WO2011120968A2 - Procédé de valorisation de l'essence - Google Patents

Procédé de valorisation de l'essence Download PDF

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Publication number
WO2011120968A2
WO2011120968A2 PCT/EP2011/054824 EP2011054824W WO2011120968A2 WO 2011120968 A2 WO2011120968 A2 WO 2011120968A2 EP 2011054824 W EP2011054824 W EP 2011054824W WO 2011120968 A2 WO2011120968 A2 WO 2011120968A2
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Prior art keywords
crystalline
catalyst
olefins
process according
stream
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PCT/EP2011/054824
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English (en)
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WO2011120968A3 (fr
Inventor
Delphine Minoux
Sander Van Donk
Nikolai Nesterenko
Metin BULUT
Original Assignee
Total Raffinage Marketing
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Application filed by Total Raffinage Marketing filed Critical Total Raffinage Marketing
Priority to US13/637,549 priority Critical patent/US20130037446A1/en
Priority to CN2011800167771A priority patent/CN102822320A/zh
Priority to EP11710517A priority patent/EP2553053A2/fr
Publication of WO2011120968A2 publication Critical patent/WO2011120968A2/fr
Publication of WO2011120968A3 publication Critical patent/WO2011120968A3/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
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/22—After treatment, characterised by the effect to be obtained to destroy the molecular sieve structure or part thereof
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/38—Base treatment
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • 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
    • B01J29/82—Phosphates
    • B01J29/83—Aluminophosphates [APO compounds]
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1096—Aromatics or polyaromatics
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

Definitions

  • the present invention relates to a process allowing the tuning of the gasoline/diesel balance by converting an initial feedstock containing olefins from 4 to 20 carbon atoms, more particularly from 4 to 15 carbon atoms, preferably from 4 to 9 carbon atoms with or without addition of aromatics, using a crystalline catalyst, preferably a zeolite-based catalyst, with reduced diffusional limitations.
  • Catalytic Cracking are olefinic in nature.
  • C4 olefins are used as feed for the alkylation and etherification units to create gasoline components with high octane number, and the higher olefins are generally directly blended into the gasoline pool.
  • This invention relates to a process for the manufacture of higher molecular weight organic molecules from a stream of lower molecular weight molecules using a catalyst, preferably a zeolite based catalyst, with reduced diffusional limitations.
  • a catalyst preferably a zeolite based catalyst
  • oligomerization processes involve contacting an initial feedstock containing 4 to 10 carbon atoms with a solid acid catalyst, such as Solid Phosphoric Acid (SPA) catalyst, crystalline molecular sieve or amorphous silica-alumina.
  • SPA Solid Phosphoric Acid
  • crystalline molecular sieve or amorphous silica-alumina.
  • SPA catalyst With SPA catalyst, the pressure drop over the catalytic bed(s) increases gradually due to coking, swelling of the catalyst, and is therefore the limiting factor of a run duration, the unit being shutdown once the maximum allowable pressure drop has been reached.
  • the amorphous silica-alumina catalysts present the advantage of operating at quite low temperatures (140- 160°C), thus allowing a larger range of operating temperature before being limited by secondary reactions (cracking.).
  • such catalytic systems are not shape selective, and the diesel cut produced exhibits bad cetane number.
  • Lurgi AG Germany (WO2006/076942), has developed the Methanol to Synfuels (MTS) process, which is in principle similar to the MOGD process.
  • MTS Methanol to Synfuels
  • the Lurgi route is a combination of simplified Lurgi MTP technology with COD technology from Slid Chemie (US5063187). This process produces gasoline (RON 80) and diesel
  • zeolitic catalysts do have shape selectivity induced by the microporosity of the zeolitic structure, thus leading to diesel cut with good cetane number.
  • micropores may also have a negative impact, which is often illustrated by the low rate access of molecules into the zeolitic crystals, on unwanted adsorption effects of reactants and/or products during the catalytic reaction.
  • oligomerization/ alkylation One of the constraints concerning the oligomerization/ alkylation is the competition between oligomerization / alkylation on one hand and cracking. To avoid these undesired reactions and enhance the selectivity of the catalyst towards heavies formation, the design of an optimally accessible catalyst is required. Shape selective zeolites appear to be the most promising catalysts, since by proper materials choice, the isomerization reaction could be limited. For light olefins conversion, typically 10 membered ring zeolites are highly suitable in their micropore size range.
  • a more generally applied strategy to obtain materials with reduced diffusional limitations is the creation of a secondary pore system consisting of mesopores (2-50 nm) inside the microporous zeolite crystals
  • Direct zeolite seed assembly using a template to shape the mesopores.
  • WO 2009/ 153421 discloses the synthesis of a crystallized material with hierarchised and organized porosity and its application in the oligomerization of light olefins.
  • a first object of the invention relates to a process allowing to upgrade gasoline into middle distillate by conversion a feedstock containing olefins from 4 to 20 carbon atoms in the presence or absence of aromatics, over a catalyst containing a crystalline compound with combined micro/ mesoporous structure allowing to reduce significantly the diffusional limitations.
  • the invention thus concerns a process for the manufacture of middle distillates from a gasoline stream, said process comprising: - processing a feedstock stream containing olefins Cn from 4 to 20 carbon atoms, with or without the presence of an aromatic containing stream,
  • the catalyst is a crystalline compound with micro / mesoporous structure chosen among crystalline aluminosilicates, crystalline aluminophosphates, crystalline silico-aluminophosphates, crystalline zeolites, or the catalyst is a composite material comprising at least
  • the mesoporous volume of the crystalline compound is at least 0.22 ml/g, preferably at least 0.25 ml/g, and most preferably at least 0.30 ml/g.
  • the mesoporous volume of the crystalline compound is at least 0.2 ml/g, most preferably at least 0.3 ml/g.
  • the microporous volume of the crystalline compound is inferior or equal to 0.20 ml/g, more preferably inferior or equal to 0.17 ml/g, most preferably inferior or equal to 0.15 ml/g.
  • the ratio mesoporous volume/ microporous volume of the crystalline compound may be superior or equal to 1 , more preferably superior or equal to 2, most preferably superior or equal to 2.5.
  • the catalyst particularly the micro-mesoporous crystalline silicates of zeolite structure, may be subjected to one or several of the following treatments :
  • a dealumination treatment (either via hydro thermal route and/ or an acid leaching), so as to (i) decrease the acidity of the material (ii) increase, though slightly, the mesoporosity of the initial material.
  • a dealumination treatment (either via hydro thermal route and/ or an acid leaching), so as to (i) decrease the acidity of the material (ii) increase, though slightly, the mesoporosity of the initial material.
  • Such treatments are described in US 5601798.
  • a careful desilication of the material by a treatment in an alkaline medium containing at least a strong inorganic base (NaOH, KOH) and/or an organic base (such as TMAOH, TPAOH...), the concentration of which ranges from 0.1 to 2M, preferably from 0.15 to 1M.
  • the alkaline treatment is performed under stirring, at a temperature ranging from ambient temperature to 100°C, preferably up to 85°C.
  • ambient temperature is to be understood a temperature ranging from 18°C to 25°C, more preferably 20°C.
  • the duration of the alkaline treatment may be comprised between 5 to 120min, preferably from 10 to 60min, advantageously from 15 to 30min.
  • the obtained material is then filtered and may be subsequently washed with large amounts of a polar solvent (by way of example, pure demineralized water).
  • the neutralization of the alkaline solution may be performed before the filtration step so as to stop the desilication reaction. Indeed, if the desilication is becoming too important, this may lead to the significant loss of the crystallinity of the zeolite structure, which may induce a decrease of the intrinsic activity of the material.
  • the material might be subjected to an ion-exchange step, typically using ammonium salts, or inorganic acids.
  • the catalyst is then generally calcined for example at a temperature of from 400 to 800°C at atmospheric pressure for a period of from 1 to 10 hours.
  • the material can be subjected to a final mild hydrothermal treatment, aiming at healing the crystalline defects generated by the alkaline treatment.
  • the catalyst used in the process of the invention may be a composite material comprising at least 20%wt of at least one crystalline compound with micro/ mesoporous structure chosen among crystalline aluminosilicates, crystalline aluminophosphates, crystalline silico-aluminophosphates, crystalline zeolites, or mixture thereof.
  • the crystalline compound(s), eventually modified as previously mentioned, may be mixed with a binder, preferably an inorganic binder, and shaped to a desired shape, e.g. pellets.
  • the binder is selected so as to be resistant to the temperature and other conditions employed in the reaction of the invention.
  • the binder is preferably an inorganic material selected from clays, silica, metal silicates, metal oxides such as ZrO2 and/ or metals, gels including mixtures of silica and metal oxides. If the binder which is used in conjunction with the crystalline compound is itself catalytically active, this may alter the conversion and/ or the selectivity of the catalyst.
  • Inactive materials for the binder may suitably serve as diluents to control the amount of conversion so that products can be obtained economically and orderly without employing other means for controlling the reaction rate. It is desirable to provide a catalyst having good crush strength. This is because in commercial use, it is desirable to prevent the catalyst from breaking down into powder-like materials. Such clay or oxide binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
  • the crystalline compound used in the process of the invention presents preferably a structure of the zeolite type.
  • the atomic ratio Si/Al of the zeolite structure, before alkaline treatment, is preferably at least 15, preferably at least 25, most preferably at least 30.
  • the atomic ratio Si/Al of the zeolite structure, before alkaline treatment, is preferably lower than 60, preferably below 50.
  • the mesoporous volume of the crystalline compound used in the present invention is at least 0.2 ml/g, most preferably at least 0.3 ml/g.
  • the microporous volume of the crystalline compound is inferior or equal to 0.20 ml/g, more preferably inferior or equal to 0.17 ml/g, most preferably inferior or equal to 0.15 ml/g.
  • the ratio mesoporous volume/ microporous volume of the crystalline compound may be superior or equal to 1 , more preferably superior or equal to 2, most preferably superior or equal to 2.5.
  • This crystalline compound may be selected from the MFI (ZSM-5, silicalite- 1 , boralite C, TS- 1), MEL (ZSM- 1 1 , silicalite-2, boralite D, TS- 2 , SSZ-46), FER (Ferrierite, FU-9, ZSM-35), MTT (ZSM-23), MWW (MCM-22, PSH-3, ITQ- 1 , MCM-49), TON (ZSM-22, Theta- 1 , NU- 10), EUO (ZSM-50, EU- 1), MTW (ZSM- 12), MAZ, SAPO- 1 1 , SAPO-5, FAU, LTL, BETA MOR, SAPO-40, SAPO-37, SAPO-41.
  • MFI ZSM-5, silicalite- 1 , boralite C, TS- 1
  • MEL ZSM- 1 1 1 , silicalite-2, boralite D, TS- 2 , SSZ-
  • the catalyst presents a structure of the ZSM-5 type.
  • the reaction will preferably be conducted under the following conditions :
  • WHSV weight hour space velocity
  • pressure from atmospheric pressure to 200barg, preferably from 15 to lOObarg, most preferably from 15 to 60barg.
  • the feed of the present invention is typically obtained from petroleum refining or petrochemicals operations.
  • it may be obtained from steam of thermal cracking or catalytic cracking.
  • Olefin containing feed can also be obtained alternatively from the dehydrogenation of hydrocarbon streams obtained from the processing of crude oils, natural gas, or field condensates. They can also be obtained by dehydrogenation of alcohols.
  • composition of the feed (amounts of olefins, aromatics, type of olefins and aromatics) depend upon the feed to the process and the conditions that are employed ; the process may be operated either with the entire gasoline fraction obtained from a catalytic or thermal cracking step or alternatively part of it. Mixture of streams can also be considered : by way of example, a reformate and a LCN gasoline fraction can also be considered.
  • the feedstock is chosen among gasolines containing olefins such as LCCS with boiling points in the range of 30 to 100°C or a mixture of olefins and aromatics such as LCN with boiling points in the range of 30 to 170°C.
  • olefins such as LCCS with boiling points in the range of 30 to 100°C
  • aromatics such as LCN with boiling points in the range of 30 to 170°C.
  • Typical feed composition can be found below in table 1 for LCCS (Light Catalytic Cracked Spirit) and in table 2 For LCN (Light Cracked naphta) .
  • Table 1 typical composition of LCCS
  • a plural reactor system may be employed with inter-reactor cooling, whereby the reaction exotherm can be carefully controlled to prevent excessive temperature above the normal moderate range.
  • T h e oligomerization/ alkylation may be performed continuously in a fixed bed reactor configuration using a series of parallel "swing" reactors.
  • the various preferred catalysts of the present invention have been found to exhibit sufficiently high stability. This enables the oligomerization and/or alkylatio n proce s s to b e pe rformed continuously in two parallel "swing" reactors wherein when one or two reactors are in operating, the other reactor is undergoing catalyst regeneration.
  • the catalyst of the present invention also can be regenerated several times.
  • a plural reactor system may be employed with inter-reactor cooling, whereby the reaction exotherm can be carefully controlled to prevent excessive temperature above the normal moderate range.
  • the maximum temperature differential across only one reactor is not exceeding 75° C.
  • the pressure differential between the two stages can be utilized in an intermediate flashing separation step.
  • Figure 1 sorption -desorption isotherms for desilicated ZSM-5 and parent sample (TPN : standard conditions : 0°C and 760 mmHg).
  • catalysts A and B are gathered below (Table 3 and figure 1) and characterized by the following methods.
  • N2 sorption-desorption isotherms at 77K were measured in an automated porosimeter (Micromeritics Tristar 3000) . Prior to the measurement, the samples were degassed in vacuum at 573K for 12h. The mesopore size distribution was obtained by the BJH model (Barett
  • Rouquerol F. Rouquerol J., Sing K., Adsorption by Powders and Porous Solids, Academic Press, San Diego, 1991
  • the t-plot method was used to discriminate between micro and mesoporosity.
  • Figure 1 shows the nitrogen sorption/desorption isotherms of catalysts A (parent sample) and B (desilicated ZSM-5). The comparison of the two N2-isotherms highlights the enhanced uptake at intermediate pressure, indicative of the formation of a hierarchical porous system combining micro and mesoporosity.
  • the mesoporous volume increases from 0.097 to 0.327 ml/g, while the microporous volume decreases from 0.161 to 0.1 19 ml/g.
  • the Si/Al ratio decreases from to 46 to 34.
  • V meso Vtotal - V micro
  • the following operating conditions were used : 55barg, WHSV (Weight Hourly Space Velocity) of 1 or 2 r 1 , temperature varying from 150 up to 200°C.
  • Cx represent alkanes with x atom of carbon
  • Cx represent olefins with x atoms of carbon

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

Abstract

La présente invention concerne un procédé permettant d'ajuster l'équilibre essence/diesel en convertissant une charge d'alimentation initiale contenant des oléfines de 4 à 20 atomes de carbone au moyen d'un catalyseur cristallin avec des limitations de diffusion réduites. Le procédé comprend : - le traitement d'un courant de charge d'alimentation contenant des oléfines de 4 à 20 atomes de carbone en présence ou en l'absence d'un courant contenant des substances aromatiques, - la mise en contact dudit ou desdits courants avec un catalyseur dans des conditions efficaces pour oligomériser au moins une partie des oléfines et finalement alkyler au moins une partie des substances aromatiques, le catalyseur étant un composé cristallin ayant une structure micro/mésoporeuse, choisi parmi les aluminosilicates cristallins, les aluminophosphates cristallins, les silico-aluminophosphates cristallins, les zéolites cristallines, ou le catalyseur étant un matériau composite comprenant au moins 20 % en poids d'au moins un des composés cristallins mentionnés ci-dessus, et le volume mésoporeux du composé cristallin étant au moins égal à 0,22 ml/g.
PCT/EP2011/054824 2010-03-30 2011-03-29 Procédé de valorisation de l'essence WO2011120968A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US13/637,549 US20130037446A1 (en) 2010-03-30 2011-03-29 Gazoline upgrading process
CN2011800167771A CN102822320A (zh) 2010-03-30 2011-03-29 汽油升级方法
EP11710517A EP2553053A2 (fr) 2010-03-30 2011-03-29 Procédé de valorisation de l'essence

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3310883A4 (fr) * 2015-06-22 2018-11-14 Patrick James Cadenhouse-Beaty Procédé de production d'un mélange de carburant pour le transport

Families Citing this family (6)

* Cited by examiner, † Cited by third party
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FR3009207B1 (fr) 2013-08-02 2021-04-30 Ifp Energies Now Modification de zeolithe de type euo et son utilisation en isomerisation des composes c8 aromatiques
KR102068312B1 (ko) * 2013-10-18 2020-01-20 에스케이이노베이션 주식회사 활성화된 eu-2 제올라이트 및 이의 용도
US9670425B2 (en) 2013-12-17 2017-06-06 Uop Llc Process for oligomerizing and cracking to make propylene and aromatics
US9732285B2 (en) 2013-12-17 2017-08-15 Uop Llc Process for oligomerization of gasoline to make diesel
US11149214B2 (en) 2018-12-17 2021-10-19 Saudi Arabian Oil Company Method and process to maximize diesel yield
CN115716651B (zh) * 2021-08-25 2024-04-30 中国石油天然气股份有限公司 Zsm-35分子筛及其制备方法、异构化催化剂及其制备方法、异构化方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4150062A (en) 1976-12-20 1979-04-17 Mobil Oil Corporation Light olefin processing
US4227992A (en) 1979-05-24 1980-10-14 Mobil Oil Corporation Process for separating ethylene from light olefin mixtures while producing both gasoline and fuel oil
US4482772A (en) 1983-11-03 1984-11-13 Mobil Oil Corporation Multistage process for converting oxygenates to hydrocarbons
US4506106A (en) 1984-01-04 1985-03-19 Mobil Oil Corporation Multistage process for converting oxygenates to distillate hydrocarbons with interstage ethene recovery
US4543435A (en) 1985-01-17 1985-09-24 Mobil Oil Corporation Multistage process for converting oxygenates to liquid hydrocarbons with ethene recycle
US5063187A (en) 1988-11-15 1991-11-05 Sud-Chemie Aktingesellschaft Catalyst based on crystalline aluminosilicate
US5601798A (en) 1993-09-07 1997-02-11 Pq Corporation Process for preparing zeolite Y with increased mesopore volume
WO2006076942A1 (fr) 2005-01-22 2006-07-27 Lurgi Ag Procede de production de combustibles synthetiques a base d'oxygenats
WO2009153421A1 (fr) 2008-05-28 2009-12-23 Ifp Catalyseur a base d1un materiau cristallise à porosité hiérarchisée et organisee et son utilisation en oligomerisat1on des olefines legeres

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8299312B2 (en) * 2005-10-28 2012-10-30 Neste Oil Oyj Process for dimerizing olefins
FR2931818B1 (fr) * 2008-05-28 2012-11-30 Inst Francais Du Petrole Procede d'oligomerisation des olefines legeres utilisant un catalyseur a base d'un materiau amorphe a porosite hierarchisee et organisee

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4150062A (en) 1976-12-20 1979-04-17 Mobil Oil Corporation Light olefin processing
US4227992A (en) 1979-05-24 1980-10-14 Mobil Oil Corporation Process for separating ethylene from light olefin mixtures while producing both gasoline and fuel oil
US4482772A (en) 1983-11-03 1984-11-13 Mobil Oil Corporation Multistage process for converting oxygenates to hydrocarbons
US4506106A (en) 1984-01-04 1985-03-19 Mobil Oil Corporation Multistage process for converting oxygenates to distillate hydrocarbons with interstage ethene recovery
US4543435A (en) 1985-01-17 1985-09-24 Mobil Oil Corporation Multistage process for converting oxygenates to liquid hydrocarbons with ethene recycle
US5063187A (en) 1988-11-15 1991-11-05 Sud-Chemie Aktingesellschaft Catalyst based on crystalline aluminosilicate
US5601798A (en) 1993-09-07 1997-02-11 Pq Corporation Process for preparing zeolite Y with increased mesopore volume
WO2006076942A1 (fr) 2005-01-22 2006-07-27 Lurgi Ag Procede de production de combustibles synthetiques a base d'oxygenats
WO2009153421A1 (fr) 2008-05-28 2009-12-23 Ifp Catalyseur a base d1un materiau cristallise à porosité hiérarchisée et organisee et son utilisation en oligomerisat1on des olefines legeres

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
A.CORMA, NATURE, vol. 396, 1998, pages 353
A.H. JANSSEN, ANGEW.CHEM.INT.ED., vol. 40, 2001, pages 1102
BARETT E.P., JOYNER L.G., HALENDA P.P, J.AM.CHEM.SOC., vol. 73, 1951, pages 373 - 380
CHRISTENSEN C.H. ET AL., JACS, vol. 125, 2003, pages 13370 - 13371
GROEN J.C., J.PHYS.CHEM.B, vol. 108, 2004, pages 13062
GROEN J.C., JACS, vol. 127, 2005, pages 10792
GROEN JC, MICROPOROUS MESOPOROUS MATERIALS, vol. 69, 2004, pages 29
OGURA M., APPL.CATAL.A GEN., vol. 219, 2001, pages 33
OGURA M., CHEM.LETT., 2000, pages 82
PEREZ-RAMIREZ J, APPL.CATAL.A, vol. 364, 2009, pages 191 - 198
ROUQUEROL F., ROUQUEROL J., SING K.: "Adsorption by Powders and Porous Solids", 1991, ACADEMIC PRESS

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3310883A4 (fr) * 2015-06-22 2018-11-14 Patrick James Cadenhouse-Beaty Procédé de production d'un mélange de carburant pour le transport
US10557090B2 (en) 2015-06-22 2020-02-11 Patrick James Cadenhouse-Beaty Process for producing transport fuel blendstock

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