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WO2012035540A1 - Procédé de production d'acroléïne et d'un catalyseur réutilisable - Google Patents

Procédé de production d'acroléïne et d'un catalyseur réutilisable Download PDF

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Publication number
WO2012035540A1
WO2012035540A1 PCT/IN2010/000755 IN2010000755W WO2012035540A1 WO 2012035540 A1 WO2012035540 A1 WO 2012035540A1 IN 2010000755 W IN2010000755 W IN 2010000755W WO 2012035540 A1 WO2012035540 A1 WO 2012035540A1
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Prior art keywords
acrolein
calcinated
range
production
catalyst
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Ganapati Dadasaheb Yadav
Suraj Onkar Katole
Rajesh Vishnudev Sharma
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    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • 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
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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

Definitions

  • the present invention is related to calcinated catalyst composition comprising divalent metal, trivalent metal, tetravalent metal and hexavalent metal and or mixture thereof with silicon as base metal wherein said catalyst composition has specific surface area is in the range of 50 m 2 /g to 1000 m 2 /g.
  • Such high specific surface area calcinated catalyst composition is useful in many solid catalysed reactions.
  • Calcinated catalyst composition is easily separable, regenerable and reusable in acrolein production process.
  • Heterogeneous solid catalyst are always been great area of interest to researcher. Thus many efforts have been made to design of better Heterogeneous solid acid catalyst with high specific area which can be easily separable, regenerable and reusable. Many inventors claim for better heterogeneous catalyst with various support but they have their own drawbacks for different reaction system.
  • Acrolein is a key intermediate for the synthesis of methionine, is a synthetic protein used as a substitute of fishmeal. Acrolein is used for preparation of a wide variety of value-added specialty and fine chemicals. Acrolein finds direct application in medicine, water treatment, and petroleum industry as biocide. Refined acrolein is used for the synthesis of agrochemical methionine, fragrances and dyes.
  • a new direct route of aqueous glycerol to acrolein is always welcome, as it will avoid multi-step energy incentive processes with waste reduction.
  • the oxidation of propylene with the atmospheric oxygen produces acrolein is the most commonly used process.
  • This process demand propylene as starting material which is obtained by steam cracking of petroleum fraction. Under the threat of depletion of petroleum and global warming, it becomes necessary to have acrolein process based on renewable resources such as glycerol.
  • Acrolein can be synthesis by double dehydration of glycerol by using either homogeneous or heterogeneous solid acid catalysts.
  • glycerol for the synthesis of value added chemicals is a theme of great Industrial interest because glycerol is formed in large amounts during the production of biodiesel from natural triglycerides.
  • Patent No. US2010/0113838 Al discloses process for production of acrolein in vapour phase dehydration of glycerol in the presence of rare earth metal salt crystals of phosphoric acid, as Nd (Neodymium) is a rare earth metal atom.
  • Nd Neodymium
  • glycerol conversion is 100 % and acrolein selectivity is 77 % after 3 hours, and it gives glycerol conversion is 100 % and acrolein selectivity is 68 % after 7 hours.
  • Patent No. WO 2009/127889 Al discloses process for dehydration of glycerol in the gas phase in the presence of cesium salt of tungustophosphoric acid (CsPW), wherein acrolein yield is 92.9% with 100% glycerol conversion, after 7 hours of reaction. At a temperature in the range of 260° C to 350° C with pressure lower than 3 arm.
  • CsPW cesium salt of tungustophosphoric acid
  • Patent No. WO 2007/058221 discloses a process for producing acrolein by dehydration reaction of glycerin in gas-phase in the presence of heteropolyacid used as a solid acid catalyst.
  • the heteropolyacid is those of group 6 elements such as tungstosilicic acid, tungstophosphoric acid and phosphomolybdic acid. These heteropolyacids are supported on bi-elemental pore silica carrier and produce acrolein at a yield of 86%.
  • This dehydration reaction of glycerin is effected without oxidation gas but using nitrogen stream as carrier gas, so that deposition of carbon increase seriously and hence there is a problem of deterioration in time of stability, activity selectivity of the catalysis.
  • Patent No. WO 2007/119528 discloses acrolein is usually produced using a catalyst for promoting intramolecular dehydration of glycerin, using yttrium salt crystals, lanthanum salt crystals, cerium salt crystals, or samarium salt crystals of phosphoric acid are used as a catalyst.
  • a catalyst for promoting intramolecular dehydration of glycerin using yttrium salt crystals, lanthanum salt crystals, cerium salt crystals, or samarium salt crystals of phosphoric acid are used as a catalyst.
  • glycerin gas when glycerin gas is employed as a raw material, the deposition of carbonaceous substance on the surface of a catalyst, which is one of the factors for the deactivation of the catalyst, is suppressed.
  • a process for producing acrolein in high yield is also inevitably desired.
  • Objective of the present invention is to design calcinated heterogeneous solid acid catalyst composition having high specific area and which can be easily separable, regenerable and reusable.
  • Another objective of the present invention is to design catalyst having specific surface area is in the range of 50 m 2 /g to 1000 m 2 /g.
  • Another objective of the present invention is to develop process for the production of acrolein by vapor phase dehydration of aqueous glycerol solution with the said calcinated catalyst composition.
  • Yet another objective of the present invention is to develop process operated at low temperature as compare to other processes reported in the scientific literature.
  • Yet another objective of the present invention is to develop an economical viable process for the production of acrolein.
  • Drawing 1 SEM (Scanning Electron Microscope) images of fresh and regenerated
  • Drawing 2 NH 3 -TPD (Temperature Program Desorption) of fresh and regenerated
  • Drawing 4 ASAP (Surface area and pore size analysis) of fresh and regenerated catalyst.
  • Drawing 5 XRD analysis of the catalyst
  • Drawing 6 EDX (Elemental analysis) of fresh, used and regenerated catalyst.
  • Glycerol is one of the potential renewable resources is obtained as a by-product in hydrolysis of fat, soap-manufacturing process and production of biodiesel.
  • the ratio of biodiesel to crude glycerol produced are about 9:1, therefore, a new application of glycerol needs to be found.
  • Dehydration of glycerol produces important commodity chemicals like acrolein. It is an important bulk chemical used as a feedstock for acrylic acid production, pharmaceuticals intermediates, fiber treatments, and methionine (used in animal feed).
  • the most significant application of acrolein is an herbicide to control the growth of aquatic plants.
  • Heterogeneous solid acid catalyst composition having high specific area and which can be easily separable, regenerable and reusable.
  • calcinated catalyst composition which comprises aluminium, zirconium, tungsten, and oxygen with silicon (hexagonal mesoporous silica) as base metal is used and has specific surface area is in the range 50 to 1000 m 2 /g.
  • silicon hexagonal mesoporous silica
  • Such high specific surface area of calcinated catalyst composition can be use in many solid catalysed reactions.
  • metal ions used in the calcinated catalyst composition can be in form of nitrate, oxide, chloride, oxychloride, carbonate, acetate, isopropoxide, sulphate, hydroxide salts of metal ions.
  • One of the embodiments of calcinated catalyst composition wherein mass percent of silicon metal is varied from at least 10.0 to 50.0 of total mass percent of calcinated catalyst composition according to type of solid acid catalyzed reaction is that metals can be present in the form of its oxides and /or in its metal compound form, according to type of solid acid catalyzed reaction.
  • One of the embodiments of calcinated catalyst composition is that metals can be supported on hexagonal mesoporous silica (HMS) to give high specific surface area.
  • HMS hexagonal mesoporous silica
  • One of the embodiments of calcinated catalyst composition is that it comprises oxygen varied from 30.0 to 60.0 mass percent of total mass percent of calcinated catalyst composition according to type of solid acid catalyzed reaction.
  • Calcinated solid acid catalyst has varying ratio of aluminum, zirconium, tungsten, silica and oxygen metal ion.
  • the catalyst is found to have excellent activity towards dehydration reactions. Also this catalyst can be activated and reused for the same or different reactions.
  • resulting calcinated catalyst composition has pore diameter in the range of 3.0 nm to 12.0 nm and pore volume in the range of 0.20cmVg to 0.50cmVg.
  • General method for production of calcinated catalyst composition comprises reaction of dodecyl amine with alcohol like ethanol along with water followed by addition of tetraethyl orthosilicate under vigorous stirring.
  • the reaction mixture is aged for 10 to 30 hours at temperature range 15 to 110 °C.
  • the clear liquid above the white colored precipitate is decanted and the precipitate of resultant is dried.
  • the dried resultant is calcined at high temperature to give catalyst base.
  • Such catalyst base is mixed with aqueous metal salt solutions by incipient wetness technique, after addition of the solid, resultant is dried in an oven at 110°C for at least 1 to 4 hours, the dried material is hydrolyzed by ammonia gas and washed with deionised water until neutral filtrate is obtained, then material is filtered and dried in oven for at least 20 to 30 hours at 110° C, then add tungustic acid at least 0.05 gm to 0.20 gm by grinding technique on previously prepared material of at least 0.5 gm to 1.5 gm, followed by hydrothermal treatment and then it is calcined at 750° C for at least 1 to 5 hours.
  • One of the embodiments of the present invention for process for manufacture of acrolein wherein reaction of aqueous glycerol solution with said heterogeneous calcinated solid acid catalyst is carried out.
  • reaction of aqueous glycerol solution with calcinated catalyst composition can be carried out in absence of any solvent.
  • the calcinated catalyst composition is used in the range of about 0.5 gm to 5.0 gm.
  • One of the embodiments of the present invention is to react aqueous glycerol solution with said calcinated solid acid catalyst in the temperature range of 80°C to 600 °C, preferably in the range 200°C to 450°C.
  • One of the embodiments of the present invention is the glycerol feed flow rate is in the range of 5.1 ml/h to 20.4 ml/h, preferably is that 5.1 ml/h.
  • nitrogen flow rate as a carrier gas is in the range of 0.72 lit/h to 3.0 lit h, preferably in the rang of 1.3 to 1.5 lit/h.
  • glycerol concentration is used in the range of 10 to 50 mass percent, preferably in the range of 10 to 20 mass percent.
  • One of the embodiments of the present invention for process for production of acrolein is that said calcinated solid acid catalyst is easily separable, regenerable and reusable up to in the range of 2 to 15 times, preferably in the rang of 2 to 8 times.
  • One of the embodiments of the present invention for process for production of acrolein is that reaction of aqueous glycerol solution with said calcinated solid acid catalyst is carried out for time of 1 to 100 hours, preferably for 1 to 22 hours, depending upon the reaction conditions.
  • the process of the invention may be carried out at desired temperature range of 80°C to 600 °C, preferably in the range 200°C to 450 °C wherein reaction is performed at pressures less than, greater than or equal to atmospheric pressure, with nitrogen as a carrier gas.
  • acrolein The production of acrolein is that the dehydration of aqueous glycerol solution was carried out at atmospheric pressure on down flow fixed bed haste alloy HC-276 reactor having 25.4mm ID and 300mm length with as upstream vaporizer and downstream condenser.
  • the liquid feed is fed by double piston (Well Chrom HPLC-pump K-120) pump to the vaporizer by using N 2 as a carrier gas.
  • the catalyst is loaded in the form of powder or pellets to form catalytic bed.
  • the temperature of the bed is maintained with the help of PID controller.
  • the product is condensed in a trap by circulating chilled water, or dry ice-acetone mixture, temperature is maintained in the range of at least -7 to 5° C.
  • Analysis is carried out by using Chemito GC 1000 equipped with an FID detector by using BPX-50 capillary column (30 m).
  • Hexagonal mesoporous silica A solution of 500g Hexadecyl amine in ethanol 4180 ml is added to 2960 ml distilled water. Silica precursor such as tetraethyl orthosilicate (2080 g) is added to it. The material was aged for 24 h at 30 °C. The solid material is filtered and dried at 40 °C for 12 h. The resulting material is subjected to calcined at 650 °C for 3 h.
  • HMS Hexagonal mesoporous silica
  • calcinated solid acid catalyst 2.39 gm of zirconium oxychloride and 0.11 gm of aluminum nitrate were dissolved in aqueous solution and added to 5.0 gm of precalcined HMS by incipient wetness technique, after addition this solid material is dried in an oven at 110° C for 3 hours. The dried material is hydrolysed by ammonia gas and washed with deionised water until a neutral filtrate is obtained, then it is filtered, dried in an oven for 24 hours at 110° C.
  • the generation of super acidic centers in to this material is made by grinding tungustic acid 0.1078 gm with 0.9 gm of zirconium hydroxide and aluminum hydroxide on HMS, followed by hydrothermal treatment 3 and then it is calcined at 750° C for 3 hours.
  • Adsorption average pore diameter 7.3 nm.
  • the reactions are carried out on fix bed catalytic reactor with nitrogen as carrier gas. Specifications of fix bed reactor, uses for all reactions are given in detailed description of invention.
  • 1 g of calcined catalyst is fixed, in the middle of the reactor, with glass beads as packing material above and below the catalyst in to the reactor.
  • the reactor is fed with an aqueous glycerol solution 20% by weight of glycerol at a mean feed flow rate of 10.2 ml/h, with the N 2 flow rate is 1.5 lit/h, preheater temperature is 275° C.
  • the aqueous glycerol solution is vaporized in the preheater and then passed over the catalyst bed.
  • the effect of temperature of the reactions is studied form 250°C to 325°C, for 4 h.
  • the sample is then analyzed by gas chromatography equipped with flame ionization detector, With BPX-50 capillary column. Then acrolein is distilled off from reaction liquid products at 45-55 °C temperature to get the desired pure acrolein.
  • the reactions are carried out with different amount of glycerol concentration, on fix bed catalytic reactor with nitrogen as carrier gas.
  • 1 g of calcined catalyst is fixed, in the middle of the reactor, with glass beads as packing material above P T/IN2010/000755 and below the catalyst in to the reactor.
  • Feed flow rate is 10.2 ml/h
  • N 2 flow rate is 1.5 lit/h
  • preheater temperature is 275° C.
  • reactor bed temperature is 275°C
  • the aqueous glycerol solution is vaporized in the preheater and then passed over the catalyst. Reactions are carried out for 4 h.
  • the effect of glycerol concentration is studied with 10%, 20% and 50% (w/w).
  • Reactions are carried out with different amount of calcined catalyst loadings 2.0, 1.0 and 0.5g to get WHSV of 5.37, 10.74 and 21.78 respectively.
  • the reactor is fed with an aqueous glycerol solution containing 20% by weight of glycerol, at a mean feed flow rate is 10.2 ml/h, N 2 flow rate is 1.5 lit/h, preheater temperature is 275°C and reactor bed temperature is 275 °C.
  • Reactions are carried out for 16h, herewith shown the difference in the conversion and selectivity for different WHSV is as follows.
  • Reactions are carried out with different feed flow rate ranging from 5.1 - 20.4 ml/h, of aqueous glycerol solution.
  • 1.0 g of calcined catalyst is loaded into the fix bed reactor.
  • the reactor is fed with an aqueous glycerol solution 20% by weight of glycerol with N 2 flow rate is 1.5 lit/h.
  • preheater temperature is 275°C and reactor bed temperature is 275 °C, reactions are carried out for 4 h.
  • Reactions are carried out with Different N 2 flow rate ranging from 0.72 - 3.0 lit/h.
  • 1.0g of calcined catalyst is loaded into the fix bed reactor.
  • the reactor is fed with an aqueous glycerol solution containing 20% by weight of glycerol, at a mean feed flow rate of 10.2 ml/h, preheater temperature is 275°C and reactor bed temperature is 275 °C.
  • the reactions are carried out for 4 h.
  • reaction stability and activity of the catalyst is evaluated by time on stream (TOS) data.
  • TOS time on stream
  • 2.0g of calcined catalyst is loaded into the fix bed reactor.
  • the reactor is fed with an aqueous glycerol solution containing 20% by weight of glycerol, at a mean feed flow rate of 10.2 ml/h, N 2 flow rate is 1.5 lit/h, preheater temperature is 275°C and reactor bed temperature is 275 °C. Reaction is carried out for 100 h.
  • Reactions are carried out for catalyst regeneration and reusability study, after completion of the reaction, the catalyst is removed from the reactor and washed with methanol up to 3 to 4 times, to remove the adsorbed polymerized material from the catalyst. Then c Catalyst is subjected to calcinations at 550 °C for 3 h, in the flowing air to burn off coke present on the catalyst. There is an inevitable loss of catalyst particles during these operations. Hence, actual amount of catalyst used in the next batch is almost 10% less than the previous batch. The loss of the catalyst is made up with fresh catalyst. Catalyst reusability is performing reactions by using 1.0g of calcined catalyst is loaded into the fix bed reactor.
  • the reactor is fed with an aqueous glycerol solution containing 20% by weight of glycerol, at a mean feed flow rate of 10.2 ml/h, N 2 flow rate is 1.5 lit/h, preheater temperature is 275°C and reactor bed temperature is 275 °C. Reactions are carried out up to 16 h. for 6 times in a row.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

L'invention concerne l'élaboration et le développement d'une composition de catalyseur calcinée contenant une composition de métaux de transition à d-blocs, de métal à p-blocs et de silicium en tant qu'atome de métal de base avec de l'oxygène, la surface active spécifique du catalyseur se situant entre 50 m2/g et 1000 m2/g. La composition des métaux de transition à d-blocs et de l'atome de métal à p-bloc est spécifiquement choisie pour une composition de catalyseur calcinée selon un besoin de réaction catalytique spécifique. L'utilisation de la composition de catalyseur calcinée permet de convertir la solution de glycérol aqueuse dans des conditions de réaction douces pour produire une acroléïne de pureté élevée.
PCT/IN2010/000755 2010-09-16 2010-11-19 Procédé de production d'acroléïne et d'un catalyseur réutilisable Ceased WO2012035540A1 (fr)

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IN2562MU2010 2010-09-16
IN2562/MUM/2010 2010-09-16

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WO2012035540A1 true WO2012035540A1 (fr) 2012-03-22

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017138016A1 (fr) * 2016-02-08 2017-08-17 Yadav, Ganapati Dadasaheb Catalyseur accordable pour méthylation en phase vapeur et sa préparation

Citations (7)

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