EP0303372B1 - Verwendung von Erdölkatalysatoren - Google Patents

Verwendung von Erdölkatalysatoren Download PDF

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Publication number
EP0303372B1
EP0303372B1 EP19880306952 EP88306952A EP0303372B1 EP 0303372 B1 EP0303372 B1 EP 0303372B1 EP 19880306952 EP19880306952 EP 19880306952 EP 88306952 A EP88306952 A EP 88306952A EP 0303372 B1 EP0303372 B1 EP 0303372B1
Authority
EP
European Patent Office
Prior art keywords
catalyst
nickel
catalyst composition
zeolite
mixed oxide
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.)
Expired - Lifetime
Application number
EP19880306952
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English (en)
French (fr)
Other versions
EP0303372A1 (de
Inventor
Andrew Paul Chapple
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.)
Ineos Silicas Ltd
Original Assignee
Unilever PLC
Unilever NV
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Publication date
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to AT88306952T priority Critical patent/ATE63569T1/de
Publication of EP0303372A1 publication Critical patent/EP0303372A1/de
Application granted granted Critical
Publication of EP0303372B1 publication Critical patent/EP0303372B1/de
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Classifications

    • 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

Definitions

  • the invention relates to cracking catalysts and to catalytic cracking, which is a major refinery process for the conversion of hydrocarbons to lower boiling fractions. More specifically, the invention relates to an improved process for cracking nickel containing feedstocks by using these catalysts.
  • Catalysts containing crystalline zeolites dispersed in an inorganic oxide matrix have been used for the catalytic cracking of petroleum-derived feedstocks for many years.
  • certain contaminants notably vanadium, nickel, and iron
  • the accumulated deposits lead to undesirable changes in the activity and selectively of the thus contaminated catalysts; see P.B. Venuto and E.T.
  • the present invention provides a method of cracking nickel contaminated hydrocarbon feedstocks with a catalyst composition and use of the catalyst composition in such a method, which catalyst composition comprises a i) crystalline zeolite, ii) a matrix material, and iii) certain crystalline mixed oxides, derived from the heavier alkaline earth elements (calcium, strontium, barium) and tin, which oxides have themselves no harmful effects on the catalytic properties but are present in amounts sufficient to passivate the dehydrogenation properties of the contaminent nickel.
  • catalyst composition comprises a i) crystalline zeolite, ii) a matrix material, and iii) certain crystalline mixed oxides, derived from the heavier alkaline earth elements (calcium, strontium, barium) and tin, which oxides have themselves no harmful effects on the catalytic properties but are present in amounts sufficient to passivate the dehydrogenation properties of the contaminent nickel.
  • the catalyst composition for use in accordance with the present invention comprises i) a crystalline zeolite, ii) a matrix material and iii) a mixed oxide selected from calcium, strontium and barium tin oxides and mixtures thereof.
  • the mixed oxides include hydroxy stannates.
  • the crystalline zeolite component which is usually present in the range from about 5% to about 40% by weight, may generally be described as a crystalline, three dimensional, stable structure enclosing cavities of molecular dimensions.
  • Most zeolites are based on aluminosilicate frameworks, the aluminium and silicon atoms being tetrahedrally coordinated by oxygen atoms.
  • zeolites similar materials in which atoms of other elements are present in the framework, such as boron, gallium, germanium, chromium, iron, and phosphorus.
  • PILCS pillared interlayered clays
  • Zeolites which can be employed in the catalysts for use in the methods of this invention can be natural or synthetic in origin. These naturally occurring zeolites include gmelinite, chabazite, dachiardite, clinoptilolite, faujasite, heulandite, analcite, levynite, erionite, sodalite, canorinite, mepheline, lazurite, scolecite, natiolite, offretite, mesolite, mordenite, brewsterite, fevierite, and the like.
  • Suitable synthetic zeolites are zeolites A, B, E, F, H, J, L, Q, T, W, X, Y, Z, alpha, beta, omega, the EU types, the Fu types, the Nu types, the 2K types, the ZSM types, the ALPO types, the SAPO types, the L2 series, and other similar materials will be obvious.
  • the effective pore size of the synthetic zeolites are preferably between 0.6 and 1.5 nanometers, and the preferred zeolites are those with the faujasite framework and silica/alumina ratios > 3, thus including synthetic zeolite Y and the various forms of Y which have been made more siliceous by chemical, hydrothermal or thermal treatments.
  • the zeolite is converted to a form which is most applicable for catalytic cracking.
  • this involves a sequence of ion-exchange and calcination treatments to introduce acid groups into the zeolite, stabilise the structure, and remove alkali metal cations.
  • the prefered method of achieving this end is to exchange the zeolite with solutions containing ammonium ions and/or rare earth ions (either a pure rare earth compound or a mixture).
  • Such treatment can be carried out either on the zeolite before it is incorporated in the catalyst, or on the finished catalyst containing the zeolite, it can be carried out on a filter press, filter table, or filter belt, or by slurrying the zeolite/catalyst in a tank.
  • the matrix into which the zeolite is incorporated can have a wide range of compositions.
  • Suitable components include: naturally occurring or synthetic clays, including kaolin, halloysite and montmorillonite; inorganic oxide gels, including binary gels such as silica, silica-alumina, silica-zirconia, silica-magnesia, aluminium phosphates, or ternary combinations such as silica-magnesia-alumina; and crystalline inorganic oxides such as silica, alumina, titania, zirconia.
  • Suitable mixed oxides for use as component (iii) are:
  • the mixed oxide additive is a discrete component of the final catalyst, and is readily identifiable in the fresh catalyst by x-ray diffraction analysis. These materials are insoluble, and are not decomposed into their component oxides over a wide range of thermal and hydrothermal treatments, and, as such are readily identifiable in hydrothermally deactivated catalyst samples.
  • the mixed oxide is present at a level of least about 0.1% by weight of the catalyst and up to about 20% by weight.
  • the chemical form of the additive is central to determining the concentration in which it is used in the catalyst composition, or indeed its method of incorporation into the catalyst formulation.
  • the additives used in methods of this invention can be prepared by various processes; for example, by calcination of intimate mixtures of the oxides or carbonates of the component elements, in the appropriate molar quantities, or by coprecipitation, or metathesis of salts of the appropriate elements.
  • the catalysts containing these additives may be prepared by any of the conventional methods used for the manufacture of FCC catalysts.
  • catalyst may be prepared by making an inorganic oxide sol at pH 3 and adding to this, aqueous slurries of the other catalyst components including zeolite and alkaline earth additive. The homogenised slurry can then be spray dried to produce catalyst microspheres, and washed free of soluble salts using for example aqueous ammonium sulphate and water.
  • the catalyst compositions used in methods of this invention are employed in the cracking of nickel containing heavy hydrocarbon feedstocks, to produce gasoline, and light distillate fraction.
  • Typical feedstocks would have an average boiling point greater than 316°C, and include such materials as gas oils, and residual oils.
  • the catalysts used in methods of this invention are effective in cracking processes even when contaminated with nickel to levels in excess of 2000 ppm, these catalysts can be used to process feedstocks containing significantly higher concentrations of nickel than those employed in conventional catalytic cracking operations.
  • These catalysts may be employed in any catalytic cracking process capable of operating with conventional microsphere fluid catalysts.
  • a catalyst was prepared by combining together 100 g Al2O3 400 g Kaolin, and 270 g of CREHY (calcined Rare Earth/Ammonium exchanged zeolite Y), in 2895 g of a silica sol (8% SiO2 w/w) at pH 3.2, to provide a homogeneous slurry. The slurry was then spray-dried to form catalyst microspheres with an average particle size of about 60 microns.
  • CREHY calcined Rare Earth/Ammonium exchanged zeolite Y
  • the spray-dried catalyst was then washed with deionized water, 0.25 M ammonium sulphate, and finally deionized water, until the conductivity of the filtrate fell below 1 milli-mho.
  • the washed catalyst was then dried at 100°C (Catalyst A).
  • a catalyst was prepared by combining together 100g Al2O3, 276g Kaolin, 124 g SrSnO3, and 270 g of CREHY, in 2875 g of a silica sol (8% SiO2 w/w) at pH 3.2, to provide a homogeneous slurry. The slurry was then spray-dried to form catalyst microspheres with an average particle size of about 60 microns.
  • the spray-dried catalyst was then washed with deionized water, 0.25 M ammonium sulphate, and finally deionized water, until the conductivity of the filtrate fell below 1 milli-mho.
  • the washed catalyst was then dried at 100°C (Catalyst B).
  • a catalyst was prepared by combining together 100g Al2O3, 300 g Kaolin, 100 g CaSnO3, and 270 g of CREHY in 2875 g of a silica sol (8% SiO2 w/w) at pH 3.2, to provide a homogeneous slurry. The slurry was then spray-dried to form catalyst microspheres with an average particle size of about 60 microns.
  • the spray-dried catalyst was then washed with deionized water, 0.25 M ammonium sulphate, and finally deionized water, until the conductivity of the filtrate fell below 1 milli-mho.
  • the washed catalyst was then dried at 100°C (Catalyst C).
  • the above catalysts (A-F) were evaluated in a microactivity test (MAT) unit. Prior to testing, the catalyst samples were thermally treated at 538°C for 3 hrs, and then deactivated in steam at atmospheric pressure, at a temperature of 788°C for a period of 5 hrs.
  • MAT microactivity test
  • a zeolite based (CREHY) spray-dried catalyst was prepared containing CaSn(OH)6 (1.1% w/w as CaO). This catalyst was impregnated with nickel, and deactivated under an atmospheric of steam in an equivalent manner to that described in the preceding examples.
  • the catalytic performance of this sample (Catalyst G) was measured by MAT, and compared to an equivalent catalyst formulation containing no hydroxy stannate component (catalyst H). The results of these tests are shown in table II.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (8)

1. Verfahren zum Kracken von mit Nickel verunreinigten Kohlenwasserstoffbeschickungen, bei dem die Beschickung mit einer Katalysatorzusammensetzung in Kontakt gebracht wird, die
i) einen kristallinen Zeolith,
ii) ein Matrixmaterial und
iii) eine das Nickel passivierende Verbindung
umfaßt, dadurch gekennzeichnet, daß die das Nickel passivierende Verbindung ein gemischtes Oxid, ausgewählt aus Calcium-, Strontium- und Bariumzinnoxiden und deren Mischungen, ist.
2. Verfahren gemäß Anspruch 1, bei dem die Katalysatorzusammensetzung mit Nickel in einer Menge über 2000 ppm verunreinigt wird.
3. Verfahren gemäß Anspruch 1 oder 2, bei dem die Katalyatorzusammensetzung etwa 5 bis etwa 40 Gew.-% Zeolith umfaßt.
4. Verfahren gemäß Anspruch 1, 2 oder 3, bei dem die Katalysatorzusammensetzung etwa 0,1 bis etwa 20 Gew.-% gemischtes Oxid umfaßt.
5. Die Verwendung einer Katalysatorzusammensetzung bei einem Verfahren zum Kracken einer mit Nickel verunreinigten Beschickung, wobei die Katalysatorzusammensetzung
i) einen kristallinen Zeolith,
ii) ein Matrixmaterial und
iii) eine das Nickel passivierende Verbindung
umfaßt, dadurch gekennzeichnet, daß die das Nickel passivierende Verbindung ein gemischtes Oxid, ausgewählt aus Calcium-, Strontium- und Bariumzinnoxiden und deren Mischungen, ist.
6. Die Verwendung gemäß Anspruch 5, bei der die Katalysatorzusammensetzung mit Nickel in einer Menge über 2000 ppm verunreinigt wird.
7. Die Verwendung gemäß Anspruch 5 oder 6, bei der die Katalysatorzusammensetzung etwa 5 bis etwa 40 Gew.-% Zeolith umfaßt.
8. Die Verwendung gemäß den Ansprüchen 5, 6 oder 7, bei der die Katalysatorzusmmensetzung etwa 0,1 bis etwa 20 Gew.-% gemischtes Oxid umfaßt.
EP19880306952 1987-07-30 1988-07-28 Verwendung von Erdölkatalysatoren Expired - Lifetime EP0303372B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88306952T ATE63569T1 (de) 1987-07-30 1988-07-28 Verwendung von erdoelkatalysatoren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8718108 1987-07-30
GB878718108A GB8718108D0 (en) 1987-07-30 1987-07-30 Petroleum catalysts

Publications (2)

Publication Number Publication Date
EP0303372A1 EP0303372A1 (de) 1989-02-15
EP0303372B1 true EP0303372B1 (de) 1991-05-15

Family

ID=10621569

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880306952 Expired - Lifetime EP0303372B1 (de) 1987-07-30 1988-07-28 Verwendung von Erdölkatalysatoren

Country Status (7)

Country Link
EP (1) EP0303372B1 (de)
AT (1) ATE63569T1 (de)
AU (1) AU600843B2 (de)
CA (1) CA1331863C (de)
DE (1) DE3862828D1 (de)
GB (1) GB8718108D0 (de)
ZA (1) ZA885529B (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2827168B2 (ja) * 1990-11-30 1998-11-18 触媒化成工業株式会社 炭化水素接触分解用触媒組成物の製法
EP2158300A1 (de) * 2007-06-08 2010-03-03 Albemarle Netherlands BV Basische krackzusammensetzungen frei von grosssporigen zeolithen
EP2167615A1 (de) * 2007-06-08 2010-03-31 Albemarle Netherlands BV Verfahren zum katalytischen cracken für hohe dieselausbeute mit geringem aromatengehalt und/oder hohe propylenausbeute
WO2008148686A1 (en) * 2007-06-08 2008-12-11 Albemarle Netherlands, B.V. Catalytic cracking and hydroprocessing process for high diesel yield with low aromatic content and/or high propylene yield
WO2009087576A2 (en) * 2008-01-09 2009-07-16 Albemarle Netherlands B.V. Fcc process employing basic cracking compositions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8514209D0 (en) * 1985-06-05 1985-07-10 Unilever Plc Catalyst additives
CA1264720A (en) * 1985-06-11 1990-01-23 Edwin L. Kugler Cracking catalysts containing water-insoluble strontium compounds and methods of using them

Also Published As

Publication number Publication date
ZA885529B (en) 1990-03-28
DE3862828D1 (de) 1991-06-20
AU600843B2 (en) 1990-08-23
ATE63569T1 (de) 1991-06-15
EP0303372A1 (de) 1989-02-15
CA1331863C (en) 1994-09-06
AU2002488A (en) 1989-02-02
GB8718108D0 (en) 1987-09-03

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