chemical Corporation Promoteurs catalytiques pour le craquage catalytique d'hydrocarbures
US6677263B2 (en) 2000-08-10 2004-01-13 China Petro Chemical Corporation Catalytic promoters for the catalytic cracking of hydrocarbons and the preparation thereof
ES2343937A1 (es) * 2009-01-29 2010-08-12 Uop Llc Catalizador fcc para produccion de olefinas ligeras.

Also Published As

Publication number Publication date
AU637238B2 (en) 1993-05-20
EP0483325A1 (fr) 1992-05-06
GB9011106D0 (en) 1990-07-04
AU7870591A (en) 1991-12-10

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