EP0490435B1 - Verfahren zur Herstellung eines Olefine enthaltenden Kohlenwasserstoffgemisches - Google Patents

Verfahren zur Herstellung eines Olefine enthaltenden Kohlenwasserstoffgemisches Download PDF

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Publication number
EP0490435B1
EP0490435B1 EP91203184A EP91203184A EP0490435B1 EP 0490435 B1 EP0490435 B1 EP 0490435B1 EP 91203184 A EP91203184 A EP 91203184A EP 91203184 A EP91203184 A EP 91203184A EP 0490435 B1 EP0490435 B1 EP 0490435B1
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EP
European Patent Office
Prior art keywords
process according
zeolite
catalyst
feedstock
olefins
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.)
Revoked
Application number
EP91203184A
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English (en)
French (fr)
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EP0490435A1 (de
Inventor
Ian Ernest Maxwell
Antonius Franziskus Heinrich Wielers
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • 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 present invention relates to a process for the preparation of an olefins-containing mixture of hydrocarbons.
  • Ethylene and propylene are valuable starting materials for chemical processes, while C4 olefins can find use as a starting material for alkylation and/or oligomerization procedures in order to produce high octane gasoline and/or middle distillates.
  • Isobutene can be usefully converted to methyl t-butyl ether.
  • the present invention relates to process for the preparation of an olefins-containing mixture of hydrocarbons, which process comprises contacting a hydrocarbonaceous feedstock with a zeolitic catalyst at a temperature above 480 °C during less than 10 seconds, whereby the catalyst/feedstock weight ratio is in the range from 5 to 150 and the zeolitic catalyst comprises a zeolite with a pore diameter of 0.3 to 0.7 nm and an average crystallite size of less than 2 micrometer.
  • the zeolitic catalyst to be applied in the process according to the present invention comprises a zeolite having an average crystallite size of less than 1 micrometer. More preferably, the zeolite has an average crystallite size in the range of 0.01 to 0.5 micrometer.
  • crystallite size in this specification is to be regarded as the size of the individual zeolite crystals. These individual crystals may agglomerate into clusters which each may comprise 3 to 10 or more individual crystals. Preferably the zeolite comprises separate individual crystals.
  • the zeolitic catalyst to be used may comprise one or more zeolites with a pore diameter of from 0.3 to 0.7 nm, preferably from 0.5 to 0.7 nm.
  • zeolite in this specification is not to be regarded as comprising only crystalline aluminosilicates.
  • the term also includes crystalline silica (silicalite), silicoaluminophosphates (SAPO), chromosilicates, gallium silicates, iron silicates, aluminium phosphates (ALPO), titanium aluminosilicates (TASO), boron silicates, titanium aluminophosphates (TAPO) and iron aluminosilicates.
  • Suitable examples include crystalline silica (silicalite), silicoaluminophosphates (SAPO), chromosilicates, gallium silicates, iron silicates, aluminium phosphates (ALPO), titanium aluminosilicates (TASO), boron silicates, titanium aluminophosphates (TAPO) and iron aluminosilicates.
  • zeolite examples include SAPO-4 and SAPO-11, which are described in US-A-4,440,871, ALPO-11, described in US-A-4,310,440, TAPO-11, desribed in US-A-4,500,651, TASO-45 described in US-A-4,254,297, aluminium silicates like erionite, ferrierite, theta and the ZSM-type zeolites such as ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSM-23, and ZSM-38.
  • the zeolite with a pore diameter of from 0.3 to 0.7 nm is selected from the group consisting of crystalline (metallo)silicates having a ZSM-5 structure, ferrierite, erionite and mixtures thereof.
  • the zeolite with a pore diameter of from 0.3 to 0.7 nm comprises a crystalline (metallo)silicate having a ZSM-5 structure.
  • Suitable examples of crystalline (metallo)silicates with ZSM-5 structure are aluminium, gallium, iron, scandium, rhodium and/or chromium silicates as described in e.g. GB-B-2,110,559.n
  • the amount of alkali metal oxide is present in the readily prepared zeolites.
  • the amount of alkali metal is removed by methods known in the art, such as ion-exchange, optionally followed by calcination, to yield the zeolite in its hydrogen form.
  • the zeolite used in the process according to the present invention is substantially in its hydrogen form.
  • the catalyst suitably further comprises a matrix comprising a refractory oxide that serves as binder material.
  • Suitable refractory oxides include alumina, silica, silica-alumina, magnesia, titania, zirconia and mixtures thereof.
  • the matrix may further comprise natural or synthetic clays.
  • the weight ratio of refractory oxide and zeolite suitably ranges from 10:90 to 99:1, preferably from 50:50 to 90:10.
  • the zeolitic catalyst may comprise up to about 40% by weight of further zeolites with a pore diameter above 0.7 nm.
  • zeolites include the faujasite-type zeolites, zeolite beta, zeolite omega and in particular zeolite X and Y.
  • the zeolitic catalyst comprises a zeolite with a pore diameter of from 0.3 to 0.7 nm.
  • the zeolitic catalyst comprises ZSM-5 and zeolite Y.
  • the hydrocarbonaceous feedstock is contacted with the zeolitic catalyst for less than 10 seconds.
  • the minimum contact time is 0.1 second. Very good results are obtained when the hydrocarbonaceous feedstock is contacted with the zeolitic catalyst during 0.2 to 6 seconds.
  • a preferred temparature range is 480 to 900 °C, more preferably 500 to 750 °C.
  • the pressure to be used in the process according to the present invention can be varied within wide ranges. It is, however, preferred that the pressure is such that at prevailing temperature the mixture of hydrocarbons obtained is substantially in its gaseous phase or brought thereto by contact with the catalyst. This can be advantageous since no expensive compressors and high-pressure vessels and other equipment are necessary.
  • a suitable pressure range is from 1 to 10 bar. Subatmospheric pressures are possible, but not preferred. It can be economically advantageous to operate at atmospheric pressure.
  • Other gaseous materials may be present during the conversion of the hydrocarbonaceous feedstock such as steam and/or nitrogen.
  • Olefin production is facilitated by the absence of hydrogen or a hydrogen donor.
  • the present invention is advantageously carried out in the absence of added hydrogen. It is, of course, possible that during the reaction some small molecules, such as hydrogen molecules are formed. However, this amount is usually negligible and will be less than than 0.5 %wt of the product.
  • the process according to the present invention may be carried out in a fixed bed. However, this would imply that extremely high space velocities be required to attain the short contact times envisaged. Therefore, the present invention is preferably carried out in a moving bed.
  • the bed of catalyst may move upwards or downwards. When the bed moves upwards a process somewhat similar to a fluidized catalytic cracking process is obtained.
  • the catalyst is regenerated by subjecting it to a treatment with an oxidizing gas, such as air.
  • an oxidizing gas such as air.
  • the coke formation does not occur at a very high rate.
  • the contact time between feedstock and catalyst should be less than 10 seconds.
  • the contact time generally corresponds with the residence time of the feedstock.
  • the residence time of the catalyst is from 1 to 20 times the residence time of the feedstock.
  • the weight ratio of the catalyst used relative to the hydrocarbonaceous feedstock to be converted may vary widely,viz. from 5 up to 150 kg catalyst per kg of the hydrocarbonaceous feedstock.
  • the weight ratio of catalyst relative to the hydrocarbonaceous feedstock is from 10 to 100, more preferably from 20 to 100.
  • the hydrocarbonaceous feedstock which is to be contacted with the zeolitic catalyst in the process of the present invention can vary within a wide boiling range.
  • suitable feedstocks are relatively light petroleum fractions such as feedstocks comprising C3 ⁇ 4 hydrocarbons (e.g. LPG), naphtha, gasoline fractions and kerosine fractions.
  • Heavier feedstocks may comprise, for example, vacuum distillates, long residues, deasphalted residual oils and atmospheric distillates, for example gas oils and vacuum gas oils.
  • Another attractive feedstock comprises a mixture of hydrocarbons obtained in a Fischer-Tropsch hydrocarbon synthesis process.
  • the hydrocarbonaceous feedstock in this experiment was a hydrowax having the following properties: IBP, °C 298 20 %wt 388 50 %wt 433 90 %wt 495 FBP 552 density 70/4 0.8057 kg/l nitrogen 1.0 ppmw
  • the feedstock was contacted in a downflow reactor by passing it downwards co-currently with a flow of catalyst particles.
  • the catalyst comprised ZSM-5 in a silica-alumina matrix (weight ratio ZSM-5/silica-alumina 25:75).
  • the ZSM-5 had an average crystallite size of 0.1 micrometer.
  • the experiment was carried out at a pressure of 2 bar. Further process conditions and the results obtained are given in Table 1 as shown hereinbelow.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural 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 (13)

  1. Verfahren zur Herstellung einer olefinhaltigen Mischung von Kohlenwasserstoffen, welches Verfahren das Kontaktieren eines kohlenwasserstoffhaltigen Ausgangsmaterials mit einem zeolithaltigen Katalysator bei einer Temperatur von mehr als 480°C während eines Zeitraums von weniger als 10 Sekunden umfaßt, wobei das Katalysator/Ausgangsmaterial-Gewichtsverhältnis im Bereich von 5:1 bis 150:1 liegt und der zeolithaltige Katalysator einen Zeolith mit einem Porendurchmesser von 0,3 bis 0,7 nm und eine durchschnittliche Kristallitgröße von weniger als 2 »m aufweist.
  2. Verfahren nach Anspruch 1, in welchem der Zeolith eine durchschnittliche Kristallitgröße von weniger als 1 »m aufweist.
  3. Verfahren nach Anspruch 2, in welchem der Zeolith eine durchschnittliche Kristallitgröße im Bereich von 0,01 bis 0,5 »m aufweist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, in welchem der Zeolith einen Porendurchmesser von 0,5 bis 0,7 nm aufweist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, in welchem der Zeolith ausgewählt ist aus kristallinen (Metallo)-Silikaten mit einer ZSM-5-Struktur, Ferrierit, Erionit und Mischungen davon.
  6. Verfahren nach einem der Ansprüche 1 bis 5, in welchem der Zeolith im wesentlichen in seiner Wasserstofform vorliegt.
  7. Verfahren nach einem der Ansprüche 1 bis 6, in welchem der zeolithaltige Katalysator bis zu 40 Gewichtsprozent eines weiteren Zeoliths mit einem Porendurchmesser von mehr als 0,7 nm enthält.
  8. Verfahren nach einem der Ansprüche 1 bis 7, in welchem das Ausgangsmaterial über einen Zeitraum von 0,2 bis 6 Sekunden mit dem zeolithaltigen Katalysator kontaktiert wird.
  9. Verfahren nach einem der Ansprüche 1 bis 8, in welchem die Temperatur 480 bis 900°C beträgt.
  10. Verfahren nach Anspruch 9, in welchem die Temperatur im Bereich von 500 bis 750°C liegt.
  11. Verfahren nach einem der Ansprüche 1 bis 10, in welchem der Druck im Bereich von 1 bis 10 Bar liegt.
  12. Verfahren nach einem der Ansprüche 1 bis 11, in welchem das Katalysator/Ausgangsmaterial-Gewichtsverhältnis im Bereich von 10:1 bis 100:1 liegt.
  13. Verfahren nach einem der Ansprüche 1 bis 12, das in einem bewegten Bett des Katalysators durchgeführt wird.
EP91203184A 1990-12-10 1991-12-04 Verfahren zur Herstellung eines Olefine enthaltenden Kohlenwasserstoffgemisches Revoked EP0490435B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB909026775A GB9026775D0 (en) 1990-12-10 1990-12-10 Process for the preparation of an olefins-containing mixture of hydrocarbons
GB9026775 1990-12-10

Publications (2)

Publication Number Publication Date
EP0490435A1 EP0490435A1 (de) 1992-06-17
EP0490435B1 true EP0490435B1 (de) 1994-08-24

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EP91203184A Revoked EP0490435B1 (de) 1990-12-10 1991-12-04 Verfahren zur Herstellung eines Olefine enthaltenden Kohlenwasserstoffgemisches

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EP (1) EP0490435B1 (de)
JP (1) JPH04352731A (de)
KR (1) KR920012398A (de)
CN (1) CN1033317C (de)
AU (1) AU645153B2 (de)
CA (1) CA2056833A1 (de)
DE (1) DE69103614T2 (de)
ES (1) ES2059044T3 (de)
GB (1) GB9026775D0 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6222087B1 (en) 1999-07-12 2001-04-24 Mobil Oil Corporation Catalytic production of light olefins rich in propylene
US6835863B2 (en) 1999-07-12 2004-12-28 Exxonmobil Oil Corporation Catalytic production of light olefins from naphtha feed
US10689586B2 (en) 2015-12-21 2020-06-23 Sabic Global Technologies B.V. Methods and systems for producing olefins and aromatics from coker naphtha

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5628978A (en) * 1994-12-23 1997-05-13 Intevep, S.A. MTW zeolite for cracking feedstock into olefins and isoparaffins
US5888378A (en) * 1997-03-18 1999-03-30 Mobile Oil Corporation Catalytic cracking process
IT1290433B1 (it) * 1997-03-24 1998-12-03 Euron Spa Processo di cracking catalitico a letto fluido caratterizzato da alta selettivita' ad olefine
EP1424128B1 (de) * 2002-12-01 2008-12-31 Süd-Chemie Ag Verwendung eines Katalysators auf der Basis von kristallinem Alumosilicat
US7582203B2 (en) 2004-08-10 2009-09-01 Shell Oil Company Hydrocarbon cracking process for converting gas oil preferentially to middle distillate and lower olefins
JP2008510032A (ja) 2004-08-10 2008-04-03 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ 炭化水素供給原料から中間留分生成物及び低級オレフィンを製造する方法及び装置
FR2875234B1 (fr) * 2004-09-15 2006-11-03 Inst Francais Du Petrole Procede de production de propylene fonctionnant en lit mobile avec recyclage d'une fraction de catalyseur use
CN101679880B (zh) 2007-04-13 2013-05-22 国际壳牌研究有限公司 用于由烃原料生产中间馏分油产物和低级烯烃的系统和方法
KR100904297B1 (ko) * 2007-10-26 2009-06-25 한국화학연구원 연속적인 2단계 촉매 반응을 이용한 합성가스로부터 경질올레핀의 제조방법
JP2012045505A (ja) * 2010-08-27 2012-03-08 Idemitsu Kosan Co Ltd 軽質オレフィン類製造用触媒、その製造方法及びそれを用いた軽質オレフィン類の製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3926782A (en) * 1973-02-09 1975-12-16 Mobil Oil Corp Hydrocarbon conversion
GB8904408D0 (en) * 1989-02-27 1989-04-12 Shell Int Research Process for the conversion of a hydrocarbonaceous feedstock

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6222087B1 (en) 1999-07-12 2001-04-24 Mobil Oil Corporation Catalytic production of light olefins rich in propylene
US6835863B2 (en) 1999-07-12 2004-12-28 Exxonmobil Oil Corporation Catalytic production of light olefins from naphtha feed
US10689586B2 (en) 2015-12-21 2020-06-23 Sabic Global Technologies B.V. Methods and systems for producing olefins and aromatics from coker naphtha

Also Published As

Publication number Publication date
KR920012398A (ko) 1992-07-27
DE69103614D1 (de) 1994-09-29
AU8895991A (en) 1992-06-11
GB9026775D0 (en) 1991-01-30
EP0490435A1 (de) 1992-06-17
CN1062339A (zh) 1992-07-01
CA2056833A1 (en) 1992-06-11
CN1033317C (zh) 1996-11-20
ES2059044T3 (es) 1994-11-01
JPH04352731A (ja) 1992-12-07
AU645153B2 (en) 1994-01-06
DE69103614T2 (de) 1995-03-02

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