EP0347003B1 - Procédé de conversion d'une charge hydrocarbonée - Google Patents

Procédé de conversion d'une charge hydrocarbonée Download PDF

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Publication number
EP0347003B1
EP0347003B1 EP89201558A EP89201558A EP0347003B1 EP 0347003 B1 EP0347003 B1 EP 0347003B1 EP 89201558 A EP89201558 A EP 89201558A EP 89201558 A EP89201558 A EP 89201558A EP 0347003 B1 EP0347003 B1 EP 0347003B1
Authority
EP
European Patent Office
Prior art keywords
feedstock
process according
catalyst
zeolite
conversion
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
EP89201558A
Other languages
German (de)
English (en)
Other versions
EP0347003A1 (fr
Inventor
Ian Ernst Maxwell
Der Eijk Jjohan Meindert Van
Jaydeep Biswas
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.)
Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Priority claimed from GB888814293A external-priority patent/GB8814293D0/en
Priority claimed from GB898904409A external-priority patent/GB8904409D0/en
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP0347003A1 publication Critical patent/EP0347003A1/fr
Application granted granted Critical
Publication of EP0347003B1 publication Critical patent/EP0347003B1/fr
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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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • 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 conversion of a hydrocarbonaceous feedstock.
  • the present invention provides a process for the conversion of a hydrocarbonaceous feedstock having an end boiling point of at most 330 °C to obtain a high yield of a predominantly olefinic C2 ⁇ 4 product, which process comprises contacting the feedstock in a reaction zone, with a zeolitic catalyst comprising a zeolite with a pore diameter of 0.3 to 0.7 nm at a temperature above 500 °C during 0.2 to 0.6 seconds, and separation of product without the use of residual oil quench before the separation.
  • a process is disclosed employing a catalyst comprising an X or Y type faujasite or a mordenite cracking component and a lower cracking activity amorphous component or an erionite, offretite or ZSM-5 small pore component for the conversion of a first stage feed comprising a recycle oil product stream of cracking and a second quench stage feed comprising a fresh residual oil whereby the effects of metal components and the coking characteristics of the residual oil feed are suppressed by means of staged injection and temperature control in individual stages.
  • Increase in octane value of residual oil conversion product is disclosed due to combined conversion with the recycle stream.
  • US-A-4,100,2108 describes a process for the preparation of LPG (saturated C3 ⁇ 4-hydrocarbons) and gasoline starting from an olefinic stream, using a catalyst with a pore diameter of less than 0.7 nm. Since it was known that such zeolitic catalysts have activity to catalyze the conversion of olefins to saturated and aromatic hydrocarbons, it is surprising that in the present process olefins are produced and relatively little saturated gaseous hydrocarbon product is formed.
  • the temperature during the reaction is above 500 °C and preferably up to 900 °C.
  • the temperature is preferably from 550 to 800 °C.
  • the zeolitic catalyst comprises one or more zeolites with a pore diameter of from 0.3 to 0.7 nm.
  • the catalyst suitably further comprises a refractory oxide that serves as binder material. Suitable refractory oxides include alumina, silica, silica-alumina, magnesia, titania, zirconia and mixtures thereof. Alumina is especially preferred.
  • the weight ratio of refractory oxide and zeolite suitably ranges from 10:90 to 90:10, preferably from 50:50 to 85:15.
  • the zeolitic catalyst preferably comprises as zeolite substantially only zeolites with a pore diameter of from 0.3 to 0.7 nm. Illustrative of the invention is the use of a zeolitic catalyst comprising a zeolite of pore diameter of 0.5 to 0.7 nm at a temperature above 500 °C and up to 750 °C.
  • zeolite in this specification is not to be regarded to comprise only crystalline aluminium silicates.
  • 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.
  • Examples of zeolites that may be used in the process of the invention and that have a pore diameter of 0.3 to 0.7 nm 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, described in US-A-4,500,651, TASO-45, described in EP-A-229,295, boron silicates, described in e.g. 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.
  • 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, described in US-A-4,500,651, TASO-45, described in EP-A-229,29
  • the zeolite is selected from the group consisting of crystalline metal silicates having a ZSM-5 structure, ferrierite, erionite and mixtures thereof.
  • crystalline metal 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.
  • an amount of alkali metal oxide is present in the readily prepared zeolite.
  • 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 present process is substantially in its hydrogen form.
  • the pressure in the present process can be varied within wide ranges. It is, however, preferred that the pressure is such that at the prevailing temperature the feedstock is substantially in its gaseous phase or brought thereinto by contact with the catalyst. Then it is easier to achieve the short contact times envisaged. Hence, the pressure is preferably relatively low. This can be advantageous since no expensive compressors and high-pressure vessels and other equipment is 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 such as steam and/or nitrogen.
  • the present process 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 after having been contacted with the feedstock to a treatment with an oxidizing gas, such as air.
  • an oxidizing gas such as air.
  • a continuous regeneration similar to the regeneration carried out in a fluidized catalytic cracking process, is especially preferred.
  • the residence time of the catalyst particles in a reaction zone is longer than the residence time of the feedstock in the reaction zone.
  • 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 catalyst/feedstock weight ratio is not critical, it is preferred that the weight ratio varies from 1 to 150 kg or more of catalyst per kg of feedstock. Preferably, the catalyst/feedstock weight ratio is from 20 to 120:1.
  • the feedstock which is to be converted in the present process comprises hydrocarbons which have an end boiling point of at most 330°C.
  • hydrocarbons which have an end boiling point of at most 330°C.
  • relatively light petroleum fractions like naphtha and kerosine, are included.
  • the feedstock has an initial boiling point of -45 °C.
  • Suitable feedstocks include C3 ⁇ 4-hydrocarbons (e.g. LPG), naphtha, gasoline fractions, kerosine fractions and mixtures thereof.
  • a feedstock with a relatively high nitrogen content may be used with substantially no effect on the catalyst activity.
  • Suitable feedstocks may have a nitrogen content of more than 25 ppmw, calculated as nitrogen.
  • the feedstock may even have a nitrogen content of 100 to 1000 ppmw, calculated as nitrogen.
  • the experiments were carried out in a down flow reactor in which co-currently a flow of feedstock and catalyst particles, having an average particle size of 74 micrometers, was passed downwards.
  • the catalyst used comprised ZSM-5 in hydrogen form in an alumina matrix (weight ratio ZSM-5/alumina was 1:3). All experiments were carried out at atmospheric pressure. Further process conditions and the results of the experiments are indicated in Table 1 below.
  • n-paraffins are preferentially cracked and yield gaseous products which comprise a significant amount of olefins, especially at temperatures above 500 °C. Above 500 °C it will be seen that there is a markedly increased C3 and C4 olefin/paraffin ratio and an overall increased conversion to lower olefins.
  • the resulting liquid product has a higher iso/normal-paraffin ratio than the starting mixture, so that, additionally, the octane number and hence the quality of the liquid product as a gasoline has been enhanced.

Claims (10)

  1. Procédé de conversion d'une charge hydrocarbonée possédant un point d'ébullition final d'au maximum 330°C en vue d'obtenir un produit à rapport paraffine en C₃ et C₄ à oléfine accru et une conversion globale en oléfines inférieures augmentée, caractérisé en ce que l'on met le charge en contact, dans une zone de réaction, avec un catalyseur zéolitique comprenant une zéolite d'un diamètre des pores de 0,3 à 0,7 nm, à une température supérieure à 500°C, pendant 0,2 à 0,6 seconde et on sépare le produit sans recourir à l'utilisation d'une suppression d'huile résiduelle avant la séparation.
  2. Procédé suivant la revendication 1, caractérisé en ce que le catalyseur zéolitique ne comprend, à titre de zéolites, qu'uniquement des zéolites possédant un diamètre des pores de 0,3 à 0,7 nm.
  3. Procédé suivant l'une quelconque des revendications 1 et 2, caractérisé en ce que la zéolite possède un diamètre des pores de 0,5 à 0,7 nm et la température s'élève jusqu'à 750°C.
  4. Procédé suivant l'une quelconque des revendications 1 à 3, caractérisé en ce que l'on choisit la zéolite dans le groupe formé par des silicates de métaux cristallins, possédant la structure ZSM-5, la ferriérite, l'érionite et leurs mélanges.
  5. Procédé suivant l'une quelconque des revendications 1 à 4, caractérisé en ce que la zéolite se présente sous sa forme hydrogène.
  6. Procédé suivant l'une quelconque des revendications 1 à 5, caractérisé en ce que la pression varie de 1 à 10 bars.
  7. Procédé suivant l'une quelconque des revendications 1 à 6, caractérisé en ce que le rapport pondéral catalyseur/charge fluctue de 1 à 150:1, de préférence, de 20 à 120:1.
  8. Procédé suivant l'une quelconque des revendications 1 à 7, caractérisé en ce qu'on l'entreprend dans un lit de catalyseur en mouvement.
  9. Procédé suivant l'une quelconque des revendications 1 à 8, caractérisé en ce que la charge possède un point d'ébullition initial d'au moins -45°C.
  10. Procédé suivant la revendication 9, caractérisé en ce que la charge comprend des hydrocarbures en C₃-C₄, du naphta, de l'essence, du kérosène ou leurs mélanges.
EP89201558A 1988-06-16 1989-06-14 Procédé de conversion d'une charge hydrocarbonée Revoked EP0347003B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB888814293A GB8814293D0 (en) 1988-06-16 1988-06-16 Process for conversion of hydrocarbonaceous feedstock
GB8814293 1988-06-16
GB898904409A GB8904409D0 (en) 1989-02-27 1989-02-27 Process for the conversion of a hydrocarbonaceous feedstock
GB8904409 1989-02-27

Publications (2)

Publication Number Publication Date
EP0347003A1 EP0347003A1 (fr) 1989-12-20
EP0347003B1 true EP0347003B1 (fr) 1996-05-08

Family

ID=26294030

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89201558A Revoked EP0347003B1 (fr) 1988-06-16 1989-06-14 Procédé de conversion d'une charge hydrocarbonée

Country Status (10)

Country Link
EP (1) EP0347003B1 (fr)
JP (1) JPH0245593A (fr)
KR (1) KR910001002A (fr)
CN (1) CN1021913C (fr)
AU (1) AU614626B2 (fr)
BR (1) BR8902859A (fr)
DE (1) DE68926408T2 (fr)
ES (1) ES2087073T3 (fr)
PH (1) PH25773A (fr)
RU (1) RU2002794C1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6069287A (en) * 1998-05-05 2000-05-30 Exxon Research And Engineering Co. Process for selectively producing light olefins in a fluid catalytic cracking process
US6093867A (en) * 1998-05-05 2000-07-25 Exxon Research And Engineering Company Process for selectively producing C3 olefins in a fluid catalytic cracking process
US6106697A (en) * 1998-05-05 2000-08-22 Exxon Research And Engineering Company Two stage fluid catalytic cracking process for selectively producing b. C.su2 to C4 olefins
US6118035A (en) * 1998-05-05 2000-09-12 Exxon Research And Engineering Co. Process for selectively producing light olefins in a fluid catalytic cracking process from a naphtha/steam feed
US6222087B1 (en) 1999-07-12 2001-04-24 Mobil Oil Corporation Catalytic production of light olefins rich in propylene
US6313366B1 (en) 1998-05-05 2001-11-06 Exxonmobile Chemical Patents, Inc. Process for selectively producing C3 olefins in a fluid catalytic cracking process
US6315890B1 (en) 1998-05-05 2001-11-13 Exxonmobil Chemical Patents Inc. Naphtha cracking and hydroprocessing process for low emissions, high octane fuels
US6803494B1 (en) 1998-05-05 2004-10-12 Exxonmobil Chemical Patents Inc. Process for selectively producing propylene in a fluid catalytic cracking process
US6835863B2 (en) 1999-07-12 2004-12-28 Exxonmobil Oil Corporation Catalytic production of light olefins from naphtha feed

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8828206D0 (en) * 1988-12-02 1989-01-05 Shell Int Research Process for conversion of hydrocarbonaceous feedstock
GB8904408D0 (en) * 1989-02-27 1989-04-12 Shell Int Research Process for the conversion of a hydrocarbonaceous feedstock
GB8908081D0 (en) * 1989-04-11 1989-05-24 Shell Int Research Process for the conversion of a hydrocarbonaceous feedstock
US5100534A (en) * 1989-11-29 1992-03-31 Mobil Oil Corporation Hydrocarbon cracking and reforming process
US5100533A (en) * 1989-11-29 1992-03-31 Mobil Oil Corporation Process for production of iso-olefin and ether
US4969987A (en) * 1989-11-29 1990-11-13 Mobil Oil Corporation Integrated process for production of gasoline and ether
GB9114390D0 (en) * 1991-07-03 1991-08-21 Shell Int Research Hydrocarbon conversion process and catalyst composition
EP0920911A1 (fr) 1997-12-05 1999-06-09 Fina Research S.A. Production de catalyseurs pour la conversion d'oléfines
US6388152B1 (en) 1998-05-05 2002-05-14 Exxonmobil Chemical Patents Inc. Process for producing polypropylene from C3 olefins selectively produced in a fluid catalytic cracking process
US6339180B1 (en) 1998-05-05 2002-01-15 Exxonmobil Chemical Patents, Inc. Process for producing polypropylene from C3 olefins selectively produced in a fluid catalytic cracking process
US6602403B1 (en) 1998-05-05 2003-08-05 Exxonmobil Chemical Patents Inc. Process for selectively producing high octane naphtha
US6455750B1 (en) 1998-05-05 2002-09-24 Exxonmobil Chemical Patents Inc. Process for selectively producing light olefins

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3140322A (en) * 1958-08-14 1964-07-07 Socony Mobil Oil Co Inc Selective catalytic conversion
US3856659A (en) * 1972-12-19 1974-12-24 Mobil Oil Corp Multiple reactor fcc system relying upon a dual cracking catalyst composition
US3886060A (en) * 1973-04-30 1975-05-27 Mobil Oil Corp Method for catalytic cracking of residual oils
US4218344A (en) * 1975-12-19 1980-08-19 Standard Oil Company (Indiana) Catalytic cracking with reduced emission of noxious gases
US4100218A (en) * 1977-05-31 1978-07-11 Mobil Oil Corporation Ethane conversion process
US4390413A (en) * 1979-12-26 1983-06-28 Chevron Research Company Hydrocarbon upgrading process
US4310440A (en) * 1980-07-07 1982-01-12 Union Carbide Corporation Crystalline metallophosphate compositions
GB8814292D0 (en) * 1988-06-16 1988-07-20 Shell Int Research Process for conversion of hydrocarbonaceous feedstock

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6069287A (en) * 1998-05-05 2000-05-30 Exxon Research And Engineering Co. Process for selectively producing light olefins in a fluid catalytic cracking process
US6093867A (en) * 1998-05-05 2000-07-25 Exxon Research And Engineering Company Process for selectively producing C3 olefins in a fluid catalytic cracking process
US6106697A (en) * 1998-05-05 2000-08-22 Exxon Research And Engineering Company Two stage fluid catalytic cracking process for selectively producing b. C.su2 to C4 olefins
US6118035A (en) * 1998-05-05 2000-09-12 Exxon Research And Engineering Co. Process for selectively producing light olefins in a fluid catalytic cracking process from a naphtha/steam feed
US6258257B1 (en) 1998-05-05 2001-07-10 Exxonmobil Research And Engineering Company Process for producing polypropylene from C3 olefins selectively produced by a two stage fluid catalytic cracking process
US6258990B1 (en) 1998-05-05 2001-07-10 Exxonmobil Research And Engineering Company Process for producing polypropylene from C3 olefins selectively produced in a fluid catalytic cracking process from a naphtha/steam feed
US6313366B1 (en) 1998-05-05 2001-11-06 Exxonmobile Chemical Patents, Inc. Process for selectively producing C3 olefins in a fluid catalytic cracking process
US6315890B1 (en) 1998-05-05 2001-11-13 Exxonmobil Chemical Patents Inc. Naphtha cracking and hydroprocessing process for low emissions, high octane fuels
US6803494B1 (en) 1998-05-05 2004-10-12 Exxonmobil Chemical Patents Inc. Process for selectively producing propylene in a fluid catalytic cracking process
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

Also Published As

Publication number Publication date
DE68926408T2 (de) 1996-10-31
CN1039046A (zh) 1990-01-24
AU614626B2 (en) 1991-09-05
BR8902859A (pt) 1990-02-01
AU3639489A (en) 1989-12-21
DE68926408D1 (de) 1996-06-13
JPH0245593A (ja) 1990-02-15
RU2002794C1 (ru) 1993-11-15
KR910001002A (ko) 1991-01-30
CN1021913C (zh) 1993-08-25
EP0347003A1 (fr) 1989-12-20
ES2087073T3 (es) 1996-07-16
PH25773A (en) 1991-10-18

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