EP2183210A1 - Verfahren zur reaktiven verdampfung von glycerol - Google Patents

Verfahren zur reaktiven verdampfung von glycerol

Info

Publication number
EP2183210A1
EP2183210A1 EP08835353A EP08835353A EP2183210A1 EP 2183210 A1 EP2183210 A1 EP 2183210A1 EP 08835353 A EP08835353 A EP 08835353A EP 08835353 A EP08835353 A EP 08835353A EP 2183210 A1 EP2183210 A1 EP 2183210A1
Authority
EP
European Patent Office
Prior art keywords
glycerol
acrolein
acrylic acid
fluidized bed
solid
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP08835353A
Other languages
English (en)
French (fr)
Inventor
Jean-Luc Dubois
Grégory PATIENCE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
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 Arkema France SA filed Critical Arkema France SA
Publication of EP2183210A1 publication Critical patent/EP2183210A1/de
Withdrawn legal-status Critical Current

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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • 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

Definitions

  • the present invention relates to an aqueous glycerol solution vaporization method in a fluidized bed containing a solid reagent, simultaneously for vaporizing the aqueous glycéroi, remove impurities present in the solution or generated during evaporation and to carry out the dehydration reaction of glycerol to acroine and / or the dehydration of glycerol to acrylic acid.
  • Glycerol is a chemical, ie 1, 2,3-propane triol, which can be obtained either by chemical synthesis from propylene or as a co-product formed during the methanolysis of vegetable oils.
  • the methanolysis of vegetable oils can be carried out according to various processes, in particular by using homogeneous catalysis such as sodium hydroxide or
  • Methyl esters are used in particular as fuels or fuels in diesel and heating oil.
  • EIVIHV methyl esters of vegetable oils
  • Glycerol from vegetable oils is a natural product of renewable origin and is thus increasingly available. In the current framework of new concept of green chemistry, and more generally of sustainable development, it becomes more and more interesting to value this product.
  • glycerin As an illustration, the following table gives the typical analyzes of different glycerines produced on different industrial sites:
  • MONG non-glycerinous organic matter: fatty acids, ester, other
  • the crude glycerin generally has a composition of about 88% glycerol, 9-10% water and 2-3% impurities.
  • it may contain impurities such as basic salts (for example sodium or potassium), non-glycerine organic compounds, methanol or residues of vegetable oils.
  • impurities such as basic salts (for example sodium or potassium), non-glycerine organic compounds, methanol or residues of vegetable oils.
  • the presence of these impurities is particularly detrimental for the reactions implemented or for the quality of the finished products.
  • the presence of sodium or potassium salts is detrimental to the catalytic dehydration reaction of glycerol to acrolein, since these salts are capable of poisoning the acid sites of the catalysts used. artwork.
  • aqueous solutions of crude glycerol or glycerin generally require prior treatment before use, or purification treatment to consider new applications.
  • evaporation, distillation, lime treatment (to neutralize residual fatty acids) followed by filtration, ion exchange or ionic exclusion treatment, osmosis separation can be carried out. reverse or electrodialysis.
  • multi-effect evaporators are used to concentrate dilute glycerol solutions.
  • a triple effect evaporator it is possible to evaporate 2.4 kg of water with 1 kg of steam.
  • Distillation is one of the techniques used to concentrate and purify glycerine. As glycerol begins to decompose at about 202 0 C 1 well below its boiling point (293 ° C), it is necessary to distil the glycerin in several stages using a reduced pressure. In some cases distillation is done by batch operations until salts and non-volatile compounds have accumulated sufficiently in the capacity. The operation is then stopped and the capacity discharged from the impurities before restarting the distillation. The evaporation is carried out under vacuum, and the partial condensation of the glycerol (which will condense before the water) at the outlet of the unit makes it possible to obtain a concentrated solution directly. Typically, pressures of 10 mmHg are used, for a temperature of 160-165 ° C., which gives low partial pressures in giycerol in the vapor phase.
  • the distilled glycerin may still contain colored compounds, it is sometimes necessary to bleach glycerin for pharmaceutical and food applications.
  • activated charcoal is added to its glycerine to discolor it.
  • Glycerin purification by ion exclusion has also been developed and uses ionic resins to separate soluble ionic salts in aqueous solution from nonionic compounds such as glycerol. It is a technique that avoids the consumption of heat and chemical regenerants, and allows to purify highly contaminated streams like raw glycerin, using only water as a chemical regenerant.
  • glycerol which are weakly contaminated with salts can be exchanged simply on acidic and basic resins.
  • the glycerol solutions thus purified can then be concentrated by evaporation.
  • the reverse osmosis technique based on a semi-permeable membrane separation by applying a pressure, has been proposed for the concentration of particularly diluted streams in glycerol.
  • Glycerine and sodium hydroxide solutions obtained after transesterification of rapeseed oil were demineralized by membrane electrodialysis to produce pure glycerine. This technique is described in the reference: Schaffner, F. et al. Proc. - World Fiitr. Congress, 7 m . 1998, Volume 2, 629-633.
  • the temperature control is very critical because some undesirable reactions can take place, such as the formation of nitrogen compounds by degradation of proteinaceous material present in glycerin, the formation of ester volatile glycerine by reaction with low mass soaps mole, the formation of polyglycerol, the formation of acr ⁇ iine which contributes to the smells of the final product. !! It is therefore important to limit the residence time of the glycerin at high temperature, as well as this temperature. The evaporation processes used conventionally therefore do not allow to have high partial pressures of glycerol in the vapor phase. Moreover, it is often necessary to combine several treatments to obtain the glycerol with a purity and a concentration suitable for the intended application.
  • the Applicant Company describes a one-step process for vaporizing an aqueous solution of glycerol and simultaneously removing impurities present in the solution or generated during evaporation.
  • This process consists in vaporizing the aqueous solution of glycerol! in contact with a fluidized bed containing an inert solid maintained at a temperature sufficient to allow instantaneous vaporization of glycerol and water.
  • the impurities present in the aqueous solution are eliminated simultaneously, because the technique of the fluidized bed makes it possible to continuously withdraw part of the solid in order to regenerate it ex situ.
  • the glycerol vapors obtained according to this process are then directly usable in a downstream process using glycerol in gas form, in particular the processes for producing acroSine or acrylic acid described, for example, in the documents WO 06/087083, WO 06/087084, WO 06/114506, WO 07/090990 and WO 07/090991, or a process for producing acrylonitrile as described in the patent application FR 2 912 742.
  • acrolein and / or acrylic acid from glycerol! in a gas phase process requires the implementation of a prior step of glycerol vaporization, a step that can be costly if the glycerol is used in the form of a dilute aqueous solution.
  • the aqueous solution of glycerol having optionally undergone preliminary purification treatment according to one of the methods described above, is vaporized in a heated chamber before passing over a catalyst suitable for the reaction envisaged, in a fixed bed reactor, fluidized bed, circulating fluidized bed or in a plate exchanger type reactor.
  • the Applicant Company has now surprisingly discovered that it is possible simultaneously to vaporize an aqueous solution of glycerol, to remove impurities present in this solution or generated during evaporation, and to carry out the dehydration reaction of the glycerol to acrolein and / or oxidizing glycerol to acrylic acid.
  • Such a method makes it possible to minimize energy costs for the production of acroine and / or acrylic acid from aqueous solutions of glycerol and constitutes a one-step process implemented in a simplified installation.
  • the present invention therefore relates to a process for reactive vaporization of aqueous solutions of glycerol (or glycerine) in a fluidized bed containing a reactive solid.
  • the aqueous solution of glycerol is injected directly into a fluidized bed containing a reactive solid maintained at a temperature sufficient to allow the instantaneous vaporization of glycerol and water, as well as the reaction of glycerol on the reactive solid.
  • the concentration of the aqueous glycerol solution can vary widely, for example from 20 to 99% by weight of glycerol, preferably 30 to 80% by weight glycerol solutions are used. It may be raw aqueous solutions, more or less diluted and containing more or less impurities, such as can be obtained from the methanolysis of vegetable oils.
  • the solid reagent is chosen from catalysts suitable for carrying out the dehydration reaction of glycerol to acrolein and / or the reaction of oxidizing hydrite of glycerol to acrylic acid.
  • the fluidization can be ensured by the vaporization of the glycerol solution, and / or by a stream of inert gas (nitrogen, CO 2 , recycle gas, etc.), or of air, of oxygen, or of a gas mixture known to those skilled in the art for optimizing the dehydration reaction of the glycerol to acrolein and / or the oxidation of glycerol to acrylic acid.
  • the temperature of the fluidized bed is generally between 18O 0 C and 40O 0 C, preferably between 22O 0 C and 350 0 C, more particularly between 26O 0 C and 32O 0 C.
  • the invention also relates to the use of a fluidized bed containing a reactive solid for simultaneously vaporizing and purifying an aqueous solution of glycerol, and effecting the dehydration reaction of glycerol to acrolein and / or of the oxidation of glycerol to acrylic acid .
  • the invention also relates to a process for preparing acrolein and / or acrylic acid from glycerol in the gas phase in a fluidized bed reactor characterized in that an aqueous glycerol solution is sent directly into the fluidized bed containing a reactive solid maintained at a temperature between 180 ° C and 4OQ 0 C, preferably between 220 0 C and 35O 0 C 1 in contact with which is performed the dehydration reaction of giycéro! acrolein and / or oxidation of glycerol to acrylic acid.
  • a reactive solid maintained at a temperature between 180 ° C and 4OQ 0 C, preferably between 220 0 C and 35O 0 C 1 in contact with which is performed the dehydration reaction of giycéro! acrolein and / or oxidation of glycerol to acrylic acid.
  • the process according to the invention leads to high partial pressures of glycerol in the vapor phase, which has the advantage of vaporizing the glycerol and reacting it with a productivity significantly higher than that obtained with the processes implementing a vaporization prior to the reaction.
  • the impurities present in the aqueous solution are eliminated simultaneously, because the fluidized bed technique allows a part of the solid to be withdrawn continuously to regenerate it ex situ.
  • the organic compounds present in the glycerol solution but also the products of decomposition of glycéroi during this evaporation step can lead to the formation of coke which is deposited on the reactive solid.
  • the aqueous glycerol solution contains salts (for example sodium chloride, or sodium sulphate), these salts are also deposited on the external surface of the reactive solid during the evaporation of the aqueous glycerol solution.
  • the solid reagent containing the coke and / or the mineral salts can then be withdrawn continuously to be regenerated in another reactor, before being recycled into the fluidized bed.
  • the regeneration can also be carried out continuously in the reactor.
  • the elimination of the inorganic salts can be carried out simply by washing with water of the solid, or any other appropriate technique. It can also be carried out by continuous attrition of the catalyst, the deposition of salt forming preferably at the periphery of the catalyst particles.
  • the regeneration of the solid consists of a combustion of the solid deposits, it is generally carried out with air in a reactor which can be for example another continuously operated fluidized bed, a circulating fluidized bed, a fixed bed, or any other reactor may be suitable. Preferably, a fluidized bed operated continuously will be used.
  • the combustion of the carbonaceous deposits on the reactive solid not only makes it possible to regenerate it but also to heat it up before returning it to the fluidized evaporation / glycerol reaction bed.
  • This combustion can be carried out in the presence of a fuel, for example methane, which helps to bring the reactive solid to the temperature necessary for the reactive evaporation of the aqueous glycerol solution.
  • the particles are moving relative to each other which causes an attrition of the solid.
  • it is sought to limit this attrition which consumes solid and produces fine particles.
  • attrition makes it possible to eliminate part of the deposits which form on the reactive solid.
  • the fine particles thus formed by attrition are removed downstream, for example by separation in a cyclone and / or by filtration, or else by electrostatic precipitation.
  • H 0 Hammett acidity
  • the solids satisfying the acidity criterion H 0 of less than +2 can be chosen from natural or synthetic siliceous materials or acidic zeolites; inorganic supports, such as oxides, covered by inorganic acids, mono, di, tri or polyacids; oxides or mixed oxides or heteropolyacids.
  • the reactive solids are chosen from zeolites, National ® composites (based on sulfonic acid of fluorinated polymers), chlorinated aluminas, acids and salts of phosphotungstic and / or si ⁇ cotungstic acids, and various oxide solids.
  • the reactive solids may also be chosen from solids containing at least one element selected from the list Mo, V, W, Re 1 Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Te, Sb, Bi, Pt. 1 Pd, Ru, Rh, present in the metal form or in the form of oxide, mixed oxides, sulphate or phosphate.
  • the solid used in the process of the invention should not only be a catalyst for dehydrating glycerol to acrolein and / or the reaction of glycerol for oxidizing glycerol to acrylic acid, but it must be resistant in terms of mechanical strength. and in particular resistant to attrition in order to optimize its use in a fluidized bed.
  • Various methods known to those skilled in the art can be used to shape the solid reagent
  • the reactive solid is previously shaped by atomization.
  • the catalyst may also be prepared from coarse particles which are milled to a particle size distribution to utilize the catalyst in a fluidized bed.
  • this type of preparation method generally leads to catalysts having an insufficient mechanical strength reducing the service life of the catalyst in the reactor, in particular by attrition wear of the cataiyzer grains.
  • a catalyst prepared by mixing a suspension of the precursors of the catalyst active material with a coiloidal solution (binder), for example silica sol or alumina, followed by drying by atomization of His suspension thus obtained, this method leading to a powder composed of spherical particles having an appropriate particle size distribution for the application in a fluidized bed.
  • a coiloidal solution for example silica sol or alumina
  • This method of preparation requires binder contents close to 50% by weight, which correspondingly reduces the amount of active material in the final catalyst.
  • the catalyst will undergo attrition which will change the granuiometric distribution over time. This reduction in particle size distribution will require the catalyst to be replaced before it is completely deactivated to avoid hydrodynamic problems in the reactor.
  • a catalyst consisting of particles formed of a core of active material coated with a harder surface layer, for example a silica shell, is used as a reactive solid.
  • a harder surface layer for example a silica shell
  • two methods are described therein: one developed by Shell consists of coating catalyst particles already formed with a silica shell and is described for example in WO 97/26313 and EP697247.
  • the other method initially developed by Du Pont, is to mix a suspension of active material with a colloidal solution of silica particles of very small diameter, in general!
  • a method of particle shaping by atomizing a slurry of macroparticles and a colloidal solution of microparticles is also disclosed in US Patent 4,477,492.
  • the catalyst consisting of particles formed of a core of active material coated with a binder-enriched surface layer such as silica, alumina, titanium oxide can also be obtained from two types of colloidal binder solutions of different granulometry, in order to maintain binder at the core of the particle while causing surface migration of another binder fraction.
  • This type of process is particularly illustrated in US Patents 5,302,568, US 8,878,688 and US 6,382,128.
  • polysiic acid is used as a source of small diameter colloidal silica.
  • an aqueous solution of giycérol or glycerol (4) is introduced into a reactor (1) containing a fluidized bed of a reactive solid.
  • the fluidization can optionally be ensured by a stream of inert gas (nitrogen, CO 2 , recycle gas ,,,), or air, oxygen, or a gas mixture known to those skilled in the art for optimize the dehydration reaction of glycerol to acrolein and / or oxidation of glycerol to acrylic acid.
  • the fluidized bed is heated via the heat exchanger (3).
  • the glycerol / acrolein / acrylic acid and water vapors are extracted from the reactor in (8) and a unit (7) makes it possible to recover the fine particles of the installation, as well as possibly the salt which has deposited on the catalyst.
  • One unit (6) allows washing the solid used in the fluidized bed to remove the deposited mineral salts.
  • the reactor (2) is a regenerator of the reactive solid in which the solid withdrawn from (1) is subjected to combustion in the presence of regeneration gas (5) containing molecular oxygen and / or fuels, the regenerated solid being returned to the reactor (1), the gases from the regeneration unit are discharged in (9).
  • the process according to the invention leads to glycerol / acrolein / acrylic acid and water vapors which are then subjected to absorption / purification steps according to techniques well known to those skilled in the art.
  • This process makes it possible to obtain acrolein and / or acrylic acid with minimized levels of by-products, such as by-hydroxyacetone, propanaldehyde or propionic acid, after the absorption step.
  • by-products such as by-hydroxyacetone, propanaldehyde or propionic acid
  • the invention also relates to acrolein and / or acrylic acid obtained by the process defined above further followed by a step of absorption, comprising a propanaldehyde by-products content, propionic acid and hydroxyacetone such that the ratio
  • the hydroxyacefone / acrolein molar is less than 0.2, preferably less than 0.05, and the molar ratio (propanaidyl + propionic acid) / (acroine + acrylic acid) is less than 0.01, preferably less than 0.005.
  • Example 1 Catalyst A of WZZrO 2 -Si Type (with Polysilicic Acid) A tungsten zirconia powder of Dai-lchi Kigenso KK (batch Z 1104), of small particle size, with characteristics of: 0Z 0 VVO 3 : 11, 1 %
  • the sodium silicate is diluted to give an 8% SiO 2 solution 39.6 g of sodium silicate (SiO 2 -Na 2 O) at 30.3% SiO 2
  • the suspension is obtained from tungsten zirconia and polysilicic acid which are mixed in the following proportions: 100.0 g of tungsten zirconia
  • the suspension is passed to the micronizer (speed of rotation of the mill: 2500 rev / min and that of the feed pump: 50 rev / min).
  • the operation of spray is performed immediately after the preparations in order to overcome one of the solution maturation problem
  • the drying gas is air.
  • the spray nozzle is based on a principle of generation of droplets by vibration from an ultrasonic generator (ultrasound frequency: 20 kHz).
  • the feed tray is kept stirring in the ice.
  • the operating conditions are:
  • the particle size distribution is analyzed after drying overnight in an oven at 80 ° C.
  • the solid is then sieved so as to eliminate the maximum of particles with a diameter of less than 50 ⁇ m and particles larger than 160 ⁇ m.
  • the heat treatment is carried out using a rotary kiln with a useful capacity of about 500 ml.
  • 50 g of solid are first treated at 300 ° C. under 80 l / h nitrogen for 4 hours and then at 500 ° C. under nitrogen (60 l / h) for two hours.
  • Final sieving is necessary to keep only the 50-160 ⁇ m fraction.
  • a batch of tungsten zirconia in the form of pellets Z1044 Pellet is used here.
  • the granules are milled to keep only the fraction between 50 and 160 microns.
  • the tungsten zirconia powder is placed in a commercial fluidized bed coating apparatus (NIRO Aeromatic STREA-1), and fluidized with air at a temperature of 80 ° C.
  • a colloidal silica solution, LUDOX AS 40, containing 40% by weight of silica, is fed into the coating machine by a pump.
  • the solution is sprayed using a nozzle with an air pressure of 1 bar.
  • the fluidization is maintained for 30 minutes to complete the drying of the solid.
  • the catalyst is recovered and calcined at 500 ° C. under a stream of nitrogen for 2 hours.
  • the silica content of the final catalyst is 15% by weight, determined by the weight gain of the tungsten zirconia.
  • the solution is heated with stirring at 90-95 0 C until complete dissolution and obtaining a clear orange-red solution (about one hour including the heating time).
  • the suspension is obtained from the dry precursor and the polysilicic acid which are mixed in the following proportions: 1000 g of telluride precursor
  • the atomization operation is carried out as indicated in Example 1 but with a feed rate of 1.3 kg / h on average and an air flow of 40 m 3 / h.
  • the heat treatment is carried out using a rotary kiln with a useful capacity of about 4385 ml. 513 g of solid are first treated at 300 ° C. under 60 l / h air for 4 hours and then at 600 ° C. under nitrogen (60 l / h) for two hours. 410 g are recovered. Final sieving is necessary to keep only the fraction 50-180 ⁇ m: 370 g.
  • the solution is heated with stirring at 99 ° C. for three hours after stabilization of the temperature. An opaque mixture of dark blue color is obtained.
  • Solution B of oxalic acid and niobic acid is poured into the solution A-colloidal silica mixture.
  • the mixture becomes cloudy with the formation of a precipitate in suspension and the color becomes orange-yellow.
  • Precursor fines (1370 g) from the previous atomization operation are added to the solution at this stage. After half an hour of additional stirring, the heating is stopped. The suspension is then recovered and micronized.
  • the dSO mean diameter of the particles in suspension measured by laser granulometry, on a HORIBA LA300 increases from 18 ⁇ m to 0.2 ⁇ m with micronization.
  • Micronization is carried out on a Netzsch Labstar device under the following operating conditions:
  • the outlet temperature of the product reaches 55 ° C.
  • micronized suspension is atomized immediately (solids content of the mixture measured with an infra-red desiccator at 33% by weight).
  • the atomization operation is carried out immediately after micronization.
  • a NIRO Minor Mobile High-Tech atomizer is used.
  • the drying chamber has a double envelope raised by 2 m and traversed by steam.
  • the drying gas is nitrogen.
  • the spray nozzle is based on a principle of generating droplets by vibration from an ultrasonic generator (Sodeva, frequency of ultrasound 20 kHz).
  • Sodeva frequency of ultrasound 20 kHz.
  • the feed tray is maintained stirring and the suspension preheated to 80 0 C with a thermostatic bath.
  • the operating conditions are: T 0 C input: 210 ° C ⁇ I o CL / output: 105 0 C Feed rate: 5.5 kg / h on average
  • the particle size distribution is analyzed by laser granulometry after drying overnight in an oven at 80 ° C.
  • the solid is then sieved so as to eliminate the maximum of particles with a diameter of less than 50 ⁇ m and particles larger than 160 ⁇ m.
  • the heat treatment is carried out using a rotary kiln (200 mm diameter, 270 mm cylindrical length, working volume of 2.5 liters). One end is closed. The gas is supplied by means of a rod to the interior of the cylinder.
  • 3319 g of solid are first treated at 310 ° C. [300-31O] under 900 l / h [100-1200] air for 4 hours and then at 800 ° C. under nitrogen (200 i / h) for two hours.
  • the temperature ramp is 4.5 ° C / min. in the average solid.
  • An oximeter connected to the nitrogen supply network measures the oxygen content of the gas: typically between 1 and 2 ppm.
  • the rotation speed of the oven is 15 rpm.
  • Catalyst Y consists of 8 batches from similar preparations and has the following characteristics:
  • Step 1 Preparation of the dry precursor: Preparation of the solution B: In a Rayneri Trimix mixer, 295 g of niobic acid (HY-340 CBMM, 81.5% Nb 2 O 5 ) are introduced.
  • Solution B of oxalic acid and niobic acid is poured into the mixture S Solution A-colloidal silica.
  • the mixture becomes cloudy with the formation of a precipitate in suspension and the color becomes orange-yellow.
  • the heating is stopped.
  • the suspension is then recovered and atomized immediately (solids content of the mixture measured using a 36% w / w infra-red desiccator).
  • the atomization operation is carried out immediately after the preparation of the suspension.
  • the NIRO Minor Mobile High-Tech Modified Atomizer is internally preferably used.
  • the drying gas is nitrogen.
  • the drying chamber. raised by 2 m has a double envelope crossed by steam.
  • the spray nozzle is based on a principle of vibration droplet generation from an ultrasonic generator (Sodeva, ultrasound frequency: 20 kHz).
  • the feed tray is kept stirring and the suspension preheated to 80 ° C. using a thermostatic bath.
  • the standard operating conditions are: CT input: 209-210 ° CT 0 C output: 105-110 0 C Feed rate: 5 kg / h on average
  • the evaporative capacity of the atomizer is 3 kg / h of water.
  • the recovered solid is then further dried overnight in a ventilated oven at
  • the heat treatment is carried out using a rotary kiln (200 mm diameter, 270 mm cylindrical length, working volume of 2.5 liters). One end is closed. The gas is brought using a rod to the inside of the cylinder. Different lots treated in a similar way were collected
  • the catalyst Z is characterized by:
  • EXAMPLE 8 The catalysts prepared according to Examples 1 to 5 are used in a fluidized bed, fed with an aqueous glycerol solution at 50% by weight and maintained at 310 ° C. A diluted air stream ensures the fluidtation of the catalyst. The glycerol solution is directly vaporized in the fluidized bed. The total pressure in the reactor is 2.2 bars, with the following glycerol / water / O 2 / N 2 molar ratios: 1/6/1/4, with a linear gas velocity of 10 cm / s.
  • the products are collected at the reactor outlet and condensed to be analyzed by chromatography.
  • the fluidized bed consists of a stainless steel tube 41 mm in diameter and a total height of 790 mm.
  • the fluidized bed is immersed in a fluidized sand bath, heated by electric elements installed inside the bath.
  • Three thermocouples recorded the temperature gradient along the tube.
  • 260 ml / min (260 lbs / min) of argon was fed air at a flow rate of 260 ml / min below a porous metal plate that distributes the gas through the diameter of the vessel. reactor.
  • Ash ⁇ 0.01% is fed by a 7 mm metal tube that goes to the bottom of the bed with a flow rate of 3 ml / min.
  • the total pressure in the fluidized bed is 1 bar and the temperature is maintained at 35O 0 C.
  • the products are collected in a fluidized bed outlet and condensed to be analyzed by liquid chromatography after stabilization with hydroquinone. 12% of the total flow is condensed in an ice trap (cooled by ice) filled with 800 ml of water.
  • the sodium content in the product is measured by atomic absorption; and the result is expressed as a percentage of the sodium initially present in the crude glycerol and is therefore expressed as a percentage of residual salt,
  • the catalyst After more than 24 hours of operation, the catalyst has passed more than 704 g of glycerol! and 41 g of salt, and still leads to almost 25% acroine yield without visible deactivation.
  • the process is capable of vaporizing the glycerol solution! gross, eliminating the se! and converting glycerol to acrolein.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP08835353A 2007-09-06 2008-09-05 Verfahren zur reaktiven verdampfung von glycerol Withdrawn EP2183210A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0757396A FR2920767B1 (fr) 2007-09-06 2007-09-06 Procede de vaporisation reactive de glycerol
PCT/FR2008/051585 WO2009044051A1 (fr) 2007-09-06 2008-09-05 Procede de vaporisation reactive de glycerol

Publications (1)

Publication Number Publication Date
EP2183210A1 true EP2183210A1 (de) 2010-05-12

Family

ID=39244680

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08835353A Withdrawn EP2183210A1 (de) 2007-09-06 2008-09-05 Verfahren zur reaktiven verdampfung von glycerol

Country Status (9)

Country Link
US (1) US8530697B2 (de)
EP (1) EP2183210A1 (de)
JP (1) JP5615707B2 (de)
KR (1) KR101566562B1 (de)
CN (1) CN101796012A (de)
BR (1) BRPI0816427A2 (de)
FR (1) FR2920767B1 (de)
MY (1) MY151959A (de)
WO (1) WO2009044051A1 (de)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2939791B1 (fr) 2008-12-16 2011-01-14 Adisseo France Sas Procede de preparation d'acroleine a partir de glycerol ou de glycerine brute
FR2945044B1 (fr) * 2009-04-30 2012-12-28 Arkema France Procede ameliore de production d'un (co) polymere d'ester acrylique
FR2954312B1 (fr) * 2009-12-21 2012-02-10 Adisseo France Sas Procede de preparation d'acroleine par deshydratation catalytique de glycerol ou glycerine
FR2961507B1 (fr) 2010-06-17 2016-03-04 Adisseo France Sas Procede de preparation d'acroleine a partir de glycerol ou de glycerine
FR2966456B1 (fr) * 2010-10-26 2013-03-15 Adisseo France Sas Procede d'obtention d'acroleine par deshydratation catalytique de glycerol ou de glycerine
FR2977809B1 (fr) 2011-07-12 2016-01-08 Arkema France Regeneration de catalyseur en continu dans un reacteur a lit fluidise
JP2014034023A (ja) * 2012-08-10 2014-02-24 Hokkaido Univ グリセリンからアクリル酸を製造するための触媒とその製造方法
FR2997398B1 (fr) * 2012-10-30 2014-11-21 Adisseo France Sas Procede de preparation de l’acroleine a partir de glycerol
CN104387249B (zh) * 2014-10-30 2017-03-01 清华大学 丙烯醛制备方法
KR101774543B1 (ko) 2014-12-19 2017-09-04 주식회사 엘지화학 글리세린 탈수 반응용 촉매, 이의 제조 방법 및 상기 촉매를 이용한 아크롤레인의 제조 방법
US20160368861A1 (en) 2015-06-19 2016-12-22 Southern Research Institute Compositions and methods related to the production of acrylonitrile
US9708249B1 (en) 2016-08-24 2017-07-18 Southern Research Institute Compositions and methods related to the production of acrylonitrile
WO2018212149A1 (ja) 2017-05-16 2018-11-22 住友化学株式会社 メチオニンの気流搬送方法
CN109304162B (zh) * 2017-07-28 2021-06-22 中国石油化工股份有限公司 甘油生产丙烯酸的方法
CN109304163B (zh) * 2017-07-28 2021-06-18 中国石油化工股份有限公司 甘油生产丙烯酸的催化剂
CN113716781A (zh) * 2021-09-07 2021-11-30 南京齐超环保科技有限公司 一种环氧树脂废水中甘油及氯化钠的回收方法

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US286384A (en) * 1883-10-09 Salt-box
US4477492A (en) 1983-04-22 1984-10-16 E. I. Du Pont De Nemours And Company Process for preparing superficially porous supports for chromatography and catalysts
US4677084A (en) 1985-11-27 1987-06-30 E. I. Du Pont De Nemours And Company Attrition resistant catalysts, catalyst precursors and catalyst supports and process for preparing same
DE4238493C1 (de) 1992-11-14 1994-04-21 Degussa Verfahren zur Herstellung von Acrolein und dessen Verwendung
US5302566A (en) 1993-01-25 1994-04-12 E. I. Du Pont De Nemours And Company Process for preparing attrition resistant catalysts
EP0697247B1 (de) 1994-07-15 1999-09-29 Shell Internationale Researchmaatschappij B.V. Verfahren zum Umwandlung von Kohlenwasserstoffeinsätzen
AR005446A1 (es) 1996-01-15 1999-06-23 Shell Int Research Un procedimiento para la conversion catalitica de una alimentacion hidrocarburica
KR20010021832A (ko) 1997-07-15 2001-03-15 아토피나 프로필렌에서 아크롤린으로의 개선된 증기상 산화
US6437193B1 (en) 1997-07-15 2002-08-20 E. I. Du Pont De Nemours And Company Vapor phase oxidation of propylene to acrolein
US6281384B1 (en) 1998-06-26 2001-08-28 E. I. Du Pont Nemours And Company Vapor phase catalytic oxidation of propylene to acrylic acid
US6107238A (en) 1998-09-30 2000-08-22 E. I. Du Pont De Nemours And Company Process for manufacture and use of improved attrition resistant catalyst
US6362128B1 (en) 1998-11-20 2002-03-26 E. I. Du Pont De Nemours And Company Process for manufacture of an attrition resistant catalyst
US6310240B1 (en) 1998-12-23 2001-10-30 E. I. Du Pont De Nemours And Company Vapor phase oxidation of acrolein to acrylic acid
JP4308372B2 (ja) * 1999-07-06 2009-08-05 株式会社日本触媒 （メタ）アクリル酸および／または（メタ）アクロレインの吸収方法及びその装置
US6878668B1 (en) 1999-07-14 2005-04-12 E. I. Du Pont De Nemours And Company Process for manufacture of an attrition resistant catalyst
FR2826959B1 (fr) 2001-07-06 2003-09-05 Atofina Procede de fabrication d'acroleine a partir du propylene par reaction redox en reacteur a lit entraine et utilisation d'une composition solide d'oxydes mixtes comme systeme redox dans ladite reaction
FR2882053B1 (fr) 2005-02-15 2007-03-23 Arkema Sa Procede de deshydratation du glycerol en acrolene
FR2882052B1 (fr) * 2005-02-15 2007-03-23 Arkema Sa Procede de deshydratation du glycerol en acroleine
FR2884818B1 (fr) * 2005-04-25 2007-07-13 Arkema Sa Procede de preparation d'acide acrylique a partir de glycerol
FR2897058B1 (fr) 2006-02-07 2008-04-18 Arkema Sa Procede de preparation d'acroleine
FR2897059B1 (fr) 2006-02-07 2008-04-18 Arkema Sa Procede de preparation d'acide acrylique
FR2903620B1 (fr) * 2006-07-13 2009-02-20 Arkema France Catalyseur membranaire pour la synthese d'acide acrylique a partir de glycerol
US8076509B2 (en) * 2006-12-01 2011-12-13 Nippon Shokubai Co., Ltd. Process for producing acrylic acid
FR2912742B1 (fr) 2007-02-16 2010-03-05 Arkema France Procede de synthese d'acrylonitrile a partir de glycerol
FR2913974A1 (fr) * 2007-03-19 2008-09-26 Arkema France Procede de vaporisation de glycerol

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009044051A1 *

Also Published As

Publication number Publication date
JP2010538050A (ja) 2010-12-09
CN101796012A (zh) 2010-08-04
WO2009044051A1 (fr) 2009-04-09
KR20100057833A (ko) 2010-06-01
US8530697B2 (en) 2013-09-10
BRPI0816427A2 (pt) 2015-03-03
FR2920767B1 (fr) 2009-12-18
MY151959A (en) 2014-07-31
US20110028760A1 (en) 2011-02-03
KR101566562B1 (ko) 2015-11-05
FR2920767A1 (fr) 2009-03-13
JP5615707B2 (ja) 2014-10-29

Similar Documents

Publication Publication Date Title
EP2183210A1 (de) Verfahren zur reaktiven verdampfung von glycerol
EP1874720B1 (de) Verfahren zur herstellung von acrylsäure aus glycerol
EP2121551B1 (de) Glycerinverdampfungsverfahren
EP2188241B1 (de) Verfahren zur herstellung von acrolein aus glycerol
EP2513027B1 (de) Verfahren zur herstellung von acrolein und/oder acrylsäure aus glycerol
EP2456743B1 (de) Verfahren zur herstellung von acrylsäure aus glycerin aus bioressourcen
EP2513026B1 (de) Verfahren zur herstellung von acrolein und/oder acrylsäure aus glycerol
WO2008007002A2 (fr) Catalyseur membranaire pour la synthèse d'acide acrylique à partir de glycérol
FR2884817A1 (fr) Procede de preparation d'acide acrylique a partir de glycerol
FR2966456A1 (fr) Procede d'obtention d'acroleine par deshydratation catalytique de glycerol ou de glycerine
EP0441685B1 (de) Katalytisches System und seine Verwendung bei der Oxydehydrierung von gesättigten Karbonsäuren
EP2882530B1 (de) Feststoffkatalysator zur katalytischen ozonierung organischer verbindungen in einem wässrigen medium
WO2015124856A1 (fr) Procede de production d'acide acrylique bio-source
EP1833603A1 (de) Verfahren zur herstellung von acrylsäure aus propan in abwesenheit von wasserdampf

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100205

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20111007

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20170401