WO2009093093A1 - Procédé de fabrication industrielle de carbonate de diéthyle (dec) au moyen d'un réacteur de synthèse catalytique hétérogène alimenté par de l'éther éthylique et du dioxyde de carbone - Google Patents

Procédé de fabrication industrielle de carbonate de diéthyle (dec) au moyen d'un réacteur de synthèse catalytique hétérogène alimenté par de l'éther éthylique et du dioxyde de carbone Download PDF

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Publication number
WO2009093093A1
WO2009093093A1 PCT/IB2008/000159 IB2008000159W WO2009093093A1 WO 2009093093 A1 WO2009093093 A1 WO 2009093093A1 IB 2008000159 W IB2008000159 W IB 2008000159W WO 2009093093 A1 WO2009093093 A1 WO 2009093093A1
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WIPO (PCT)
Prior art keywords
reactor
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dec
preferably around
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Prior art date
Application number
PCT/IB2008/000159
Other languages
English (en)
Inventor
Rosario Rocco Tulino
Letizia Santino
Original Assignee
Rosario Rocco Tulino
Letizia Santino
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 Rosario Rocco Tulino, Letizia Santino filed Critical Rosario Rocco Tulino
Priority to PCT/IB2008/000159 priority Critical patent/WO2009093093A1/fr
Publication of WO2009093093A1 publication Critical patent/WO2009093093A1/fr

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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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
    • B01J19/2465—Stationary reactors without moving elements inside provoking a loop type movement of the reactants externally, i.e. the mixture leaving the vessel and subsequently re-entering it
    • 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
    • B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • B01J10/007—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
    • 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
    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00805—Details of the particulate material
    • B01J2208/00814—Details of the particulate material the particulate material being provides in prefilled containers
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00083—Coils
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/0015—Controlling the temperature by thermal insulation means
    • B01J2219/00155—Controlling the temperature by thermal insulation means using insulating materials or refractories
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/302—Basic shape of the elements
    • B01J2219/30203—Saddle
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the organic carbonates are functional derivatives of carbonic acid and they are generally called dialkyl carbonates; thanks to their physical chemical characteristics they are subject of growing attention by the chemical industry and the plastic materials.
  • the diethyl carbonate (DEC) obtained by the synthesis between ethylic ether and carbon dioxide, can use CO 2 coming from the sequestration of the thermal stations releases, aiding in such way the reduction of the CO 2 rate in the atmosphere and the reduction of greenhouse effect.
  • the ethylic ether used in the synthesis might derive from the dewatering of ethylic alcohol coming from the biomasses fermentation (no fossil origin), therefore the so obtained DEC might be considered as a renewable energetic vector.
  • the diethyl carbonate molecule shows some peculiar capacities inside the combustion chamber of endothermic motors because it is able to carry out an oxygenating and octaning vigorous action (octane number 124) within the field of additives for vehicles ecological fuels.
  • DEC in small percentages in motor fuel (between 3% and 8%),causes a pulling down of polluting emissions and it is fully compatible with the basic fuels without showing out negative sides (toxicity, corrosion, volatility, low flammability point, clouding, solubility gaps).
  • the use of diethyl carbonate as organic solvent combines the best capacity of solvent action with a non-toxic behaviour and of easy storage (group III).
  • group III For a large and massive use of this mixture (fuels reformulation, solvent, intermediate for urethanes and polycarbonates synthesis) it is necessary a low cost availability that can be obtained with a simple and efficient manufacture process.
  • Some production processes are based on direct alcohol synthesis at high pressures, with long times of conversion, using toxic catalyses and expensive production plant.
  • the tubular reactor with vertical axis shown in Fig. 1, carries out the direct synthesis between ethyl ether (CH 3 CH 2 ) 2 O, introduced at liquid condition, and carbon dioxide CO 2 , introduced at gaseous condition in a temperature range between 115°C and 235°C and a pressure interval between 15 bar and 55 bar. So limited parameters values with consequent construction easiness are feasible thanks to the use of a catalytic complex able to carry out a high activity with the aid of reaction promoters.
  • the support typology and structure make easier the synthesis action of the catalyzing complex between CO 2 and ethyl ether molecules.
  • the potassium carbonate along with the cobalt oxide and the ethyl iodide, absorbed on the support made by alumina and zeolite type 3A, quickly catalyze the DEC bonds formation.
  • the form of the catalytic complex consists of several circular rings with radial crossing of the gaseous stream during steam phase with reagent continuous recirculation through suitable centrifugal compressor at magnetic dragging.
  • This catalyst layout has a high permeability to gases (CO 2 specifically) as the support, after the impregnation and the mixing with the catalyzing complex, is put inside containers made with perforated stainless steel sheet and mesh net.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un complexe de carbonate de diéthyle liquide (DEC - C2H5OCOOC2H5) au moyen d'un réacteur de synthèse catalytique dans une phase hétérogène alimentée par de l'éther éthylique (C2H5OC2H5) (liquide) et du dioxyde de carbone CO2 (gaz). La synthèse du composé se produit dans le réacteur tubulaire vertical fonctionnant sous une pression située entre 15 bar et 55 bar et dans une plage de température située entre 115 °C et 235 °C. Les nombreux secteurs différents, avec une forme d'anneau circulaire, sont empilés dans la zone d'entrée du réacteur. Le catalyseur est composé de carbonate de potassium (K2CO3) et d'oxyde de cobalt (CoO) comme promoteur de réaction et d'iodure d'éthyle (IC2H5) comme activateur de réaction. Le support est fabriqué par un secteur d'éponge de type 3A d'alumine plus zéolite, dont plusieurs sites actifs permettent une conversion de rendement élevée à un carbonate organique pour chaque réactif qui passe dans un recyclage poussé par le compresseur centrifuge à entraînement magnétique.
PCT/IB2008/000159 2008-01-21 2008-01-21 Procédé de fabrication industrielle de carbonate de diéthyle (dec) au moyen d'un réacteur de synthèse catalytique hétérogène alimenté par de l'éther éthylique et du dioxyde de carbone WO2009093093A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/IB2008/000159 WO2009093093A1 (fr) 2008-01-21 2008-01-21 Procédé de fabrication industrielle de carbonate de diéthyle (dec) au moyen d'un réacteur de synthèse catalytique hétérogène alimenté par de l'éther éthylique et du dioxyde de carbone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2008/000159 WO2009093093A1 (fr) 2008-01-21 2008-01-21 Procédé de fabrication industrielle de carbonate de diéthyle (dec) au moyen d'un réacteur de synthèse catalytique hétérogène alimenté par de l'éther éthylique et du dioxyde de carbone

Publications (1)

Publication Number Publication Date
WO2009093093A1 true WO2009093093A1 (fr) 2009-07-30

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115975170A (zh) * 2023-03-17 2023-04-18 江苏正力新能电池技术有限公司 一种聚合物电解质聚碳酸乙醚酯及其制备方法与应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0555697A1 (fr) * 1992-02-10 1993-08-18 Bayer Ag Procédé de préparation de carbonates de dialkyle
EP0634389A2 (fr) * 1993-07-15 1995-01-18 Bayer Ag Procédé de préparation de carbonates de dialkyle
EP1121976A1 (fr) * 2000-02-03 2001-08-08 Engelhard Corporation Procédé chimique dans un réacteur ayant catalyseur structuré

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0555697A1 (fr) * 1992-02-10 1993-08-18 Bayer Ag Procédé de préparation de carbonates de dialkyle
EP0634389A2 (fr) * 1993-07-15 1995-01-18 Bayer Ag Procédé de préparation de carbonates de dialkyle
EP1121976A1 (fr) * 2000-02-03 2001-08-08 Engelhard Corporation Procédé chimique dans un réacteur ayant catalyseur structuré

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115975170A (zh) * 2023-03-17 2023-04-18 江苏正力新能电池技术有限公司 一种聚合物电解质聚碳酸乙醚酯及其制备方法与应用

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