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WO2008014920A2 - Craquage catalytique de composés organiques au moyen de zéolite itq-33 - Google Patents

Craquage catalytique de composés organiques au moyen de zéolite itq-33 Download PDF

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Publication number
WO2008014920A2
WO2008014920A2 PCT/EP2007/006629 EP2007006629W WO2008014920A2 WO 2008014920 A2 WO2008014920 A2 WO 2008014920A2 EP 2007006629 W EP2007006629 W EP 2007006629W WO 2008014920 A2 WO2008014920 A2 WO 2008014920A2
Authority
WO
WIPO (PCT)
Prior art keywords
catalytic cracking
process according
zeolitic material
cracking process
itq
Prior art date
Application number
PCT/EP2007/006629
Other languages
English (en)
Other versions
WO2008014920A3 (fr
Inventor
Avelino CORMA CANÓS
María José DIAZ CABAÑAS
Maria Cristina Martinez Sanchez
Manuel Moliner Marin
Original Assignee
Universidad Politecnica De Valencia
Consejo Superior De Investigaciones Cientificas
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 Universidad Politecnica De Valencia, Consejo Superior De Investigaciones Cientificas filed Critical Universidad Politecnica De Valencia
Publication of WO2008014920A2 publication Critical patent/WO2008014920A2/fr
Publication of WO2008014920A3 publication Critical patent/WO2008014920A3/fr

Links

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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • B01J29/80—Mixtures of different zeolites
    • 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
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta

Definitions

  • Catalytic cracking especially produces a large amount of propylene, one of the olefins in greatest demand.
  • FCC contributes approximately 30% of the gasoline stream in a refinery, and at the present time when there is, especially in Europe, an excess global production of gasoline, selectivity to propylene in the FCC unit may be increased, optimizing the economic yield of the unit.
  • Propylene production in the FCC may be increased by modifying the operating conditions in the unit, such as for example increasing the temperature of the reactor. Nevertheless, this solution produces a significant increase in gases, and especially of the undesirable dry gas. Better results are obtained using novel catalyst compositions that involve the use of zeolite mixtures.
  • the use of zeolite ZSM-5 as an additive in FCC catalysts also leads to an increase in C 3 and C 4 olefins (see for example US-3758403, US-3769202; US-3894931 ; US-3894933; US-3894934; US-3926782; US-4309280; US-4309279; US-437458 and Buchanan, J. S.
  • the present invention relates to a cracking process for organic compounds and preferably for oil-derived or synthetic hydrocarbon fractions, using the zeolitic material called ITQ-33 as the active zeolitic component, the structure of which is defined by a characteristic X-ray diffractogram.
  • ITQ-33 the zeolitic material
  • the relative positions, widths, and intensities of the diffraction peaks may be modified according to the chemical composition of the material, as well as by the degree of hydration and the crystal size of the zeolite.
  • this zeolitic material will be shown to provide it with activity for cracking the feeds of catalytic cracking units, as well as for producing, surprisingly, on its own and/or in combination with other zeolites, and at the same time, a high yield of diesel and a high yield of light olefins, especially propylene.
  • the present invention relates to a catalytic cracking process for organic compounds that uses at least one zeolitic material called ITQ-33.
  • This zeolitic material ITQ-33 used as a catalyst in the process of the present invention exhibits a three-directional channel system, with straight ultra-large pore channels parallel to the c axis, defined by circular openings formed by 18 atoms in tetrahedral coordination. These channels are interconnected by a system of channels or windows formed by 10 atoms in tetrahedral coordination located in the ab plane, and with openings of 6.1 x 4.3 A.
  • This zeolitic material exhibits a new structure or topology that is characterized by a specific X-ray diffraction pattern.
  • VW very weak corresponds to a value of less than 20, W (weak) from 20 to 40, M (medium) between 40 and 60, S (strong) between 60 and 80 and VS (very strong) between 80 and 100.
  • the crystalline structure of zeolite ITQ-33 is characterized by an X- ray diffraction pattern the most characteristic lines of which are shown in Table 2.
  • VW very weak
  • M medium
  • S strong
  • VS very strong
  • Zeolite ITQ-33 may be synthesized in fluoride medium or in OH " medium, using an organic structure-directing agent, such as for example the hexamethonium cation, and forming a gel containing in its composition the source of at least one T IV element, amongst which Si and Ge are preferred, and of one or more T elements, amongst which Al, B, Fe and Ga are preferred, preferably Al, B or a mixture of both, the ⁇ IV / ⁇ m ratio being at least 5.
  • an organic structure-directing agent such as for example the hexamethonium cation
  • the synthesized zeolite is subjected to an elimination process to eliminate any organic matter occluded inside the material, which is performed by means of extraction, thermal treatment at temperatures greater than 25O 0 C for a period of time between 2 minutes and 25 hours, or a combination of both, such that, directly or via conventional ion exchanges, including exchanges with rare earths, the acid form that is the preferred form in the catalytic composition is obtained.
  • the present invention relates to a process for the catalytic cracking of organic compounds characterized in that it comprises at least: a. introducing at least one first zeolitic material, ITQ-33, inside a reactor, b. feeding the reactor with at least one organic compound, c. allowing the zeolitic material ITQ-33 and the organic compound to remain in contact for the time necessary for the reaction to occur.
  • said catalytic cracking process comprises, as well as the zeolitic material ITQ-33, a second zeolitic material.
  • the zeolitic material ITQ-33 used in the process of the present invention may form part, as a single zeolitic component, of catalytic cracking catalysts for organic compounds, or it may also combine with one or more zeolitic components.
  • the second zeolitic material that combines with ITQ-33 is chosen from zeolites with structures containing pores delimited by rings chosen from 14-membered rings, 12-membered rings, 1 1-membered rings, 10-membered rings and combinations thereof.
  • the second zeolitic material is preferably chosen from CIT-5, UTD-I, zeolite Beta, ITQ-7, zeolite Y, SSZ-33; NU-86; ZSM- 5, SAPO-1 1, MCM-22 and combinations thereof.
  • the second zeolitic material is chosen from zeolite Y, zeolite Beta, ZSM-5 and combinations thereof.
  • the first zeolitic material ITQ-33 and the second zeolitic material may be present in the same catalyst particle or in separate particles. In both cases the composition of the cracking products is determined by the combined effect of the different zeolitic components.
  • the zeolitic material ITQ-33 may be incorporated in a matrix via a mixture made up of this zeolite as the single zeolitic component, or this zeolite together with another or other zeolite(s) according to that disclosed in the previous paragraph, as well as the binder and any other conventional additives in catalytic cracking catalysts, such as for example kaolin, silica, alumina.
  • this second zeolitic material may be found in a proportion by weight with regard to the first zeolitic material ITQ-33 of between 2 and 80%.
  • the first zeolitic material ITQ-33 may be modified by ion exchange preferably chosen from total or partial ion exchange.
  • the ions involved in the ion exchange are chosen from divalent ions, trivalent ions, rare earth cations and combinations thereof.
  • the catalytic cracking process of the present invention may be performed at a temperature between 400 and 800°C, and preferably between 450 and 650°C.
  • the catalytic cracking process described above is a catalytic cracking process for organic compounds.
  • said organic compound is at least a hydrocarbon fraction.
  • This hydrocarbon fraction may be derived from oil or be synthetic.
  • the catalytic cracking process of the present invention may be used preferably between deep catalytic cracking (DCC) processes and fluid catalytic cracking (FCC) processes.
  • DCC deep catalytic cracking
  • FCC fluid catalytic cracking
  • the amount of the first zeolitic material ITQ-33 in the catalytic cracking catalyst or catalytic cracking additive is between 2 and 60% by weight.
  • Figure 1 X-ray diffraction pattern for uncalcined ITQ-33.
  • Example 1 Synthesis of a sample of the zeolitic component ITQ-33.
  • the gel is heated to 175°C without stirring for 20 hours in steel autoclaves with an internal Teflon sheath.
  • the solid obtained after filtering, washing with distilled water and drying at 100°C is ITQ-33.
  • Example 2 Activation by means of calcination of the zeolitic component ITQ- 33.
  • the zeolite obtained from Example 1 is calcined in air flow at 540°C for 3 hours.
  • the X-ray diffraction pattern of the calcined material is shown in Table 4.
  • Table 4 Calcined zeolite ITQ-33.
  • Example 3 Catalytic cracking of a vacuum gas oil with a catalyst containing ITQ-33.
  • a first catalyst, Catalyst A was prepared in this example, with the zeolite from Example 1.
  • the uncalcined zeolite was first pelleted, ground in a mortar and sieved, taking the fraction between 0.59 and 0.84 mm in diameter. 0.67 g of this sample were mixed with SiO 2 (2.5 g) sieved to a particle size of 0.25-0.42 mm, and this mixture was calcined "in-situ" for 3 hours at 540°C in air flow (100 ml/min).
  • the catalytic cracking reaction of the vacuum gas oil (Table 5) with this catalyst was carried out in a fixed bed reactor of the "Microactivity Test” (MAT) type, at 500°C, with a 60-second feed time, and at different catalyst/feed ratios expressed by weight of zeolite/feed weight.
  • MAT Microactivity Test
  • Aromatic carbon (weight %) 22.96
  • Naphthenic carbon weight %) 15.16
  • Table 6 shows the interpolated yields at 86% total transformation, the transformation being defined as the sum of gasoline, diesel (LCO), gases and coke yields.
  • Example 4 Catalytic cracking of a vacuum gas oil with a catalyst containing ITQ-33 combined with zeolite ZSM-5.
  • Example 5 Quality of the gasoline obtained during catalytic cracking of a vacuum gas oil using ITQ-33 as the zeolitic component.
  • Catalyst A Catalyst B Catalyst D Catalyst E
  • Aromatics 52.2 55.1 64.0 69.6 weight % Others, 11.6 5.6 10.5 4.5 weight %

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un processus de craquage catalytique de composés organiques qui se caractérise en ce qu'il comprend au moins les étapes suivantes: (a) introduction d'au moins un premier matériau zéolitique, ITQ-33, à l'intérieur d'un réacteur, (b) alimentation de ce réacteur avec au moins un composé organique, (c) maintien de contact du matériau zéolitique ITQ-33 et du composé organique pendant le temps nécessaire pour que la réaction se fasse.
PCT/EP2007/006629 2006-08-01 2007-07-25 Craquage catalytique de composés organiques au moyen de zéolite itq-33 WO2008014920A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES200602179A ES2303448B1 (es) 2006-08-01 2006-08-01 Craqueo catalitico de compuestos organicos utilizando la zeolita itq-33.
ESP200602179 2006-08-01

Publications (2)

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WO2008014920A2 true WO2008014920A2 (fr) 2008-02-07
WO2008014920A3 WO2008014920A3 (fr) 2008-04-10

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012171090A1 (fr) * 2011-06-16 2012-12-20 Universidade Federal Do Rio Grande Do Sul-Ufrgs Zéolite et matériaux mésoporeux organisés utilisés comme charge pour la formulation de composés de caoutchouc, de caoutchouc thermoplastique et de plastique, ainsi que pour la fabrication de produits
WO2014001587A1 (fr) 2012-06-29 2014-01-03 Consejo Superior De Investigaciones Científicas (66%) Craquage catalytique de composé organiques au moyen d'une zéolite modifiée
CN105038851A (zh) * 2015-08-04 2015-11-11 陕西延长石油（集团）有限责任公司榆林炼油厂 一种dcc裂解轻油加工工艺
WO2017223546A1 (fr) 2016-06-24 2017-12-28 Albemarle Corporation Zéolite zsm-22 mésoporeuse pour la production accrue de propylène

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1445297A1 (fr) * 2001-10-04 2004-08-11 Consejo Superior De Investigaciones Cientificas Utilisation de la zeolite itq-21 dans le craquage catalytique de composes organiques
WO2005095550A1 (fr) * 2004-04-01 2005-10-13 Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk Procede de production de combustible pour moteur
WO2006010316A1 (fr) * 2004-07-29 2006-02-02 China Petroleum & Chemical Corporation Catalyseur de craquage pour hydrocarbures et son procede de preparation
WO2006020547A1 (fr) * 2004-08-10 2006-02-23 Shell Internationale Research Maatschappij B.V. Méthode et appareillage permettant d’obtenir un distillat moyen et des oléfines légères à partir d’une charge d’hydrocarbures
WO2006075041A1 (fr) * 2005-01-17 2006-07-20 Consejo Superior De Investigaciones Científicas Materiau cristallin microporeux, la zeolite itq-33, son procede de preparation et son utilisation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1445297A1 (fr) * 2001-10-04 2004-08-11 Consejo Superior De Investigaciones Cientificas Utilisation de la zeolite itq-21 dans le craquage catalytique de composes organiques
WO2005095550A1 (fr) * 2004-04-01 2005-10-13 Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk Procede de production de combustible pour moteur
WO2006010316A1 (fr) * 2004-07-29 2006-02-02 China Petroleum & Chemical Corporation Catalyseur de craquage pour hydrocarbures et son procede de preparation
WO2006020547A1 (fr) * 2004-08-10 2006-02-23 Shell Internationale Research Maatschappij B.V. Méthode et appareillage permettant d’obtenir un distillat moyen et des oléfines légères à partir d’une charge d’hydrocarbures
WO2006075041A1 (fr) * 2005-01-17 2006-07-20 Consejo Superior De Investigaciones Científicas Materiau cristallin microporeux, la zeolite itq-33, son procede de preparation et son utilisation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A. CORMA ET AL.: "High-througput synthesis and catalytic properties of a molecular sieve with 18- and 10-member rings" NATURE, vol. 443, October 2006 (2006-10), pages 842-845, XP002467965 *
R.F. LOBO: "The promise of emptiness" NATURE, vol. 443, October 2006 (2006-10), pages 757-758, XP002467966 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012171090A1 (fr) * 2011-06-16 2012-12-20 Universidade Federal Do Rio Grande Do Sul-Ufrgs Zéolite et matériaux mésoporeux organisés utilisés comme charge pour la formulation de composés de caoutchouc, de caoutchouc thermoplastique et de plastique, ainsi que pour la fabrication de produits
WO2014001587A1 (fr) 2012-06-29 2014-01-03 Consejo Superior De Investigaciones Científicas (66%) Craquage catalytique de composé organiques au moyen d'une zéolite modifiée
CN105038851A (zh) * 2015-08-04 2015-11-11 陕西延长石油（集团）有限责任公司榆林炼油厂 一种dcc裂解轻油加工工艺
WO2017223546A1 (fr) 2016-06-24 2017-12-28 Albemarle Corporation Zéolite zsm-22 mésoporeuse pour la production accrue de propylène
US10981152B2 (en) 2016-06-24 2021-04-20 Albemarle Corporation Mesoporous ZSM-22 for increased propylene production

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Publication number Publication date
ES2303448B1 (es) 2009-06-22
WO2008014920A3 (fr) 2008-04-10
ES2303448A1 (es) 2008-08-01

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