EP1539668A1 - Method for producing acrylic acid from propane, in the absence of molecular oxygen - Google Patents

Method for producing acrylic acid from propane, in the absence of molecular oxygen

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Publication number
EP1539668A1
EP1539668A1 EP03769539A EP03769539A EP1539668A1 EP 1539668 A1 EP1539668 A1 EP 1539668A1 EP 03769539 A EP03769539 A EP 03769539A EP 03769539 A EP03769539 A EP 03769539A EP 1539668 A1 EP1539668 A1 EP 1539668A1
Authority
EP
European Patent Office
Prior art keywords
limits included
catalyst
reactor
gases
propane
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Withdrawn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
EP03769539A
Other languages
German (de)
French (fr)
Inventor
Jean-Luc Dubois
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 SA
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Filing date
Publication date
Application filed by Arkema SA filed Critical Arkema SA
Publication of EP1539668A1 publication Critical patent/EP1539668A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C07C57/04—Acrylic acid; Methacrylic acid
    • 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
    • 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
    • B01J23/90—Regeneration or reactivation
    • B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/28—Regeneration or reactivation
    • B01J27/30—Regeneration or reactivation of catalysts comprising compounds of sulfur, selenium or tellurium
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
    • C07C27/20—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxo-reaction
    • C07C27/24—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxo-reaction with moving catalysts
    • 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
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to the production of acrylic acid from propane in the absence of molecular oxygen.
  • the object of the invention is therefore to have a process for the production of acrylic acid from propane and in the absence of molecular oxygen, which makes it possible to obtain a high conversion of propane while having a selectivity high.
  • the advantages of this new process are the following: the limitation of the overoxidation of the products formed which takes place in the presence of molecular oxygen; according to the present invention, because one operates in the absence of molecular oxygen, the formation of CO x (carbon monoxide and carbon dioxide), degradation products, is reduced, which makes it possible to increase the selectivity for acrylic acid; the selectivity for acrylic acid remains at a good level; the conversion is increased without loss of selectivity; the catalyst undergoes only a small reduction and therefore a progressive loss of its activity; it can be easily regenerated by heating in the presence of oxygen or an oxygen-containing gas after a certain period of use; after regeneration, the catalyst returns to its initial activity and can be used in a new reaction cycle; in addition, the separation of the stages of reduction of the catalyst and of regeneration thereof makes it possible to increase the partial pressure of propane, such a partial pressure of propane supply being no longer limited by the existence of a zone explosive created by the propane + oxygen mixture.
  • the present invention therefore relates to a process for the manufacture of acrylic acid from propane, in which: a) a gaseous mixture devoid of molecular oxygen and comprising propane, steam is introduced, as well as , where appropriate, an inert gas, in a first reactor with a transported catalyst bed, b) at the outlet of the first reactor, the gases are separated from the catalyst; c) the catalyst is returned to a regenerator; d) the gases are introduced into a second reactor with a transported catalyst bed; e) at the outlet of the second reactor, the gases are separated from the catalyst and the acrylic acid contained in the separated gases is recovered; f) the catalyst is returned to the regenerator; g) regenerated catalyst from the regenerator is reintroduced into the first and second reactors; and in which the catalyst comprises molybdenum, vanadium, tellurium or antimony, oxygen and at least one other element X chosen from niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium,
  • This process makes it possible to obtain a selectivity for acrylic acid of almost 60% and a high propane conversion.
  • the gaseous mixture comprising propane, steam, as well as, if necessary, an inert gas, is introduced into a first reactor (Riser 1) containing the transportable catalyst bed.
  • the effluents are separated into gases and the catalyst transported.
  • the catalyst is sent to a regenerator.
  • the gases are introduced into a second reactor (Riser 2) also containing a transportable catalyst bed.
  • the effluents are separated into gases and the catalyst transported.
  • the catalyst is sent to a regenerator.
  • the gases are treated in a known manner, generally by absorption and purification, with a view to recovering the acrylic acid produced.
  • the regenerated catalyst is reintroduced into the first reactor as well as into the second reactor.
  • the single regenerator can be replaced by two or more regenerators.
  • the first and second reactors are vertical and the catalyst is transported upward by the flow of gases.
  • the conversion of propane to acrylic acid by means of the catalyst it is carried out according to the following redox reaction (1):
  • this redox reaction (1) is carried out at a temperature of 200 to 500 ° C, preferably from 250 to 450 ° C, more preferably still, from 350 to 400 ° C.
  • the pressure in the reactors is generally from 1.01.10 4 to 1.01.10 6 Pa (0.1 to 10 atmospheres), preferably from 5.05.10 4 to 5.05.10 5 Pa (0.5-5 atmospheres).
  • the residence time in each reactor is generally from 0.01 to 90 seconds, preferably from 0.1 to 30 seconds.
  • the propane / water vapor volume ratio in the gas phase is not critical and can vary within wide limits.
  • inert gas which can be helium, krypton, a mixture of these two gases, or else nitrogen, carbon dioxide, etc. is also not critical and can also vary within wide limits.
  • the proportions of its constituent elements can satisfy the following conditions:
  • r Mo , r v , r Te or r sb and r x represent the molar fractions, respectively, of Mo, V, Te and X, with respect to the sum of the numbers of moles of all elements of the catalyst, except oxygen.
  • Such a catalyst can be prepared according to the teachings of the aforementioned European patent application No. 608,838. We can refer in particular to the catalyst of formula M ⁇ V 0 , 3 Te 0 , 3 Nb 0, ⁇ 2 O n , the preparation of which is described in Example 1 of this patent application.
  • the catalyst corresponds to the following formula (I) or to the formula (Ibis):
  • - x is the quantity of oxygen linked to the other elements and depends on their oxidation states.
  • the oxides of the different metals used in the composition of the catalyst of formula (I) or (Ibis) can be used as raw materials in the preparation of this catalyst, but the raw materials are not limited to oxides; as other raw materials, there may be mentioned: - in the case of molybdenum, ammonium molybdate, ammonium paramolybdate, ammonium heptamolybdate, molybdic acid, halides or oxyhalides of molybdenum such as MoCl 5 , organometallic molybdenum compounds such as molybdenum alkoxides such as Mo (OC 2 H 5 ) 5 , acetylacetone molybdenyl;
  • vanadium, ammonium metavanadate, vanadium halides or oxyhalides such as VC1 / VC1 5 or V0C1 3 , organometallic compounds of vanadium such as vanadium alkoxides such as VO (OC 2 H 5 ) 3 ;
  • niobium in the case of niobium, niobic acid, Nb 2 (C 2 0) 5 , niobium tartrate, niobium hydrogen oxalate, oxotrioxalatoammonium niobiate
  • the source of silicon generally consists of colloidal silica and / or polysilicic acid.
  • the catalyst of formula (I) can be prepared by mixing, with stirring, aqueous solutions of niobic acid, ammonium heptamolybdate, ammonium metavanadate, telluric acid, adding preferably colloidal silica, then precalcining in air at about 300 ° C and calcining under nitrogen at about 600 ° C.
  • - a is between 0.09 and 0.8, limits included
  • reaction (2) the catalyst undergoes a reduction and a progressive loss of its activity. This is why, once the catalyst has at least partially gone to the reduced state, its regeneration is carried out according to reaction (2):
  • the process is generally carried out until the reduction rate of the catalyst is between 0.1 and 10 g of oxygen per kg of catalyst.
  • One mode of operation can be used with a single pass or with recycling of the products leaving the second reactor.
  • the propylene produced as a secondary product and / or the unreacted propane are recycled (or returned) to the inlet of the reactor, c that is to say that they are reintroduced at the inlet of the first reactor, in admixture or in parallel with the starting mixture of propane, steam and, if appropriate, inert gas (ies).
  • the gas mixture also passes over a co-catalyst.
  • At least one of the reactors comprises a cocatalyst having the following formula (II):
  • Such a co-catalyst can be prepared in the same way as the catalyst of formula (I).
  • the oxides of the various metals used in the composition of the cocatalyst of formula (II) can be used as raw materials in the preparation of this cocatalyst, but the raw materials are not limited to oxides; as other raw materials, mention may be made in the case of nickel, cobalt, bismuth, iron or potassium, the corresponding nitrates.
  • the co-catalyst is present in the form of a transportable bed and it is regenerated and circulates in the same way as the catalyst.
  • - f is between 0 and 0.4, limits included;
  • - g ' is between 0 and 0.4, limits included;
  • the mass ratio of the catalyst to the co-catalyst is generally greater than 0.5 and preferably at least 1.
  • the cocatalyst is present in the two reactors.
  • the catalyst and the cocatalyst are in the form of solid catalytic compositions.
  • They can each be in the form of grains, generally from 20 to 300 ⁇ m in diameter, the grains of catalyst and of cocatalyst being generally mixed before the implementation of the method according to the invention.
  • the catalyst and the cocatalyst can also be in the form of a solid catalytic composition composed of grains, each of which comprises both the catalyst and the cocatalyst.
  • x is the quantity of oxygen linked to the other elements and depends on their oxidation states.
  • the conversion ratio is the mass of catalyst (in kg) necessary to convert 1 kg of propane.
  • 640 g of distilled water are introduced into a 5 l beaker, followed by 51.2 g of niobic acid (ie 0.304 moles of niobium). 103.2 g (0.816 mole) of oxalic acid dihydrate are then added.
  • the oxalic acid / niobium molar ratio is therefore 2.69.
  • the solution obtained above is heated at 60 ° C for 2 hours, covering to avoid evaporation and stirring.
  • a white suspension is thus obtained which is allowed to cool with stirring to 30 ° C, which lasts for about 2 hours.
  • Ludox silica containing 40% by weight of silica, supplied by the company Dupont
  • the latter retains its clarity and red coloration.
  • the niobium solution prepared above is then added. This gives a fluorescent orange gel after a few minutes of agitation. This solution is then spray dried.
  • the atomizer used is a laboratory atomizer (ATSELAB from the company Sodeva). The atomization takes place under a nitrogen atmosphere (in order to avoid any oxidation and any untimely combustion of the oxalic acid present in the slip).
  • the operating parameters are globally:
  • the recovered product (355.2 g), which has a particle size of less than 40 microns, is then placed in an oven at 130 ° C. overnight in a teflon-coated tray. 331 g of dry product are thus obtained.
  • the 331 g of the precursor obtained previously is precalcined for 4 hours at 300 ° C. under an air flow of 47.9 ml / min / g of precursor.
  • the solid obtained is then calcined for 2 hours at 600 ° C. under a nitrogen flow of 12.8 ml / min / g of solid.
  • the desired catalyst is thus obtained.
  • Example 2 Catalyst Tests a) Apparatus
  • laboratory simulations were carried out in a laboratory fixed bed reactor, generating propane pulses and oxygen pulses.
  • propane pulses and oxygen pulses By using a loading of the reactor having two superimposed catalyst beds, it is thus possible to simulate the behavior of the catalyst and what it would have undergone in two successive reactors with rising transport bed called “risers”.
  • the apparatus is the same as above, except that the seventh height of 5 ml of silicon carbide is replaced by 5 g of catalyst diluted with 5 ml of 0.062 mm of silicon carbide, like the third height of catalyst.
  • the reactor is then heated to 250 ° C and the evaporator to 200 ° C.
  • the electric priming of the water pump is activated. Once the reactor and the vaporizer have reached the temperatures indicated above, the water pump is activated and the temperature of the reactor is raised to the desired test temperature.
  • the reactor hot spot is then allowed to stabilize for 30 minutes.
  • the catalyst is considered to be completely oxidized when the temperature of the hot spot has stabilized, that is to say when there is no longer any exotherm due to the reaction (by following the temperature of the catalyst measured by means of 'a thermocouple placed in the catalytic bed, we can see the temperature fluctuations as a function of the pulses).
  • the pressure at the inlet of the reactor was approximately 1.2 to 1.8 bar (absolute) and the pressure drop across the reactor was approximately 0.2 to 0.8 bar (relative).
  • a redox cycle represents: - 13.3 seconds of propane in a continuous flow of helium-krypton / water, - 45 seconds of continuous flow of helium-krypton / water, - 20 seconds of oxygen in a continuous flow of helium-krypton / water,
  • Liquid effluents are analyzed on an HP 6890 chromatograph, after performing a specific calibration.
  • the gases are analyzed during the balance on a micro-GC Chrompack chromatograph.
  • An acidity assay is performed on each bottle during the assessment, to determine the exact number of moles of acid produced and to validate the chromatographic analyzes.
  • a balance sheet is made up of 60 cycles with partial pressures of propane and oxygen corresponding to the following ratios: for the reaction: Propane / He-Kr / H0: 10/45/45 for the regeneration: 0 2 / He-Kr / H 2 O: 20/45/45
  • the ratio conversion is calculated taking into account only one bed, as it reflects the flow of solid required to convert 1 kg of propane. Since the unit must operate at a maximum density (limited by the flow of catalyst), the only way to further increase the conversion is therefore to take out the spent catalyst and replace it with fresh catalyst, without changing the flow. of catalyst. It is therefore the conversion ratio on 1 bed which sizes the unit.
  • the conversion of propane (Pan) with the process according to the invention is significantly higher than that of the process used comparatively, it is practically twice as high as 360 ° C.
  • the acrylic acid yields are greater than 17.5% at all the temperatures tested, while according to the comparative process they are less than 15.5%.
  • the use of the two reactors makes it possible to obtain a gain in conversion per pass, without loss of selectivity.
  • This makes it possible to reduce the conversion ratio, recalculated per reactor, but taking into account the total conversion, because the use of a second reactor amounts to increasing the flow of catalyst, in a unit which is already often at maximum solid density .

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

The invention concerns a method for producing acrylic acid from propane, in the absence of molecular oxygen which consists in: a) introducing a gas mixture free of molecular oxygen and comprising propane, water vapour, and, optionally, an inert gas, into a first reactor with fluidized catalytic bed, b) at the first reactor output, separating the gases from the catalyst, c) recycling the catalyst into a regenerator, d) introducing the gases into a second reactor with fluidized catalytic bed, e) at the second reactor output, separating the gases from the catalyst and recovering acrylic acid contained in the separated gases, f) recycling the catalyst into the regenerator, and g) reintroducing the regenerated catalyst from the regenerator into the first and second reactors.

Description

PROCEDE DE FABRICATION D'ACIDE ACRYLIQUE A PARTIR DE PROPANE, PROCESS FOR THE MANUFACTURE OF ACRYLIC ACID FROM PROPANE,
EN L'ABSENCE D'OXYGENE MOLECULAIREIN THE ABSENCE OF MOLECULAR OXYGEN
La présente invention concerne la production d'acide acrylique à partir de propane en l'absence d'oxygène moléculaire .The present invention relates to the production of acrylic acid from propane in the absence of molecular oxygen.
Il est connu d'après la demande de brevet européen n°EP-A- 608838 de préparer un acide carboxylique insaturé à partir d'un alcane selon une réaction d'oxydation catalytique en phase vapeur en présence d'un catalyseur contenant un oxyde métallique mixte comprenant comme composants essentiels, Mo, V, Te, O, ainsi qu'au moins un élément choisi dans le groupe constitué par le niobium, le tantale, le tungstène, le titane, l'aluminium, le zirconium, le chrome, le manganèse, le fer, le ruthénium, le cobalt, le rhodium, le nickel, le palladium, le platine, l'antimoine, le bismuth, le bore, 1 ' indium et le cérium, ces éléments étant présents dans des proportions bien précises. Les utilisations d'un tel catalyseur dépourvu de silicium décrites dans les exemples de ce document conduisent à de bonnes sélectivités en acide acrylique mais elles sont mises en œuvre en présence d'air.It is known from European patent application No. EP-A-608838 to prepare an unsaturated carboxylic acid from an alkane according to a catalytic oxidation reaction in the vapor phase in the presence of a catalyst containing a metal oxide mixed comprising essential components, Mo, V, Te, O, as well as at least one element selected from the group consisting of niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, antimony, bismuth, boron, indium and cerium, these elements being present in very precise proportions. The uses of such a catalyst devoid of silicon described in the examples of this document lead to good selectivities for acrylic acid but they are used in the presence of air.
Par ailleurs, il existe des brevets tels que les brevets américains n° 4 606 810, 4 966 681, 4 874 503, 4 830 728, 5 198 590 et 6 287 522 utilisant deux réacteurs ou plus, appelés « Risers », cependant ces brevets ne concernent que des applications dans le raffinage des coupes pétrolières.Furthermore, there are patents such as US Pat. Nos. 4,606,810, 4,966,681, 4,874,503, 4,830,728, 5,198,590 and 6,287,522 using two or more reactors, called "Risers", however these patents relate only to applications in the refining of petroleum fractions.
L'invention a donc pour but de disposer d'un procédé de production de fabrication d'acide acrylique à partir de propane et en l'absence d'oxygène moléculaire, qui permette d'obtenir une conversion du propane élevée tout en ayant une sélectivité élevée.The object of the invention is therefore to have a process for the production of acrylic acid from propane and in the absence of molecular oxygen, which makes it possible to obtain a high conversion of propane while having a selectivity high.
La Demanderesse a découvert que l'on peut atteindre ce but en faisant passer un mélange gazeux de propane et de vapeur d'eau, et le cas échéant, d'un gaz inerte, sur un catalyseur particulier, lequel agit comme système rédox et fournit l'oxygène nécessaire à la réaction et en utilisant un appareillage présentant deux zones réactionnelles .The Applicant has discovered that this goal can be achieved by passing a gaseous mixture of propane and water vapor, and if necessary, an inert gas, over a particular catalyst, which acts as a redox system and provides the oxygen necessary for the reaction and using an apparatus having two reaction zones.
Les avantages de ce nouveau procédé sont les suivants : la limitation de la suroxydation des produits formés qui a lieu en présence d'oxygène moléculaire ; selon la présente invention, du fait que l'on opère en l'absence d'oxygène moléculaire, la formation de COx (monoxyde de carbone et dioxyde de carbone) , produits de dégradation, est réduite, ce qui permet d'augmenter la sélectivité en acide acrylique ; la sélectivité en acide acrylique se maintient à un bon niveau ; la conversion est augmentée sans perte de sélectivité ; le catalyseur ne subit qu'une faible réduction et donc une perte progressive de son activité ; il est facilement régénérable par chauffage en présence d'oxygène ou d'un gaz contenant de l'oxygène après une certaine période d'utilisation ; après la régénération, le catalyseur retrouve son activité initiale et peut être utilisé dans un nouveau cycle de réaction ; en outre, la séparation des étapes de réduction du catalyseur et de régénération de celui-ci permet d'augmenter la pression partielle en propane, une telle pression partielle d'alimentation en propane n'étant plus limitée par l'existence d'une zone explosive créée par le mélange propane + oxygène. La présente invention a donc pour objet un procédé de fabrication de l'acide acrylique à partir de propane, dans lequel : a) on introduit un mélange gazeux dépourvu d'oxygène moléculaire et comprenant du propane, de la vapeur d'eau, ainsi que, le cas échéant, un gaz inerte, dans un premier réacteur à lit de catalyseur transporté, b) à la sortie du premier réacteur, on sépare les gaz du catalyseur ; c) on renvoie le catalyseur dans un régénérateur ; d) on introduit les gaz dans un second réacteur à lit de catalyseur transporté ; e) à la sortie du second réacteur, on sépare les gaz du catalyseur et on récupère l'acide acrylique contenu dans les gaz séparés ; f) on renvoie le catalyseur dans le régénérateur ; g) on réintroduit du catalyseur régénéré provenant du régénérateur dans les premier et second réacteurs ; et dans lequel le catalyseur comprend du molybdène, du vanadium, du tellure ou de l'antimoine, de l'oxygène et au moins un autre élément X choisi parmi le niobium, le tantale, le tungstène, le titane, l'aluminium, le zirconium, le chrome, le manganèse, le fer, le ruthénium, le cobalt, le rhodium, le nickel, le palladium, le platine, l'antimoine, le bismuth, le bore, 1 ' indium et le cerium.The advantages of this new process are the following: the limitation of the overoxidation of the products formed which takes place in the presence of molecular oxygen; according to the present invention, because one operates in the absence of molecular oxygen, the formation of CO x (carbon monoxide and carbon dioxide), degradation products, is reduced, which makes it possible to increase the selectivity for acrylic acid; the selectivity for acrylic acid remains at a good level; the conversion is increased without loss of selectivity; the catalyst undergoes only a small reduction and therefore a progressive loss of its activity; it can be easily regenerated by heating in the presence of oxygen or an oxygen-containing gas after a certain period of use; after regeneration, the catalyst returns to its initial activity and can be used in a new reaction cycle; in addition, the separation of the stages of reduction of the catalyst and of regeneration thereof makes it possible to increase the partial pressure of propane, such a partial pressure of propane supply being no longer limited by the existence of a zone explosive created by the propane + oxygen mixture. The present invention therefore relates to a process for the manufacture of acrylic acid from propane, in which: a) a gaseous mixture devoid of molecular oxygen and comprising propane, steam is introduced, as well as , where appropriate, an inert gas, in a first reactor with a transported catalyst bed, b) at the outlet of the first reactor, the gases are separated from the catalyst; c) the catalyst is returned to a regenerator; d) the gases are introduced into a second reactor with a transported catalyst bed; e) at the outlet of the second reactor, the gases are separated from the catalyst and the acrylic acid contained in the separated gases is recovered; f) the catalyst is returned to the regenerator; g) regenerated catalyst from the regenerator is reintroduced into the first and second reactors; and in which the catalyst comprises molybdenum, vanadium, tellurium or antimony, oxygen and at least one other element X chosen from niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, antimony, bismuth, boron, indium and cerium.
Ce procédé permet d'obtenir une sélectivité en acide acrylique de près de 60% et une conversion du propane élevée.This process makes it possible to obtain a selectivity for acrylic acid of almost 60% and a high propane conversion.
D'autres caractéristiques et avantages de l'invention vont maintenant être décrits en détail dans l'exposé qui suit et qui est donné en référence à la figure unique annexée, qui représente schematiquement un appareillage apte à la mise en œuvre du procédé selon l'invention.Other characteristics and advantages of the invention will now be described in detail in the description which follows and which is given with reference to the single appended figure, which diagrammatically represents an apparatus suitable for implementing the method according to invention.
EXPOSE DETAILLE DE L'INVENTION Le fonctionnement du procédé selon l'invention peut être expliqué en se référant à la figure annexée.DETAILED DESCRIPTION OF THE INVENTION The operation of the process according to the invention can be explained by referring to the appended figure.
Le mélange gazeux comprenant du propane, de la vapeur d'eau, ainsi que, le cas échéant, un gaz inerte, est introduit dans un premier réacteur (Riser 1) contenant le lit de catalyseur transportable.The gaseous mixture comprising propane, steam, as well as, if necessary, an inert gas, is introduced into a first reactor (Riser 1) containing the transportable catalyst bed.
Ensuite, à la sortie du premier réacteur, les effluents sont séparés en des gaz et le catalyseur transporté. Le catalyseur est envoyé dans un régénérateur. Les gaz sont introduits dans un second réacteur (Riser 2) contenant également un lit de catalyseur transportable.Then, at the outlet of the first reactor, the effluents are separated into gases and the catalyst transported. The catalyst is sent to a regenerator. The gases are introduced into a second reactor (Riser 2) also containing a transportable catalyst bed.
A la sortie du second réacteur, les effluents sont séparés en des gaz et le catalyseur transporté. Le catalyseur est envoyé dans un régénérateur. Les gaz sont traités de façon connue, généralement par absorption et purification, en vue de la récupération de l'acide acrylique produit. Le catalyseur régénéré est réintroduit dans le premier réacteur ainsi que dans le second réacteur.At the outlet of the second reactor, the effluents are separated into gases and the catalyst transported. The catalyst is sent to a regenerator. The gases are treated in a known manner, generally by absorption and purification, with a view to recovering the acrylic acid produced. The regenerated catalyst is reintroduced into the first reactor as well as into the second reactor.
Le procédé fonctionne ainsi de façon continue, la circulation du catalyseur entre les réacteurs et le régénérateur s'effectue de façon régulière et généralement continue.The process thus works continuously, the circulation of the catalyst between the reactors and the regenerator takes place regularly and generally continuously.
Bien entendu, l'unique régénérateur peut être remplacé par deux ou plus régénérateurs .Of course, the single regenerator can be replaced by two or more regenerators.
En outre, il est possible d'ajouter à la suite du second réacteur d'autres réacteurs ayant eux aussi un catalyseur circulant entre chacun de ces réacteurs et le régénérateur ou d'autres régénérateurs.In addition, it is possible to add following the second reactor other reactors also having a catalyst circulating between each of these reactors and the regenerator or other regenerators.
De préférence, les premier et second réacteurs sont verticaux et le catalyseur est transporté vers le haut par le flux des gaz. En ce qui concerne la conversion du propane en acide acrylique au moyen du catalyseur, elle s'effectue selon la réaction rédox (1) suivante :Preferably, the first and second reactors are vertical and the catalyst is transported upward by the flow of gases. As regards the conversion of propane to acrylic acid by means of the catalyst, it is carried out according to the following redox reaction (1):
SOLIDEoxydé + PROPANE -> SOLIDEréduit + ACIDE ACRYLIQUE (1)SOLID oxidized + PROPANE -> SOLID reduced + ACRYLIC ACID (1)
Généralement, cette réaction rédox (1) est conduite à une température de 200 à 500°C, de préférence de 250 à 450°C, plus préférentiellement encore, de 350 à 400°C.Generally, this redox reaction (1) is carried out at a temperature of 200 to 500 ° C, preferably from 250 to 450 ° C, more preferably still, from 350 to 400 ° C.
La pression dans les réacteurs est généralement de 1,01.104 à 1,01.106 Pa (0,1 à 10 atmosphères), de préférence de 5,05.104 à 5,05.105 Pa (0,5-5 atmosphères).The pressure in the reactors is generally from 1.01.10 4 to 1.01.10 6 Pa (0.1 to 10 atmospheres), preferably from 5.05.10 4 to 5.05.10 5 Pa (0.5-5 atmospheres).
Le temps de séjour dans chaque réacteur est généralement de 0,01 à 90 secondes, de préférence, de 0,1 à 30 secondes.The residence time in each reactor is generally from 0.01 to 90 seconds, preferably from 0.1 to 30 seconds.
Le rapport en volume propane/vapeur d'eau dans la phase gazeuse n'est pas critique et peut varier dans de larges limites .The propane / water vapor volume ratio in the gas phase is not critical and can vary within wide limits.
De même, la proportion de gaz inerte, qui peut être de l'hélium, du krypton, un mélange de ces deux gaz, ou bien de l'azote, du dioxyde de carbone, etc., n'est pas non plus critique et peut aussi varier dans de larges limites.Similarly, the proportion of inert gas, which can be helium, krypton, a mixture of these two gases, or else nitrogen, carbon dioxide, etc. is also not critical and can also vary within wide limits.
Comme ordre de grandeur des proportions du mélange de départ, on peut citer le ratio suivant (en volumes) : propane/inerte (He-Kr) /H20 (vapeur) : 10-30/40-50/40-50As an order of magnitude of the proportions of the starting mixture, the following ratio (by volume) can be cited: propane / inert (He-Kr) / H 2 0 (vapor): 10-30 / 40-50 / 40-50
Pour ce qui est du catalyseur, les proportions de ses éléments constitutifs peuvent satisfaire aux conditions suivantes :As regards the catalyst, the proportions of its constituent elements can satisfy the following conditions:
0,25 < rMo < 0, 980.25 <r Mo <0.98
0, 003 < rv < 0,50.003 <r v <0.5
0,003 < rTe ou rsb < 0,50.003 <r Te or r sb <0.5
0, 003 < rx < 0,5 dans lesquelles rMo, rv, rTe ou rsb et rx représentent les fractions molaires, respectivement, de Mo, V, Te et X, par rapport à la somme des nombres de moles de tous les éléments du catalyseur, à l'exception de l'oxygène. Un tel catalyseur peut être préparé selon les enseignements de la demande de brevet européen n° 608 838 précitée. On peut se référer en particulier, au catalyseur de formule MθιV0,3Te0, 3Nb0,ι2On, dont la préparation est décrite dans l'exemple 1 de cette demande de brevet .0.003 <r x <0.5 in which r Mo , r v , r Te or r sb and r x represent the molar fractions, respectively, of Mo, V, Te and X, with respect to the sum of the numbers of moles of all elements of the catalyst, except oxygen. Such a catalyst can be prepared according to the teachings of the aforementioned European patent application No. 608,838. We can refer in particular to the catalyst of formula MθιV 0 , 3 Te 0 , 3 Nb 0, ι 2 O n , the preparation of which is described in Example 1 of this patent application.
Selon un mode de réalisation préféré de l'invention, le catalyseur répond à la formule (I) ou à la formule (Ibis) suivantes :According to a preferred embodiment of the invention, the catalyst corresponds to the following formula (I) or to the formula (Ibis):
MOiVaTebNbcSidOx (I) MoxVaSbbNbcSidOx (Ibis) dans lesquelles :MOiVaTe b NbcSidOx (I) MoxVaSbbNbcSi d O x (Ibis) in which:
- a est compris entre 0,006 et 1, bornes incluses- a is between 0.006 and 1, limits included
- b est compris entre 0,006 et 1, bornes incluses- b is between 0.006 and 1, limits included
- c est compris entre 0,006 et 1, bornes incluses - d est compris entre 0 et 3,5, bornes incluses ; et- c is between 0.006 and 1, limits included - d is between 0 and 3.5, limits included; and
- x est la quantité d'oxygène lié aux autres éléments et dépend de leurs états d'oxydation.- x is the quantity of oxygen linked to the other elements and depends on their oxidation states.
Avantageusement :Advantageously:
- a est compris entre 0,09 et 0,8, bornes incluses ; - b est compris entre 0,04 et 0,6, bornes incluses ;- a is between 0.09 and 0.8, limits included; - b is between 0.04 and 0.6, limits included;
- c est compris entre 0,01 et 0,4, bornes incluses ; et- c is between 0.01 and 0.4, limits included; and
- d est compris entre 0,4 et 1,6, bornes incluses.- d is between 0.4 and 1.6, limits included.
Les oxydes des différents métaux entrant dans la composition du catalyseur de formule (I) ou (Ibis) peuvent être utilisés comme matières premières dans la préparation de ce catalyseur, mais les matières premières ne sont pas limitées aux oxydes ; comme autres matières premières, on peut citer : - dans le cas du molybdène, le molybdate d'ammonium, le paramolybdate d'ammonium, 1 ' heptamolybdate d'ammonium, l'acide molybdique, les halogénures ou oxyhalogénures de molybdène tels que MoCl5, les composés organométalliques du molybdène comme les alkoxydes de molybdène tels que Mo(OC2H5)5, le molybdényle d' acétylacétone ;The oxides of the different metals used in the composition of the catalyst of formula (I) or (Ibis) can be used as raw materials in the preparation of this catalyst, but the raw materials are not limited to oxides; as other raw materials, there may be mentioned: - in the case of molybdenum, ammonium molybdate, ammonium paramolybdate, ammonium heptamolybdate, molybdic acid, halides or oxyhalides of molybdenum such as MoCl 5 , organometallic molybdenum compounds such as molybdenum alkoxides such as Mo (OC 2 H 5 ) 5 , acetylacetone molybdenyl;
- dans le cas du vanadium, le métavanadate d'ammonium, les halogénures ou oxyhalogénures de vanadium tels que VC1 / VC15 ou V0C13, les composés organométalliques du vanadium comme les alkoxydes de vanadium tels que VO(OC2H5)3 ;- in the case of vanadium, ammonium metavanadate, vanadium halides or oxyhalides such as VC1 / VC1 5 or V0C1 3 , organometallic compounds of vanadium such as vanadium alkoxides such as VO (OC 2 H 5 ) 3 ;
- dans le cas du tellure, le tellure, l'acide tellurique et Te02 ;- in the case of tellurium, tellurium, telluric acid and Te0 2 ;
- dans le cas du niobium, l'acide niobique, Nb2(C20 )5, le tartrate de niobium, l'hydrogéno-oxalate de niobium, le niobiate d' oxotrioxalatoammonium- in the case of niobium, niobic acid, Nb 2 (C 2 0) 5 , niobium tartrate, niobium hydrogen oxalate, oxotrioxalatoammonium niobiate
{ (NH4)3 [Nb0(C204)3] •1,5H20}, l'oxalate de niobium et d'ammonium, l'oxalate de niobium et de tartrate, les halogénures ou oxyhalogénures de nobium tels que NbCl3, NbCl5 et les composés organométalliques du niobium comme les alkoxydes de niobium tels que Nb(OC2H5)5, Nb (O-n-Bu) 5 ; et, d'une manière générale, tous les composés susceptibles de former un oxyde par calcination, à savoir, les sels métalliques d'acides organique, les sels métalliques d'acides minéraux, les composés métalliques complexes, etc. La source de silicium est généralement constituée de silice colloïdale et/ou d'acide polysilicique .{(NH 4 ) 3 [Nb0 (C 2 0 4 ) 3 ] • 1.5H 2 0}, niobium and ammonium oxalate, niobium and tartrate oxalate, halides or oxyhalides of nobium such as NbCl 3 , NbCl 5 and the organometallic compounds of niobium such as niobium alkoxides such as Nb (OC 2 H 5 ) 5 , Nb (On-Bu) 5 ; and, in general, all the compounds capable of forming an oxide by calcination, namely, the metal salts of organic acids, the metal salts of mineral acids, complex metal compounds, etc. The source of silicon generally consists of colloidal silica and / or polysilicic acid.
Conformément à des modes de réalisation particuliers, on peut préparer le catalyseur de formule (I) en mélangeant sous agitation des solutions aqueuses d'acide niobique, d' heptamolybdate d'ammonium, de métavanadate d'ammonium, d'acide tellurique, en ajoutant de préférence de la silice colloïdale, puis en précalcinant sous air à environ 300°C et en calcinant sous azote à environ 600°C.According to particular embodiments, the catalyst of formula (I) can be prepared by mixing, with stirring, aqueous solutions of niobic acid, ammonium heptamolybdate, ammonium metavanadate, telluric acid, adding preferably colloidal silica, then precalcining in air at about 300 ° C and calcining under nitrogen at about 600 ° C.
De préférence, dans le catalyseur de formule (I) ou (Ibis) : - a est compris entre 0,09 et 0,8, bornes inclusesPreferably, in the catalyst of formula (I) or (Ibis): - a is between 0.09 and 0.8, limits included
- b est compris entre 0,04 et 0,6, bornes incluses- b is between 0.04 and 0.6, limits included
- c est compris entre 0,01 et 0,4, bornes incluses ; et- c is between 0.01 and 0.4, limits included; and
- d est compris entre 0,4 et 1,6, bornes incluses.- d is between 0.4 and 1.6, limits included.
Au cours de la réaction rédox (1) , le catalyseur subit une réduction et une perte progressive de son activité. C'est pourquoi, une fois que le catalyseur est au moins partiellement passé à l'état réduit, on conduit sa régénération selon la réaction (2) :During the redox reaction (1), the catalyst undergoes a reduction and a progressive loss of its activity. This is why, once the catalyst has at least partially gone to the reduced state, its regeneration is carried out according to reaction (2):
SOLIDEréduit + 02 -> SOLIDEoxydé (2) par chauffage en présence d'oxygène ou d'un gaz contenant de l'oxygène à une température de 250 à 500°C, pendant le temps nécessaire à la réoxydation du catalyseur.SOLID reduced + 0 2 -> SOLIDoxidized (2) by heating in the presence of oxygen or an oxygen-containing gas at a temperature of 250 to 500 ° C, for the time necessary for the reoxidation of the catalyst.
On met en général le procédé en œuvre jusqu'à ce que le taux de réduction du catalyseur soit compris entre 0,1 et 10 g d'oxygène par kg de catalyseur.The process is generally carried out until the reduction rate of the catalyst is between 0.1 and 10 g of oxygen per kg of catalyst.
Ce taux de réduction peut être surveillé au cours de la réaction par la quantité de produits obtenus. On calcule alors la quantité d'oxygène équivalente. On peut aussi le suivre parThis reduction rate can be monitored during the reaction by the quantity of products obtained. The equivalent amount of oxygen is then calculated. We can also follow him by
1 ' exothermicité de la réaction. Après la régénération, qui peut être effectuée dans des conditions de température et de pression identiques à, ou différentes de celles de la réaction rédox, le catalyseur retrouve une activité initiale et peut être réintroduit dans les réacteurs .1 exothermicity of the reaction. After the regeneration, which can be carried out under conditions of temperature and pressure identical to, or different from those of the redox reaction, the catalyst regains initial activity and can be reintroduced into the reactors.
On peut utiliser un mode de fonctionnement à un seul passage ou avec recyclage des produits sortant du deuxième réacteur.One mode of operation can be used with a single pass or with recycling of the products leaving the second reactor.
Selon un mode de réalisation préféré de l'invention, après traitement des gaz issus du deuxième réacteur, le propylene produit comme produit secondaire et/ou le propane n'ayant pas réagi sont recyclés (ou renvoyés) à l'entrée du réacteur, c'est-à-dire qu'ils sont réintroduits à l'entrée du premier réacteur, en mélange ou parallèlement avec le mélange de départ de propane, de vapeur d'eau et le cas échéant de gaz inerte (s) .According to a preferred embodiment of the invention, after treatment of the gases from the second reactor, the propylene produced as a secondary product and / or the unreacted propane are recycled (or returned) to the inlet of the reactor, c that is to say that they are reintroduced at the inlet of the first reactor, in admixture or in parallel with the starting mixture of propane, steam and, if appropriate, inert gas (ies).
Selon un mode de réalisation avantageux de l'invention, le mélange gazeux passe également sur un co-catalyseur .According to an advantageous embodiment of the invention, the gas mixture also passes over a co-catalyst.
Ceci a pour avantage de réduire la production d'acide propionique, qui est généralement un sous-produit de la réaction de conversion et qui pose des problèmes dans certaines applications de l'acide acrylique lorsqu'il est présent en trop grande quantité.This has the advantage of reducing the production of propionic acid, which is generally a by-product of the conversion reaction and which poses problems in certain applications of acrylic acid when it is present in too large a quantity.
Ainsi, on réduit fortement le rapport acide propionique/acide acrylique en sortie de réacteur.Thus, the propionic acid / acrylic acid ratio is greatly reduced at the outlet of the reactor.
En outre, la formation d'acétone, qui est aussi un sous- produit de la fabrication d'acide acrylique à partir de propane, est diminuée.In addition, the formation of acetone, which is also a by-product of the manufacture of acrylic acid from propane, is reduced.
A cet effet, l'un au moins des réacteurs comprend un co- catalyseur ayant la formule (II) suivante :To this end, at least one of the reactors comprises a cocatalyst having the following formula (II):
MθιBia-Feb'Coc-Nid'Ke'Sbf.Tig.Sih'Cai.N j'Tek.Pbi' m.Cun- (II) dans laquelle : - a' est compris entre 0,006 et 1, bornes incluses ;MθιBi a -Fe b ' Co c -Ni d' K e ' Sbf.Tig.Si h' Cai.N j ' Te k .Pbi ' m .Cu n - (II) in which: - a 'is between 0.006 and 1, terminals included;
- b' est compris entre 0 et 3,5, bornes incluses- b 'is between 0 and 3.5, limits included
- c' est compris entre 0 et 3,5, bornes incluses- it is between 0 and 3.5, limits included
- d' est compris entre 0 et 3,5, bornes incluses - e' est compris entre 0 et 1 , bornes incluses- d is between 0 and 3.5, limits included - e 'is between 0 and 1, limits included
- f est compris entre 0 et 1, bornes incluses- f is between 0 and 1, limits included
- g' est compris entre 0 et 1 , bornes incluses- g 'is between 0 and 1, limits included
- h' est compris entre 0 et 3,5, bornes incluses - i' est compris entre 0 et 1, bornes incluses- h 'is between 0 and 3.5, limits included - i' is between 0 and 1, limits included
- j' est compris entre 0 et 1 , bornes incluses- i is between 0 and 1, limits included
- k' est compris entre 0 et 1, bornes incluses- k 'is between 0 and 1, limits included
- l' est compris entre 0 et 1 , bornes incluses- l is between 0 and 1, limits included
- m' est compris entre 0 et 1 , bornes incluses ; et - n' est compris entre 0 et 1, bornes incluses.- m 'is between 0 and 1, limits included; and - is between 0 and 1, limits included.
Un tel co-catalyseur peut être préparé de la même manière que le catalyseur de formule (I) .Such a co-catalyst can be prepared in the same way as the catalyst of formula (I).
Les oxydes des différents métaux entrant dans la composition du co-catalyseur de formule (II) peuvent être utilisés comme matières premières dans la préparation de ce co-catalyseur, mais les matières premières ne sont pas limitées aux oxydes ; comme autres matières premières, on peut citer dans le cas du nickel, du cobalt, du bismuth, du fer ou du potassium, les nitrates correspondants. De manière générale, le co-catalyseur est présent sous forme de lit transportable et il est régénéré et circule de la même manière que le catalyseur.The oxides of the various metals used in the composition of the cocatalyst of formula (II) can be used as raw materials in the preparation of this cocatalyst, but the raw materials are not limited to oxides; as other raw materials, mention may be made in the case of nickel, cobalt, bismuth, iron or potassium, the corresponding nitrates. Generally, the co-catalyst is present in the form of a transportable bed and it is regenerated and circulates in the same way as the catalyst.
De préférence, dans le co-catalyseur de formule (II) :Preferably, in the co-catalyst of formula (II):
- a' est compris entre 0,01 et 0,4, bornes incluses ; - b' est compris entre 0,2 et 1,6, bornes incluses- a 'is between 0.01 and 0.4, limits included; - b 'is between 0.2 and 1.6, limits included
- c' est compris entre 0,3 et 1,6, bornes incluses- it is between 0.3 and 1.6, limits included
- d' est compris entre 0,1 et 0,6, bornes incluses- d is between 0.1 and 0.6, limits included
- e' est compris entre 0,006 et 0,01, bornes incluses- e 'is between 0.006 and 0.01, limits included
- f est compris entre 0 et 0,4, bornes incluses ; - g' est compris entre 0 et 0,4, bornes incluses ;- f is between 0 and 0.4, limits included; - g 'is between 0 and 0.4, limits included;
- h' est compris entre 0,01 et 1,6, bornes incluses ;- h 'is between 0.01 and 1.6, limits included;
- i' est compris entre 0 et 0,4, bornes incluses- i 'is between 0 and 0.4, limits included
- j' est compris entre 0 et 0,4, bornes incluses- i is between 0 and 0.4, limits included
- k' est compris entre 0 et 0,4, bornes incluses - l' est compris entre 0 et 0,4, bornes incluses- k 'is between 0 and 0.4, limits included - l' is between 0 and 0.4, limits included
- m' est compris entre 0 et 0,4, bornes incluses ; et- m 'is between 0 and 0.4, limits included; and
- n' est compris entre 0 et 0,4, bornes incluses. Le rapport massique du catalyseur au co-catalyseur est généralement supérieur à 0,5 et de préférence d'au moins 1.- is between 0 and 0.4, limits included. The mass ratio of the catalyst to the co-catalyst is generally greater than 0.5 and preferably at least 1.
Avantageusement, le co-catalyseur est présent dans les deux réacteurs . Le catalyseur et le co-catalyseur se présentent sous la forme de compositions solides catalytiques .Advantageously, the cocatalyst is present in the two reactors. The catalyst and the cocatalyst are in the form of solid catalytic compositions.
Ils peuvent être chacun sous la forme de grains, généralement de 20 à 300 μm de diamètre, les grains de catalyseur et de co-catalyseur étant généralement mélanges avant la mise en œuvre du procédé selon l'invention.They can each be in the form of grains, generally from 20 to 300 μm in diameter, the grains of catalyst and of cocatalyst being generally mixed before the implementation of the method according to the invention.
Le catalyseur et le co-catalyseur peuvent aussi se présenter sous la forme d'une composition solide catalytique composée de grains dont chacun comprend à la fois le catalyseur et le co-catalyseur.The catalyst and the cocatalyst can also be in the form of a solid catalytic composition composed of grains, each of which comprises both the catalyst and the cocatalyst.
ExemplesExamples
Les exemples suivants illustrent la présente invention sans toutefois en limiter la portée .The following examples illustrate the present invention without, however, limiting its scope.
Dans les formules indiquées dans l ' exemple 1 , x est la quantité d' oxygène lié aux autres éléments et dépend de leurs états d' oxydation .In the formulas given in Example 1, x is the quantity of oxygen linked to the other elements and depends on their oxidation states.
Les conversions , sélectivités et rendements sont définis comme suit :Conversions, selectivities and yields are defined as follows:
Nombre de moles de propane ayant réagiNumber of moles of propane reacted
Conversion ( %) = x 100 du propane Nombre de moles de propane introduitesConversion (%) = x 100 of propane Number of moles of propane introduced
Nombre de moles d' acide acrylique formées Sélectivité (% ) = x 100 en acide acrylique Nombre de moles de propane ayant réagiNumber of moles of acrylic acid formed Selectivity (%) = x 100 of acrylic acid Number of moles of propane that reacted
Nombre de moles d' acide acrylique formées Rendement ( %) = x 100 en acide acrylique Nombre de moles de propane introduites Les sélectivités et rendements relatifs aux autres composés sont calculées de manière similaire.Number of moles of acrylic acid formed Yield (%) = x 100 of acrylic acid Number of moles of propane introduced The selectivities and yields relative to the other compounds are calculated in a similar manner.
Le ratio conversion est la masse de catalyseur (en kg) nécessaire pour convertir 1 kg de propane.The conversion ratio is the mass of catalyst (in kg) necessary to convert 1 kg of propane.
Exemple 1Example 1
Préparation du catalyseur de formule Mo1V0/ 33Nbo, ιι e0, 22Sio, 9sOx a) Préparation d'une solution de niobiumPreparation of Mo catalyst of formula 1 V 0/33 Nbo, ιι e 0, 22 Sio 9 sO x a) Preparation of a solution of niobium
Dans un bêcher de 5 1 , on introduit 640 g d'eau distillée puis 51,2 g d'acide niobique (soit 0,304 moles de niobium) . On ajoute ensuite 103,2 g (0,816 mole) d'acide oxalique dihydraté .640 g of distilled water are introduced into a 5 l beaker, followed by 51.2 g of niobic acid (ie 0.304 moles of niobium). 103.2 g (0.816 mole) of oxalic acid dihydrate are then added.
Le rapport molaire acide oxalique/niobium est donc de 2,69.The oxalic acid / niobium molar ratio is therefore 2.69.
On chauffe la solution obtenue précédemment à 60 °C pendant 2 heures, en couvrant pour éviter 1 ' evaporation et en agitant.The solution obtained above is heated at 60 ° C for 2 hours, covering to avoid evaporation and stirring.
On obtient ainsi une suspension blanche que l'on laisse refroidir sous agitation jusqu'à 30°C , ce qui dure environ 2 heures .A white suspension is thus obtained which is allowed to cool with stirring to 30 ° C, which lasts for about 2 hours.
b) Préparation d'une solution de Mo, V et Teb) Preparation of a solution of Mo, V and Te
Dans un bêcher de 5 1, on introduit 2120 g d'eau distillée, 488 g d' heptamolybdate d'ammonium (soit 2,768 moles de molybdène), 106,4 g de métavanadate d'ammonium NH4V03 (soit 0,912 mole de vanadium) et 139,2 g d'acide tellurique (fournisseur : FLUKA) (soit 0,608 mole de tellure).2120 g of distilled water, 488 g of ammonium heptamolybdate (i.e. 2.768 moles of molybdenum), 106.4 g of ammonium metavanadate NH 4 V0 3 (i.e. 0.912 moles of vanadium) are introduced into a 5 l beaker. ) and 139.2 g of telluric acid (supplier: FLUKA) (i.e. 0.608 mole of tellurium).
On chauffe la solution obtenue précédemment à 60°C pendant 1 heure et 20 minutes, en couvrant pour éviter 1 ' evaporation et en agitant. On obtient ainsi une solution limpide rouge que l'on laisse refroidir sous agitation jusqu'à 30°C, ce qui dure environ 2 heures.The solution obtained above is heated at 60 ° C for 1 hour and 20 minutes, covering to avoid evaporation and stirring. This gives a clear red solution which is allowed to cool with stirring to 30 ° C, which lasts for about 2 hours.
c) Introduction de la silicec) Introduction of silica
393,6 g de silice Ludox (contenant 40% en poids de silice, fournie par la société Dupont) sont introduits sous agitation dans la solution de Mo, V et Te préparée précédemment. Cette dernière conserve sa limpidité et sa coloration rouge.393.6 g of Ludox silica (containing 40% by weight of silica, supplied by the company Dupont) are introduced with stirring into the solution of Mo, V and Te prepared above. The latter retains its clarity and red coloration.
On ajoute ensuite la solution de niobium préparée précédemment. On obtient ainsi un gel orange fluo au bout de quelques minutes d'agitation. On sèche alors par atomisation cette solution. L'atomiseur utilisé est un atomiseur de laboratoire (ATSELAB de la société Sodeva) . L' atomisation se déroule sous atmosphère d'azote (afin d'éviter toute oxydation et toute combustion intempestive de l'acide oxalique présent dans la barbotine) .The niobium solution prepared above is then added. This gives a fluorescent orange gel after a few minutes of agitation. This solution is then spray dried. The atomizer used is a laboratory atomizer (ATSELAB from the company Sodeva). The atomization takes place under a nitrogen atmosphere (in order to avoid any oxidation and any untimely combustion of the oxalic acid present in the slip).
Les paramètres de marche sont globalement :The operating parameters are globally:
- débit d'azote de l'ordre de 45 Nm3/h ;- nitrogen flow rate of the order of 45 Nm 3 / h;
- débit de barbotine de l'ordre de 500 g/h ; - température d'entrée des gaz comprise entre 155°C et 170°C ;- slip flow of the order of 500 g / h; - gas inlet temperature between 155 ° C and 170 ° C;
- température de sortie des gaz comprise entre 92 °C et 100°C.- gas outlet temperature between 92 ° C and 100 ° C.
On met ensuite le produit récupéré (355,2 g), qui présente une granulometrie inférieure à 40 microns à l'étuve à 130°C pendant une nuit, dans un plateau téfloné. On obtient ainsi 331 g de produit sec.The recovered product (355.2 g), which has a particle size of less than 40 microns, is then placed in an oven at 130 ° C. overnight in a teflon-coated tray. 331 g of dry product are thus obtained.
d) Calcination Les précalcinations et calcinations ont été faites sous flux d'air et d'azote dans des capacités en acier. Ces capacités sont directement installées dans des fours à moufles et l'alimentation en air se fait par la cheminée. Un puits thermométrique interne permet un juste contrôle de la température. Le couvercle est utile pour éviter un retour d'air vers le catalyseur.d) Calcination The precalcinations and calcinations were carried out under air and nitrogen flow in steel tanks. These capacities are directly installed in muffle furnaces and the air supply is through the chimney. An internal thermowell allows proper temperature control. The cover is useful to avoid a return of air to the catalyst.
Tout d'abord, on précalcine les 331 g du précurseur obtenu précédemment pendant 4 heures à 300°C sous flux d'air de 47,9 ml/min/g de précurseur. Le solide obtenu est ensuite calciné pendant 2 heures à 600°C sous un flux d'azote de 12,8 ml/min/g de solide. On obtient ainsi le catalyseur souhaité.First of all, the 331 g of the precursor obtained previously is precalcined for 4 hours at 300 ° C. under an air flow of 47.9 ml / min / g of precursor. The solid obtained is then calcined for 2 hours at 600 ° C. under a nitrogen flow of 12.8 ml / min / g of solid. The desired catalyst is thus obtained.
Exemple 2 Tests du catalyseur a) Apparei11âge Afin de simuler le procédé selon l'invention, on a effectué des simulations en laboratoire dans un réacteur en lit fixe de laboratoire, en générant des impulsions de propane et des impulsions d'oxygène. En utilisant un chargement du réacteur ayant deux lits de catalyseur superposés, on peut ainsi simuler le comportement du catalyseur et ce qu'il aurait subi dans deux réacteurs successifs à lit transporté montant appelés « risers ».Example 2 Catalyst Tests a) Apparatus In order to simulate the method according to the invention, laboratory simulations were carried out in a laboratory fixed bed reactor, generating propane pulses and oxygen pulses. By using a loading of the reactor having two superimposed catalyst beds, it is thus possible to simulate the behavior of the catalyst and what it would have undergone in two successive reactors with rising transport bed called “risers”.
i) Un seul réacteur (à titre comparatif) : test dit « simple RISER » On charge, du bas vers le haut, dans un réacteur vertical de forme cylindrique et en pyrex :i) A single reactor (for comparison): so-called "simple RISER" test We load, from bottom to top, into a vertical reactor of cylindrical shape and in pyrex:
- une première hauteur de 1 ml de carbure de silicium sous forme de particules de 0,125 mm de diamètre,- a first height of 1 ml of silicon carbide in the form of particles of 0.125 mm in diameter,
- une seconde hauteur de 1 ml de carbure de silicium sous forme de particules de 0,062 mm de diamètre,- a second height of 1 ml of silicon carbide in the form of particles of 0.062 mm in diameter,
- une troisième hauteur de 5 g de catalyseur sous forme de particules de 0,02 à 1 mm dilué avec 5 ml de carbure de silicium sous forme de particules de 0,062 mm de diamètre,a third height of 5 g of catalyst in the form of particles of 0.02 to 1 mm diluted with 5 ml of silicon carbide in the form of particles of 0.062 mm in diameter,
- une quatrième hauteur de 1 ml de carbure de silicium sous forme de particules de 0,062 mm de diamètre,- a fourth height of 1 ml of silicon carbide in the form of particles of 0.062 mm in diameter,
- une cinquième hauteur de 3 ml de carbure de silicium sous forme de particules de 0,125 mm de diamètre,- a fifth height of 3 ml of silicon carbide in the form of particles of 0.125 mm in diameter,
- une sixième hauteur de 1 ml de carbure de silicium sous forme de particules de 0,062 mm de diamètre,- a sixth height of 1 ml of silicon carbide in the form of particles of 0.062 mm in diameter,
- une septième hauteur de 5 ml de carbure de silicium sous forme de particules de 0,062 mm de diamètre, - une huitième hauteur de 1 ml de carbure de silicium sous forme de particules de 0,062 mm de diamètre,- a seventh height of 5 ml of silicon carbide in the form of particles of 0.062 mm in diameter, - an eighth height of 1 ml of silicon carbide in the form of particles of 0.062 mm in diameter,
- une neuvième hauteur de 2 ml de carbure de silicium sous forme de particules de 0,125 mm de diamètre,- a ninth height of 2 ml of silicon carbide in the form of particles of 0.125 mm in diameter,
- puis, une dixième hauteur de carbure de silicium sous forme de particules de 1,19 mm de manière à remplir la totalité du réacteur. ii) Deux réacteurs (selon l'invention) : test dit « double RISER »- Then, a tenth height of silicon carbide in the form of particles of 1.19 mm so as to fill the entire reactor. ii) Two reactors (according to the invention): so-called “double RISER” test
L'appareillage est le même que précédemment, sauf que la septième hauteur de 5 ml carbure de silicium est remplacée par 5 g de catalyseur dilué avec 5 ml de carbure de silicium 0,062 mm, comme la troisième hauteur de catalyseur.The apparatus is the same as above, except that the seventh height of 5 ml of silicon carbide is replaced by 5 g of catalyst diluted with 5 ml of 0.062 mm of silicon carbide, like the third height of catalyst.
On a donc chargé deux lits de catalyseur, l'un au-dessus de l'autre dans le réacteur, ce qui permet de simuler le comportement d'un appareil à 2 réacteurs tel que celui représenté sur la figure annexée.Two catalyst beds were therefore loaded, one above the other, into the reactor, which makes it possible to simulate the behavior of an apparatus with 2 reactors such as that shown in the appended figure.
b) Mode opératoireb) Procedure
Le réacteur est ensuite chauffé à 250°C et le vaporiseur à 200°C. L'amorçage électrique de la pompe à eau est activé. Une fois que le réacteur et le vaporiseur ont atteint les températures indiquées ci-dessus, on active la pompe à eau et on fait monter la température du réacteur à la température de test voulue .The reactor is then heated to 250 ° C and the evaporator to 200 ° C. The electric priming of the water pump is activated. Once the reactor and the vaporizer have reached the temperatures indicated above, the water pump is activated and the temperature of the reactor is raised to the desired test temperature.
On laisse ensuite le point chaud du réacteur se stabiliser pendant 30 minutes.The reactor hot spot is then allowed to stabilize for 30 minutes.
Puis, de l'oxygène est introduit en 10 impulsions de 23 secondes chacune pour bien oxyder le catalyseur. Le catalyseur est considéré comme totalement oxydé lorsque la température du point chaud s'est stabilisée, c'est-à-dire quand il n'y a plus d'exothermie due à la réaction (en suivant la température du catalyseur mesurée au moyen d'un thermocouple placé dans le lit catalytique, on peut voir les fluctuations de température en fonction des impulsions) .Then, oxygen is introduced in 10 pulses of 23 seconds each to oxidize the catalyst well. The catalyst is considered to be completely oxidized when the temperature of the hot spot has stabilized, that is to say when there is no longer any exotherm due to the reaction (by following the temperature of the catalyst measured by means of 'a thermocouple placed in the catalytic bed, we can see the temperature fluctuations as a function of the pulses).
La pression à l'entrée du réacteur était d'environ 1,2 à 1,8 bar (absolu) et la perte de charge à travers le réacteur est d'environ 0,2 à 0,8 bar (relatif).The pressure at the inlet of the reactor was approximately 1.2 to 1.8 bar (absolute) and the pressure drop across the reactor was approximately 0.2 to 0.8 bar (relative).
Pour ce qui est de la production d'acide acrylique proprement dite, un bilan rédox est composé de 60 cycles rédox. Un cycle rédox représente : - 13,3 secondes de propane dans un flux continu d'hélium- krypton/eau, - 45 secondes de flux continu d'hélium- krypton/eau, - 20 secondes d'oxygène dans un flux continu d'hélium- krypton/eau,With regard to the production of acrylic acid proper, a redox balance is made up of 60 redox cycles. A redox cycle represents: - 13.3 seconds of propane in a continuous flow of helium-krypton / water, - 45 seconds of continuous flow of helium-krypton / water, - 20 seconds of oxygen in a continuous flow of helium-krypton / water,
- 45 secondes de flux continu d'hélium-krypton/eau. Pendant le bilan, quatre prélèvements sont faits, chacun représentant 15 cycles. On effectue aussi 4 prélèvements de gaz à l'aide de poches à gaz, chaque prélèvement représentant 15 cycles. (Les prélèvements de gaz sont effectués sur une durée correspondant à un multiple de la durée d'un cycle, pour pouvoir connaître la quantité théorique de propane injectée) . Chaque petit flacon laveur (de 25 ml de contenance et rempli de 20 ml d'eau) est équipé d'une poche à gaz, et lorsque l'on connecte le flacon à la sortie du réacteur (dès que le liquide fait des bulles) , la poche est ouverte et le chronomètre est déclenché. Pour vérifier l'état d'oxydation du catalyseur, une nouvelle série de 10 impulsions de 23 secondes d'oxygène est effectuée. Elle montre que l'état d'oxydation du solide a été maintenu pendant le bilan (pas d'exothermie) .- 45 seconds of continuous helium-krypton / water flow. During the assessment, four samples are taken, each representing 15 cycles. 4 gas samples are also taken using gas bags, each sample representing 15 cycles. (The gas samples are taken over a period corresponding to a multiple of the duration of a cycle, in order to be able to know the theoretical quantity of propane injected). Each small washing bottle (25 ml capacity and filled with 20 ml water) is equipped with a gas pocket, and when the bottle is connected to the outlet of the reactor (as soon as the liquid bubbles) , the pocket is opened and the stopwatch is started. To check the oxidation state of the catalyst, a new series of 10 pulses of 23 seconds of oxygen is carried out. It shows that the solid state of oxidation was maintained during the balance (no exotherm).
Les effluents liquides sont analysés sur un chromâtographe HP 6890, après avoir effectué un étalonnage spécifique.Liquid effluents are analyzed on an HP 6890 chromatograph, after performing a specific calibration.
Les gaz sont analysés pendant le bilan sur un chromatographe micro-GC Chrompack.The gases are analyzed during the balance on a micro-GC Chrompack chromatograph.
Un dosage de l'acidité est effectué sur chaque flacon en cours de bilan, pour déterminer le nombre exact de moles d'acide produites et valider les analyses chromatographiques.An acidity assay is performed on each bottle during the assessment, to determine the exact number of moles of acid produced and to validate the chromatographic analyzes.
c) Résultatsc) Results
Les résultats finals correspondent à la moyenne des microbilans effectués sur les 4 flacons laveurs et les 4 poches à gaz. Un bilan est composé de 60 cycles avec des pressions partielles en propane et en oxygène correspondant aux ratios suivants : pour la réaction : Propane/He-Kr/H0 : 10/45/45 pour la régénération : 02/He-Kr/H2O : 20/45/45 Le débit d'He/Kr est de 4,325 Nl/h (Ni = litre de gaz à 0°C et sous 760 mm Hg)The final results correspond to the average of the microbilans carried out on the 4 washing bottles and the 4 gas pockets. A balance sheet is made up of 60 cycles with partial pressures of propane and oxygen corresponding to the following ratios: for the reaction: Propane / He-Kr / H0: 10/45/45 for the regeneration: 0 2 / He-Kr / H 2 O: 20/45/45 The flow rate of He / Kr is 4.325 Nl / h (Ni = liter of gas at 0 ° C and under 760 mm Hg)
Les résultats sont regroupés dans le tableau suivant : The results are grouped in the following table:
(*) : dans le test double RISER, la consommation d'oxygène a été calculée sur la masse totale de catalyseur (somme des deux lits) .(*): in the double RISER test, the oxygen consumption was calculated on the total mass of catalyst (sum of the two beds).
On voit que sur 1 ou 2 lits, on extrait la même quantité d'oxygène du catalyseur (en g/kg catalyseur), et avec le même débit (même valeurs de Flux g/kg. s). Par contre, le ratio conversion est calculé en ne tenant compte que d'un seul lit, car il reflète le débit de solide nécessaire pour convertir 1 kg de propane. L'unité devant fonctionner à une densité maximale (limitée par le flux de catalyseur) , le seul moyen d'augmenter encore la conversion est donc de sortir le catalyseur usé et de le remplacer par du catalyseur frais, et ce, sans changer le flux de catalyseur. C'est donc le ratio conversion sur 1 lit qui dimensionne l'unité.We see that on 1 or 2 beds, the same amount of oxygen is extracted from the catalyst (in g / kg catalyst), and with the same flow rate (same flux values g / kg. S). However, the ratio conversion is calculated taking into account only one bed, as it reflects the flow of solid required to convert 1 kg of propane. Since the unit must operate at a maximum density (limited by the flow of catalyst), the only way to further increase the conversion is therefore to take out the spent catalyst and replace it with fresh catalyst, without changing the flow. of catalyst. It is therefore the conversion ratio on 1 bed which sizes the unit.
Les résultats sont bons, la sélectivité en acide acrylique (AA) étant proche de 60% à 360°C et à 380°C.The results are good, the selectivity for acrylic acid (AA) being close to 60% at 360 ° C and 380 ° C.
La conversion du propane (Pan) avec le procédé selon l'invention est nettement supérieure à celle du procédé utilisé comparativement, elle est pratiquement deux fois supérieure à 360°C. Les rendements en acide acrylique sont supérieurs à 17,5% à toutes les températures testées, alors que selon le procédé comparatif ils sont inférieurs à 15,5%.The conversion of propane (Pan) with the process according to the invention is significantly higher than that of the process used comparatively, it is practically twice as high as 360 ° C. The acrylic acid yields are greater than 17.5% at all the temperatures tested, while according to the comparative process they are less than 15.5%.
Ainsi, l'utilisation des deux réacteurs permet d'obtenir un gain en conversion par passe, sans perte de sélectivité. Ceci permet de diminuer le ratio conversion, recalculé par réacteur, mais en tenant compte de la conversion totale, car l'utilisation d'un second réacteur revient à augmenter le flux de catalyseur, dans une unité qui est déjà souvent au maximum de densité solide. Thus, the use of the two reactors makes it possible to obtain a gain in conversion per pass, without loss of selectivity. This makes it possible to reduce the conversion ratio, recalculated per reactor, but taking into account the total conversion, because the use of a second reactor amounts to increasing the flow of catalyst, in a unit which is already often at maximum solid density .

Claims

REVENDICATIONS
1. Procédé de fabrication d'acide acrylique a partir de propane, dans lequel : a) on introduit un mélange gazeux dépourvu d'oxygène moléculaire et comprenant du propane, de la vapeur d'eau, ainsi que, le cas échéant, un gaz inerte, dans un premier réacteur à lit de catalyseur transporté, b) à la sortie du premier réacteur, on sépare les gaz du catalyseur ; c) on renvoie le catalyseur dans un régénérateur ; d) on introduit les gaz dans un second réacteur à lit de catalyseur transporté ; e) à la sortie du second réacteur, on sépare les gaz du catalyseur et on récupère l'acide acrylique contenu dans les gaz séparés ; f) on renvoie le catalyseur dans le régénérateur ; g) on réintroduit du catalyseur régénéré provenant du régénérateur dans les premier et second réacteurs ; et dans lequel le catalyseur comprend du molybdène, du vanadium, du tellure ou de l'antimoine, de l'oxygène et au moins un autre élément X choisi parmi le niobium, le tantale, le tungstène, le titane, l'aluminium, le zirconium, le chrome, le manganèse, le fer, le ruthénium, le cobalt, le rhodium, le nickel, le palladium, le platine, l'antimoine, le bismuth, le bore, l'indium et le cerium.1. Process for the manufacture of acrylic acid from propane, in which: a) a gaseous mixture devoid of molecular oxygen and comprising propane, water vapor and, where appropriate, a gas is introduced inert, in a first reactor with a transported catalyst bed, b) at the outlet of the first reactor, the gases are separated from the catalyst; c) the catalyst is returned to a regenerator; d) the gases are introduced into a second reactor with a transported catalyst bed; e) at the outlet of the second reactor, the gases are separated from the catalyst and the acrylic acid contained in the separated gases is recovered; f) the catalyst is returned to the regenerator; g) regenerated catalyst from the regenerator is reintroduced into the first and second reactors; and in which the catalyst comprises molybdenum, vanadium, tellurium or antimony, oxygen and at least one other element X chosen from niobium, tantalum, tungsten, titanium, aluminum, zirconium, chromium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, antimony, bismuth, boron, indium and cerium.
2. Procédé selon la revendication 1, dans lequel les premier et second réacteurs sont verticaux et le catalyseur est transporté vers le haut par le flux des gaz.2. The method of claim 1, wherein the first and second reactors are vertical and the catalyst is transported upward by the flow of gases.
3. Procédé selon la revendication 1 ou la revendication 2, dans lequel la température des réacteurs est comprise entre 200 à 500°C et de préférence entre 250 à 450°C. 3. The method of claim 1 or claim 2, wherein the reactor temperature is between 200 to 500 ° C and preferably between 250 to 450 ° C.
4. Procédé selon l'une des revendications 1 à 3, dans lequel la pression dans les réacteurs est comprise entre 1,01.104 et 1,01.106 Pa (0,1 à 10 atmosphères) et de préférence entre 5,05.104 et 5,05.105 Pa (0,5-5 atmosphères).4. Method according to one of claims 1 to 3, wherein the pressure in the reactors is between 1.01.10 4 and 1.01.10 6 Pa (0.1 to 10 atmospheres) and preferably between 5.05.10 4 and 5.05.10 5 Pa (0.5-5 atmospheres).
5. Procédé selon l'une des revendications 1 à 4, dans lequel le temps de séjour des gaz dans chaque réacteur est compris entre 0,01 et 90 secondes et de préférence entre 0,1 et 30 secondes.5. Method according to one of claims 1 to 4, wherein the residence time of the gases in each reactor is between 0.01 and 90 seconds and preferably between 0.1 and 30 seconds.
6. Procédé selon l'une des revendications 1 à 5, dans lequel la régénération du catalyseur est réalisée par chauffage en présence d'oxygène ou d'un gaz contenant de l'oxygène, à une température de 250 à 500°C.6. Method according to one of claims 1 to 5, wherein the regeneration of the catalyst is carried out by heating in the presence of oxygen or an oxygen-containing gas, at a temperature of 250 to 500 ° C.
7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que le propylene produit provenant des gaz séparés à l'étape e) et/ou le propane n'ayant pas réagi sont recyclés à l'entrée du réacteur.7. Method according to one of claims 1 to 6, characterized in that the propylene produced from the gases separated in step e) and / or the unreacted propane are recycled to the inlet of the reactor.
8. Procédé selon l'une des revendications 1 à 7, dans lequel les proportions des éléments du catalyseur satisfont aux conditions suivantes :8. Method according to one of claims 1 to 7, in which the proportions of the elements of the catalyst satisfy the following conditions:
0,25 < rMo < 0, 98 0, 003 < rv < 0,50.25 <r Mo <0.98 0.003 <r v <0.5
0,003 < rTe ou r sb < 0,5 0, 003 < rx < 0,5 dans lesquelles rMo, rv, rTe et rx représentent les fractions molaires, respectivement, de Mo, V, Te et X, par rapport à la somme des nombres de moles de tous les éléments du catalyseur, à l'exception de l'oxygène.0.003 <r Te or r sb <0.5 0, 003 <r x <0.5 in which r Mo , r v , r Te and r x represent the molar fractions, respectively, of Mo, V, Te and X, based on the sum of the mole numbers of all elements of the catalyst, except oxygen.
9. Procédé selon l'une des revendications 1 à 8, dans lequel le catalyseur répond à la formule (I) ou à la formule (Ibis) suivantes :9. Method according to one of claims 1 to 8, in which the catalyst corresponds to the following formula (I) or to the formula (Ibis):
MOiVaTetNbcSidOx (I) MoiVaSbbNbcSidOx (Ibis) dans lesquelles :MOiV a Te t Nb c Si d O x (I) MoiV a Sb b Nb c Si d O x (Ibis) in which :
- a est compris entre 0,006 et 1, bornes incluses- a is between 0.006 and 1, limits included
- b est compris entre 0,006 et 1, bornes incluses- b is between 0.006 and 1, limits included
- c est compris entre 0,006 et 1, bornes incluses- it is between 0.006 and 1, limits included
- d est compris entre 0 et 3,5, bornes incluses ; et- d is between 0 and 3.5, limits included; and
- x est la quantité d'oxygène lié aux autres éléments et dépend de leurs états d'oxydation.- x is the quantity of oxygen linked to the other elements and depends on their oxidation states.
10. Procédé selon la revendication 9, dans lequel, dans la formule (I) ou (Ibis) :10. The method of claim 9, in which, in formula (I) or (Ibis):
- a est compris entre 0,09 et 0,8, bornes incluses- a is between 0.09 and 0.8, limits included
- b est compris entre 0,04 et 0,6, bornes incluses- b is between 0.04 and 0.6, limits included
- c est compris entre 0,01 et 0,4, bornes incluses ; et- c is between 0.01 and 0.4, limits included; and
- d est compris entre 0,4 et 1,6, bornes incluses.- d is between 0.4 and 1.6, limits included.
11. Procédé selon l'une des revendications l à 10, dans lequel, l'un au moins des deux réacteurs comprend un co- catalyseur répondant à la formule (II) suivante : MθιBia'Feb'CoC'Nid'Ke'Sbf.Tig.Sih.Cai.Nbj.Te .Pbι. m-Cun' (II) dans laquelle :11. Method according to one of claims l to 10, in which at least one of the two reactors comprises a cocatalyst corresponding to the following formula (II): MθιBia'Feb'Co C ' Nest ' Ke ' Sb f .Tig . If h .Cai.Nbj.Te .Pbι. m -None '(II) in which:
- a' est compris entre 0,006 et 1, bornes incluses ;- a 'is between 0.006 and 1, limits included;
- b' est compris entre 0 et 3,5, bornes incluses - c' est compris entre 0 et 3,5, bornes incluses- b 'is between 0 and 3.5, limits included - c' is between 0 and 3.5, limits included
- d' est compris entre 0 et 3,5, bornes incluses- d is between 0 and 3.5, limits included
- e' est compris entre 0 et 1, bornes incluses- e 'is between 0 and 1, limits included
- f est compris entre 0 et 1, bornes incluses- f is between 0 and 1, limits included
- g' est compris entre 0 et 1, bornes incluses - h' est compris entre 0 et 3,5, bornes incluses ;- g 'is between 0 and 1, limits included - h' is between 0 and 3.5, limits included;
- i' est compris entre 0 et 1, bornes incluses- i 'is between 0 and 1, limits included
- j' est compris entre 0 et 1, bornes incluses- i is between 0 and 1, limits included
- k' est compris entre 0 et 1, bornes incluses- k 'is between 0 and 1, limits included
- l' est compris entre 0 et 1 , bornes incluses - m' est compris entre 0 et 1, bornes incluses ; et- l is between 0 and 1, limits included - m 'is between 0 and 1, limits included; and
- n' est compris entre 0 et 1, bornes incluses. - is between 0 and 1, limits included.
12. Procédé selon la revendication 11, dans lequel le co- catalyseur est régénéré et circule de la même manière que le catalyseur.12. The method of claim 11, wherein the cocatalyst is regenerated and circulates in the same manner as the catalyst.
13. Procédé selon la revendication 11 ou la revendication13. The method of claim 11 or claim
12, dans lequel, dans le co-catalyseur de formule (II) :12, in which, in the co-catalyst of formula (II):
- a' est compris entre 0,01 et 0,4, bornes incluses ;- a 'is between 0.01 and 0.4, limits included;
- b' est compris entre 0,2 et 1,6, bornes incluses- b 'is between 0.2 and 1.6, limits included
- c' est compris entre 0,3 et 1,6, bornes incluses - d' est compris entre 0,1 et 0,6, bornes incluses- it is between 0.3 and 1.6, limits included - d is between 0.1 and 0.6, limits included
- e' est compris entre 0,006 et 0,01, bornes incluses ;- e 'is between 0.006 and 0.01, limits included;
- f est compris entre 0 et 0,4, bornes incluses ;- f is between 0 and 0.4, limits included;
- g' est compris entre 0 et 0,4, bornes incluses ;- g 'is between 0 and 0.4, limits included;
- h' est compris entre 0,01 et 1,6, bornes incluses ; - i' est compris entre 0 et 0,4, bornes incluses- h 'is between 0.01 and 1.6, limits included; - i 'is between 0 and 0.4, limits included
- j' est compris entre 0 et 0,4, bornes incluses- i is between 0 and 0.4, limits included
- k' est compris entre 0 et 0,4, bornes incluses- k 'is between 0 and 0.4, limits included
- l' est compris entre 0 et 0,4, bornes incluses- l is between 0 and 0.4, limits included
- m' est compris entre 0 et 0,4, bornes incluses ; et - n' est compris entre 0 et 0,4, bornes incluses.- m 'is between 0 and 0.4, limits included; and - is between 0 and 0.4, limits included.
14. Procédé selon l'une des revendications 11 à 13, dans lequel, on utilise un rapport massique du catalyseur au co- catalyseur supérieur à 0,5 et de préférence d'au moins 1.14. Method according to one of claims 11 to 13, in which a mass ratio of the catalyst to the cocatalyst is greater than 0.5 and preferably at least 1.
15. Procédé selon l'une des revendications 12 à 14, dans lequel le catalyseur et le co-catalyseur sont mélangés.15. Method according to one of claims 12 to 14, wherein the catalyst and the cocatalyst are mixed.
16. Procédé selon l'une des revendications 12 à 15, dans lequel le catalyseur et le co-catalyseur se présentent sous la forme de grains, chaque grain comprenant à la fois le catalyseur et le co-catalyseur. 16. Method according to one of claims 12 to 15, wherein the catalyst and the cocatalyst are in the form of grains, each grain comprising both the catalyst and the cocatalyst.
EP03769539A 2002-09-10 2003-08-29 Method for producing acrylic acid from propane, in the absence of molecular oxygen Withdrawn EP1539668A1 (en)

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FR0211196A FR2844262B1 (en) 2002-09-10 2002-09-10 PROCESS FOR THE MANUFACTURE OF ACRYLIC ACID FROM PROPANE, IN THE ABSENCE OF MOLECULAR OXYGEN
FR0211196 2002-09-10
PCT/FR2003/002608 WO2004024664A1 (en) 2002-09-10 2003-08-29 Method for producing acrylic acid from propane, in the absence of molecular oxygen

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FR2844262B1 (en) 2004-10-15
US20060004225A1 (en) 2006-01-05
US7282604B2 (en) 2007-10-16
CN1681765A (en) 2005-10-12
JP2005538171A (en) 2005-12-15
CN100345811C (en) 2007-10-31

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