WO2004056943A1 - Procede et reacteur pour la production d'olefines par reaction de vapocraquage de charges d'hydrocarbures liquides en presence d'un catalyseur - Google Patents

Procede et reacteur pour la production d'olefines par reaction de vapocraquage de charges d'hydrocarbures liquides en presence d'un catalyseur Download PDF

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Publication number
WO2004056943A1
WO2004056943A1 PCT/EP2003/014780 EP0314780W WO2004056943A1 WO 2004056943 A1 WO2004056943 A1 WO 2004056943A1 EP 0314780 W EP0314780 W EP 0314780W WO 2004056943 A1 WO2004056943 A1 WO 2004056943A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
reactor
ranging
process according
along
Prior art date
Application number
PCT/EP2003/014780
Other languages
English (en)
Inventor
Massimo Romagnoli
Paolo Pollesel
Caterina Rizzo
Giuseppe Bellussi
Carlo Perego
Gabriele Carlo Ettore Clerici
Francesca Galimberti
Original Assignee
Polimeri Europa S.P.A.
Enitecnologie S.P.A.
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 Polimeri Europa S.P.A., Enitecnologie S.P.A. filed Critical Polimeri Europa S.P.A.
Priority to AU2003293978A priority Critical patent/AU2003293978A1/en
Priority to EA200500844A priority patent/EA200500844A1/ru
Priority to CA002510878A priority patent/CA2510878A1/fr
Publication of WO2004056943A1 publication Critical patent/WO2004056943A1/fr
Priority to EGNA2005000315 priority patent/EG23828A/xx

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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
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • 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
    • 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
    • C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed

Definitions

  • the present invention relates to a process and a reactor for the production of light olefins by steam cracking reactions of liquid hydrocarbon feeds in the presence of a suitable catalyst.
  • the most widely-used method for the production of light olefins, in particular ethylene and propylene, is the steam cracking process, in which a hydrocarbon feed is heated, in the presence of water vapour, in specific ovens for producing a gaseous stream rich in olefins.
  • Steam cracking is a thermal process which, on an industrial scale, is carried out without catalysts.
  • the catalyst is based on Al 2 0 3 /CaO and contains, as gasification promoters, compounds of alkaline metals.
  • This technology can only be applied, however, to conventionally designed cracking plants and operating with conventional feeds . From literature, it therefore emerges that catalysts based on calcium aluminate can be used in steam cracking reactions for the production of ethylene and propylene.
  • the calcium aluminates which can be formed are the following, in an increasing order of calcium content: CaO»6Al 2 0 3 , CaO»2Al 2 0 3 , 3CaO * 5Al 2 0 3 , CaO»Al 2 0 3 , 5CaO»3Al 2 0 3 ,
  • the residence time of the gas in the catalytic bed should be minimum, preferably less than 0.1 s; • the pressure drops must be limited;
  • the tubular element of the reactor should not be subjected to a quantity of heat per surface unit higher than 25,000 Btu/h/ft 2 ;
  • the operating temperature of the wall of the reaction tube is preferably lower than 1050°C.
  • the presence of the internal cylindrical element allows a lower contact time and limits pressure drops.
  • the process for the production of light olefins, object of the present invention, by the steam cracking reac- tion of liquid hydrocarbon feeds, preferably selected from naphtha, kerosene, atmospheric gas oil, vacuum gas oil and oil residues, alone or mixed with each other, in the presence of a suitable catalyst, is characterized in that it is carried out at a reaction temperature ranging from 700 to 850°C, at a pressure ranging from 1.1 to 4.5 absolute At and for a contact time ranging from 0.02 to 0.3 sec, preferably from 0.05 to 0.15 sec, in one or more reaction zones whose transversal section is in the form of a circular crown, the ratio between the area of said circular crown and the circular section ranging from 0.35 to 0.99, preferably from 0.75 to 0.95.
  • the catalyst used can be uniformly distributed along the reaction zone or it can be deposited, preferably by means of laying, along the internal concave wall with a higher radius and/or along the internal convex wall with a lower radius .
  • the results can be improved, allowing even more reduced ⁇ to be adopted with respect to the basic case or with tubes having a greater length, if the catalyst is formed in such a way as to reduce the pressure drops .
  • the catalyst can therefore be in the form of spheres with suitable dimensions or in particular in extruded form suitably shaped to give the least possible resistance to the flow of the feed (rings, saddles, trilobates, etc.) or structured (of the honeycomb type or similar) , which offer a high exposed surface with low pressure drops .
  • the catalytic material is suitable for being processed to produce extruded or structured products.
  • the structured products can entirely consist of calcium- aluminate catalyst or the catalyst can be deposited on a metallic carrier.
  • the catalyst consist of one or more crystalline calcium aluminates and molybdenum and/or vanadium oxides.
  • structured products under the same conditions, produce much lower pressure drops with respect to a packed bed is demonstrated both by theoretical calculations and experimental data.
  • a reduction of 2-3 orders of magnitude is indicated, with the same linear gas rate, by the use of monolithic catalysts (structured) instead of a bed packed with spherical particles (E. Tronconi . , A. Beretta, Catalysis Today, 52 (1999), 249).
  • Hot recovery fumes can be optionally sent along the tubular-shaped area obtained, enclosed by the reaction zone, to contribute to the heating of the process itself.
  • a further object of the present patent application relates to the reactor for effecting steam cracking reac- tions , which is characterized in that it comprises one or more cylindrical tubes, with the same or different section, consisting of a tubular core and a reaction zone whose transversal section is in the form of a circular crown, the ratio between the area of said circular crown and the cir- cular section ranging from 0.35 to 0.99, preferably from 0 . 75 to 0 . 95 .
  • the catalyst can be uniformly distributed in the reactor along the reaction zone or it can be deposited, optionally by means of laying, along the internal concave wall with a higher radius and/or along the internal convex wall with a lower radius .
  • the tubular core can be made of inert material or it can be hollow using a hollow tube, in which hot recovery fumes from the cracking process flow, thus contributing to the heating (or diminishing the thermal dispersions) of the process .
  • the tube or tubes contained in the reactor are represented in figures 2, 3, 4, 5, 6 and 7; more particularly, the tube is illustrated in figure 2 in a perspective view, in figure 3 in a partially sectional perspective view, in figure 4 in a longitudinal section, in figure 5 in a transversal section with the core filled with inert material and with the catalyst uniformly distributed, in figure 6 in a transversal section with the core hollow and with the catalyst uniformly distributed and in figure 7 in a longitudi- nal section with the core hollow and with the catalyst laid along both the internal concave wall with a higher radius
  • EXAMPLE 1 (Comparative) Reactor filled with a catalytic bed consisting of spherical particles having a diameter of 5 mm.
  • Reactor with an inert cylindrical element having a diameter of 5 mm Reactor with an inert cylindrical element having a diameter of 5 mm.
  • Reactor with an inert cylindrical element having a diameter of 10 mm Reactor with an inert cylindrical element having a diameter of 10 mm.

Landscapes

  • 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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

L'invention concerne un procédé de production d'oléfines légères par réaction de vapocraquage de charges d'hydrocarbures liquides, de préférence sélectionnés parmi naphtha, kérosène, gazole atmosphérique, gazole sous vide et résidus d'hydrocarbures, seuls ou en combinaison, en présence d'un catalyseur approprié, à une température de réaction comprise entre 700 et 850 °C, à une pression comprise entre 1,1 et 4,5 atm absolues et pendant un temps de mise en contact compris entre 0,02 et 0,3 s; de préférence entre 0,05 et 0,15 s; dans un réacteur comprenant un ou plusieurs tuyaux cylindriques, de section identique ou différente, constitués d'une partie centrale tubulaire et d'une zone de réaction dont la section transversale se présente sous forme de couronne circulaire, le rapport entre la surface de cette couronne circulaire et la section circulaire étant compris entre 0,35 et 0,99; de préférence entre 0,75 et 0,95.
PCT/EP2003/014780 2002-12-20 2003-12-11 Procede et reacteur pour la production d'olefines par reaction de vapocraquage de charges d'hydrocarbures liquides en presence d'un catalyseur WO2004056943A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU2003293978A AU2003293978A1 (en) 2002-12-20 2003-12-11 Process and reactor for the production of olefins by the steam cracking reaction of liquid hydrocarbon feeds in the presence of a catalyst
EA200500844A EA200500844A1 (ru) 2002-12-20 2003-12-11 Способ и реактор для получения олефинов при помощи реакции парового крекинга жидкостного углеводородного сырья в присутствии катализатора
CA002510878A CA2510878A1 (fr) 2002-12-20 2003-12-11 Procede et reacteur pour la production d'olefines par reaction de vapocraquage de charges d'hydrocarbures liquides en presence d'un catalyseur
EGNA2005000315 EG23828A (en) 2002-12-20 2005-06-18 Process and reactor for the production of olefins by the steam craking reaction of liquid hydrocarbon feeds in the presence of a catalyst

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2002A002710 2002-12-20
ITMI20022710 ITMI20022710A1 (it) 2002-12-20 2002-12-20 Procedimento e reattore per la produzione di olefine leggere mediante reazione di steam cracking di cariche idrocarburiche liquide in presenza di catalizzatore

Publications (1)

Publication Number Publication Date
WO2004056943A1 true WO2004056943A1 (fr) 2004-07-08

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/014780 WO2004056943A1 (fr) 2002-12-20 2003-12-11 Procede et reacteur pour la production d'olefines par reaction de vapocraquage de charges d'hydrocarbures liquides en presence d'un catalyseur

Country Status (7)

Country Link
CN (1) CN100360645C (fr)
AU (1) AU2003293978A1 (fr)
CA (1) CA2510878A1 (fr)
EA (1) EA200500844A1 (fr)
EG (1) EG23828A (fr)
IT (1) ITMI20022710A1 (fr)
WO (1) WO2004056943A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2904502A (en) * 1954-02-19 1959-09-15 Hercules Powder Co Ltd Method of cracking hydrocarbons
US3650946A (en) * 1969-09-10 1972-03-21 Gulf Oil Corp Fluid catalytic cracking in a dense catalyst bed
EP0282371A1 (fr) * 1987-02-11 1988-09-14 Compagnie De Raffinage Et De Distribution Total France Procédé et dispositif pour le craquage catalytique de charges d'hydrocarbures
US5625111A (en) * 1992-08-20 1997-04-29 Bp Chemicals Limited Process for the production of mono-olefins

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2904502A (en) * 1954-02-19 1959-09-15 Hercules Powder Co Ltd Method of cracking hydrocarbons
US3650946A (en) * 1969-09-10 1972-03-21 Gulf Oil Corp Fluid catalytic cracking in a dense catalyst bed
EP0282371A1 (fr) * 1987-02-11 1988-09-14 Compagnie De Raffinage Et De Distribution Total France Procédé et dispositif pour le craquage catalytique de charges d'hydrocarbures
US5625111A (en) * 1992-08-20 1997-04-29 Bp Chemicals Limited Process for the production of mono-olefins

Also Published As

Publication number Publication date
AU2003293978A1 (en) 2004-07-14
CA2510878A1 (fr) 2004-07-08
CN1742069A (zh) 2006-03-01
ITMI20022710A1 (it) 2004-06-21
CN100360645C (zh) 2008-01-09
EA200500844A1 (ru) 2006-02-24
AU2003293978A8 (en) 2004-07-14
EG23828A (en) 2007-09-26

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