WO2008025917A2 - Method of manufacturing hydrogen peroxide - Google Patents
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- WO2008025917A2 WO2008025917A2 PCT/FR2007/051803 FR2007051803W WO2008025917A2 WO 2008025917 A2 WO2008025917 A2 WO 2008025917A2 FR 2007051803 W FR2007051803 W FR 2007051803W WO 2008025917 A2 WO2008025917 A2 WO 2008025917A2
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229910052786 argon Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 230000005495 cold plasma Effects 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001994 activation Methods 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000008246 gaseous mixture Substances 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000000678 plasma activation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000002912 waste gas Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000012224 working solution Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/029—Preparation from hydrogen and oxygen
- C01B15/0295—Preparation from hydrogen and oxygen by electrical discharge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
Definitions
- the present invention relates to a process for preparing an aqueous solution of hydrogen peroxide from steam, oxygen and argon. More particularly, it relates to a process for preparing an aqueous solution of hydrogen peroxide in which a mixture consisting of water vapor, oxygen and argon is brought into contact with a cold plasma.
- Hydrogen peroxide is manufactured industrially according to a method based on the technique of auto-oxidation of an anthraquinone derivative, of the type comprising a step (a) of catalytic hydrogenation, in a hydrogenator, of a working solution containing at least one anthraquinone derivative in solution in at least one organic solvent; followed by a step (b) of oxidation, in an oxidizer, of the hydrogenated working solution by means of an oxygen-containing fluid, in particular by means of air and a step (c) of separation by water, in an extractor, of hydrogen peroxide and the oxidized working solution and finally a step (d) of recycling to the hydrogenator of the oxidized working solution and recovered in (c).
- the direct synthesis of an aqueous solution of hydrogen peroxide in a stirred reactor was studied.
- the reactor generally comprises an aqueous zone occupied by the working solution (generally aqueous acid solution) and the catalyst, and an area occupied by the gases located above the aqueous zone.
- the reactor is provided with a stirring system that both agitates the aqueous zone and disperses the gases in the aqueous phase. This direct synthesis requires operating at high pressure.
- Cold plasma is generally associated with a gaseous medium ionized at low temperature and atmospheric pressure.
- the cold plasma is produced in a confined chamber generally under partial vacuum more or less advanced, into which the "plasmagene" gas is introduced, to which energy is transferred by means of a controlled electric discharge.
- the plasma gas can be a mixture that can ionize easily, thus becoming a conductor of electricity.
- As for the electric discharge it is obtained either between two electrodes (discharge under electric field, low pressure luminescent or crown at atmospheric pressure), or by a device without electrodes, under variable electromagnetic field of high frequency type (13,56 MHz) or microwaves (2.45 GHz).
- the present invention provides a process for producing hydrogen peroxide comprising (i) a step in which a gaseous mixture of water vapor, oxygen and argon is activated by cold plasma.
- This process is characterized in that at the end of this step, the gaseous effluent is subjected to a condensation step to give on the one hand an aqueous solution of hydrogen peroxide and on the other hand a mixture of gases. waste which is then recycled to the cold plasma activation step.
- argon is present at more than 50% by volume in the gaseous mixture of the activation step.
- the activation step (i) can be carried out at a pressure of between 0.01 and 10 bar absolute. Operation at atmospheric pressure is preferred.
- the mixture of the activation step may comprise hydrogen.
- the mixture comprises hydrogen
- the composition of the mixture of the activation step consists of either a hydrogen content of less than 3.2% by volume or an oxygen content of less than 5% by volume.
- a composition of the mixture of the activation step consisting of a hydrogen content of less than 3.2% by volume and an oxygen content of less than 21% by volume with a hydrogen content greater than
- the process according to the present invention is very interesting in terms of energy balance when hydrogen is present.
- the activation step may comprise a liquid medium, preferably an aqueous medium.
- the activation step can be carried out in the presence of a catalyst.
- the catalyst is preferably an acidic solid having a Hammett acidity of less than +2.
- the acidity of Hammett is determined by amine titration using indicators or adsorption of a base in the gas phase.
- K. Tanabe et al. in "Studies in Surface Science and Catalysis", Vol 51, 1989.
- Catalysts meeting the Hammett acidity criterion of less than +2 can be selected from natural or synthetic siliceous materials or acidic zeolites; inorganic supports, such as coated oxides by inorganic acids, mono, di, tri or polyacids; oxides or mixed oxides or heteropolyacids.
- the process can be carried out continuously or batchwise in a cold plasma reactor.
- the source of oxygen it is possible to use oxygen from the air containing approximately 1% by volume of argon. Air enriched with oxygen is however preferred.
- oxygen obtained by cryogenic separation is used.
- gaseous oxygen generators of the type VSA Vacuum Swing Adsorption
- VSA Vauum Swing Adsorption
- this route can be used both as a source of oxygen and argon.
- the process can be implemented in a cold plasma reactor equipped with at least one inlet (1) for oxygen and argon, an inlet (2) for steam and possibly an inlet for hydrogen and an outlet.
- the effluent at the outlet (3) of the reactor is then subjected to a condensation step to give an aqueous solution of hydrogen peroxide (4) and a gaseous flow comprising oxygen, argon and optionally hydrogen which is totally or partially recycled (6) to the cold plasma reactor after a possible purge of argon (5).
- the cold plasma reactor may comprise a catalyst.
- the catalyst can be deposited directly on the electrodes, for example by impregnation and deposition technique.
- the catalyst optionally in the form of powder or grain, can be placed in a fixed or fluidized bed between the electrodes.
- the central electrode may comprise several trays on which the catalyst may be deposited ( Figure 2).
- the process according to the present invention makes it possible to obtain concentrated aqueous solutions of hydrogen peroxide with very good productivity.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
The present invention relates to a method of preparation of an aqueous solution of hydrogen peroxide from water vapor, oxygen and argon. Its more particular object is a method of preparing an aqueous solution of hydrogen peroxide in which a mixture made of water vapor, oxygen and argon and optionally hydrogen is put into contact with cold plasma.
Description
PROCEDE DE FABRICATION DU PEROXYDE D'HYDROGENE PROCESS FOR PRODUCING HYDROGEN PEROXIDE
La présente invention concerne un procédé de préparation d'une solution aqueuse de peroxyde d'hydrogène à partir de vapeur d'eau, d'oxygène et d'argon. Elle a plus particulièrement pour objet un procédé de préparation d'une solution aqueuse de peroxyde d'hydrogène dans lequel un mélange constitué de vapeur d'eau, d'oxygène et d'argon est mis en contact avec un plasma froid.The present invention relates to a process for preparing an aqueous solution of hydrogen peroxide from steam, oxygen and argon. More particularly, it relates to a process for preparing an aqueous solution of hydrogen peroxide in which a mixture consisting of water vapor, oxygen and argon is brought into contact with a cold plasma.
Le peroxyde d'hydrogène est fabriqué industriellement selon un procédé basé sur la technique d'auto-oxydation d'un dérivé anthraquinonique, du type comprenant une étape (a) d'hydrogénation catalytique, dans un hydrogénateur, d'une solution de travail contenant au moins un dérivé anthraquinonique en solution dans au moins un solvant organique ; suivie d'une étape (b) d'oxydation, dans un oxydeur, de la solution de travail hydrogénée au moyen d'un fluide contenant de l'oxygène, notamment au moyen de l'air et d'une étape (c) de séparation par de l'eau, dans un extracteur, du peroxyde d'hydrogène et de la solution de travail oxydée et enfin une étape (d) de recyclage vers l'hydrogénateur de la solution de travail oxydée et récupérée en (c).Hydrogen peroxide is manufactured industrially according to a method based on the technique of auto-oxidation of an anthraquinone derivative, of the type comprising a step (a) of catalytic hydrogenation, in a hydrogenator, of a working solution containing at least one anthraquinone derivative in solution in at least one organic solvent; followed by a step (b) of oxidation, in an oxidizer, of the hydrogenated working solution by means of an oxygen-containing fluid, in particular by means of air and a step (c) of separation by water, in an extractor, of hydrogen peroxide and the oxidized working solution and finally a step (d) of recycling to the hydrogenator of the oxidized working solution and recovered in (c).
La synthèse directe d'une solution aqueuse de peroxyde d'hydrogène dans un réacteur agité a été étudiée. Le réacteur comprend en général une zone aqueuse, occupée par la solution de travail (généralement solution aqueuse acide) et le catalyseur, et une zone, occupée par les gaz, située au- dessus de la zone aqueuse. Le réacteur est muni d'un système d'agitation permettant à la fois d'agiter la zone aqueuse et de disperser les gaz dans la phase aqueuse. Cette synthèse directe nécessite d'opérer à pression élevée. Outre le réacteur agité, il a été proposé de conduire la synthèse directe de peroxyde d'hydrogène dans un réacteur tubulaire constitué d'un tube de grande longueur rempli de solution de travail dans laquelle le catalyseur est mis en suspension et l'oxygène et l'hydrogène gazeux sont injectés sous forme de petites bulles dans des proportions au-dessus de la limite inférieure d'inflammabilité du mélange hydrogène-oxygène (US 5194242). La sécurité d'un tel procédé n'est assurée qu'à la condition de maintenir les réactifs gazeux dans le réacteur sous forme de petites bulles. Selon le document US 5641467,
celles-ci ne peuvent être obtenues qu'avec une grande vitesse de circulation de la solution de travail.The direct synthesis of an aqueous solution of hydrogen peroxide in a stirred reactor was studied. The reactor generally comprises an aqueous zone occupied by the working solution (generally aqueous acid solution) and the catalyst, and an area occupied by the gases located above the aqueous zone. The reactor is provided with a stirring system that both agitates the aqueous zone and disperses the gases in the aqueous phase. This direct synthesis requires operating at high pressure. In addition to the stirred reactor, it has been proposed to carry out the direct synthesis of hydrogen peroxide in a tubular reactor consisting of a long tube filled with working solution in which the catalyst is suspended and the oxygen and the Hydrogen gas is injected as small bubbles in proportions above the lower limit of flammability of the hydrogen-oxygen mixture (US 5194242). The safety of such a process is ensured only if the gaseous reactants are kept in the reactor in the form of small bubbles. According to US 5641467, these can only be obtained with a high speed of circulation of the working solution.
Il est également connu de faire réagir de l'hydrogène et de l'oxygène à pression atmosphérique à l'aide d'une décharge électrique, connue sous la dénomination « plasma froid » (B. K. Morinaga, Bull-Chem. Soc. Jp , 1962, 32, p. 345). Plus récemment, J. Zhou et al. (Chem. Commun. 2005, p. 1631-1633) ont activé le mélange gazeux constitué d'hydrogène et d'oxygène à l'aide d'une décharge électrique barrière.It is also known to react hydrogen and oxygen at atmospheric pressure by means of an electric discharge, known under the name "cold plasma" (BK Morinaga, Bull-Chem Soc Jp, 1962). 32: 345). More recently, J. Zhou et al. (Chem Commun 2005, pp. 1631-1633) activated the gaseous mixture of hydrogen and oxygen with a barrier electric discharge.
Par ailleurs, l'étude de B. Dodet et al. (J. Adv. Oxid. Technol. Vol. 8 No. 1 , 2005) porte sur la préparation du peroxyde d'hydrogène dans une phase après décharge d'un système de décharge électrique barrière à pression atmosphérique et température ambiante dans un milieu comprenant de l'oxygène, de l'argon et de la vapeur d'eau.In addition, the study by B. Dodet et al. (J. Adv Oxid Technol Vol 8 No. 1, 2005) relates to the preparation of hydrogen peroxide in a phase after discharge of a barrier electric discharge system at atmospheric pressure and ambient temperature in a medium comprising oxygen, argon and water vapor.
On associe généralement le plasma froid à un milieu gazeux ionisé à faible température et pression atmosphérique. Le plasma froid est produit dans une enceinte confinée généralement sous vide partiel plus ou moins poussé, dans laquelle on introduit le gaz « plasmagène » à qui on transfère de l'énergie par le biais d'une décharge électrique contrôlée. Le gaz plasmagène peut être un mélange qui peut s'ioniser facilement, devenant ainsi conducteur de l'électricité. Quant à la décharge électrique, elle s'obtient soit entre deux électrodes (décharge sous champ électrique, luminescente à basse pression ou couronne à pression atmosphérique), soit par un dispositif sans électrodes, sous champ électromagnétique variable de type hautes fréquences (13,56 MHz) ou micro-ondes (2,45 GHz). La présente invention fournit un procédé de fabrication du peroxyde d'hydrogène comprenant (i) une étape au cours de laquelle un mélange gazeux constitué de vapeur d'eau, d'oxygène et d'argon est activé par plasma froid. Ce procédé est caractérisé en ce qu'à l'issue de cette étape, l'effluent gazeux est soumis à une étape de condensation pour donner d'une part une solution aqueuse de peroxyde d'hydrogène et d'autre part un mélange de gaz résiduaires qui est ensuite recyclé à l'étape d'activation par plasma froid.
Avantageusement l'argon est présent à plus de 50 % en volume dans le mélange gazeux de l'étape d'activation.Cold plasma is generally associated with a gaseous medium ionized at low temperature and atmospheric pressure. The cold plasma is produced in a confined chamber generally under partial vacuum more or less advanced, into which the "plasmagene" gas is introduced, to which energy is transferred by means of a controlled electric discharge. The plasma gas can be a mixture that can ionize easily, thus becoming a conductor of electricity. As for the electric discharge, it is obtained either between two electrodes (discharge under electric field, low pressure luminescent or crown at atmospheric pressure), or by a device without electrodes, under variable electromagnetic field of high frequency type (13,56 MHz) or microwaves (2.45 GHz). The present invention provides a process for producing hydrogen peroxide comprising (i) a step in which a gaseous mixture of water vapor, oxygen and argon is activated by cold plasma. This process is characterized in that at the end of this step, the gaseous effluent is subjected to a condensation step to give on the one hand an aqueous solution of hydrogen peroxide and on the other hand a mixture of gases. waste which is then recycled to the cold plasma activation step. Advantageously, argon is present at more than 50% by volume in the gaseous mixture of the activation step.
L'étape d'activation (i) peut être mise en œuvre à une pression comprise entre 0,01 et 10 bars absolus. La mise en œuvre à pression atmosphérique est préférée.The activation step (i) can be carried out at a pressure of between 0.01 and 10 bar absolute. Operation at atmospheric pressure is preferred.
Outre la vapeur d'eau, l'oxygène et l'argon, le mélange de l'étape d'activation peut comprendre de l'hydrogène.In addition to water vapor, oxygen and argon, the mixture of the activation step may comprise hydrogen.
Lorsque le mélange comprend de l'hydrogène, on préfère opérer avec une composition en-dehors de la zone d'inflammabilité. Avantageusement, la composition du mélange de l'étape d'activation est constituée soit d'une teneur en hydrogène inférieure à 3,2 % en volume, soit d'une teneur en oxygène inférieure à 5 % en volume.When the mixture comprises hydrogen, it is preferred to operate with a composition outside the flammability zone. Advantageously, the composition of the mixture of the activation step consists of either a hydrogen content of less than 3.2% by volume or an oxygen content of less than 5% by volume.
Une composition du mélange de l'étape d'activation constituée soit d'une teneur en hydrogène inférieure à 3,2 % en volume et une teneur en oxygène inférieure à 21 % en volume soit d'une teneur en hydrogène supérieure àA composition of the mixture of the activation step consisting of a hydrogen content of less than 3.2% by volume and an oxygen content of less than 21% by volume with a hydrogen content greater than
76,5 % en volume et une teneur en oxygène inférieure à 5 % en volume est particulièrement préférée.76.5% by volume and an oxygen content of less than 5% by volume is particularly preferred.
Le procédé selon la présente invention est très intéressant au niveau du bilan énergétique lorsque l'hydrogène est présent. L'étape d'activation peut comprendre un milieu liquide, de préférence un milieu aqueux.The process according to the present invention is very interesting in terms of energy balance when hydrogen is present. The activation step may comprise a liquid medium, preferably an aqueous medium.
Selon la présente invention, l'étape d'activation peut être mise en œuvre en présence d'un catalyseur. Le catalyseur est de préférence un solide acide ayant une acidité de Hammett inférieure à +2. L'acidité de Hammett est déterminée par titration aminé à l'aide d'indicateurs ou par adsorption d'une base en phase gazeuse. On peut se reporter à l'article de K. Tanabe et al. dans « Studies in Surface Science and Catalysis », Vol 51 , 1989.According to the present invention, the activation step can be carried out in the presence of a catalyst. The catalyst is preferably an acidic solid having a Hammett acidity of less than +2. The acidity of Hammett is determined by amine titration using indicators or adsorption of a base in the gas phase. One can refer to the article by K. Tanabe et al. in "Studies in Surface Science and Catalysis", Vol 51, 1989.
Les catalyseurs répondant au critère d'acidité de Hammett inférieure à +2, peuvent être choisis parmi des matériaux siliceux naturels ou de synthèse ou les zéolithes acides ; des supports minéraux, tels que des oxydes recouverts
par des acides inorganiques, mono, di, tri ou polyacides ; des oxydes ou oxydes mixtes ou encore des hétéropolyacides.Catalysts meeting the Hammett acidity criterion of less than +2 can be selected from natural or synthetic siliceous materials or acidic zeolites; inorganic supports, such as coated oxides by inorganic acids, mono, di, tri or polyacids; oxides or mixed oxides or heteropolyacids.
Le procédé peut être mis en œuvre en continu ou discontinu dans un réacteur à plasma froid. Comme source d'oxygène, on peut utiliser de l'oxygène de l'air contenant environ 1 % en volume d'argon. De l'air enrichi en oxygène est toutefois préféré. Avantageusement, on utilise de l'oxygène obtenu par séparation cryogénique.The process can be carried out continuously or batchwise in a cold plasma reactor. As the source of oxygen, it is possible to use oxygen from the air containing approximately 1% by volume of argon. Air enriched with oxygen is however preferred. Advantageously, oxygen obtained by cryogenic separation is used.
On préfère cependant utiliser des générateurs d'oxygène gazeux du type VSA (Vacuum Swing Adsorption) qui font appel à une technologie non- cryogénique reposant sur l'adsorption de l'azote à travers un tamis moléculaire sous des variations de pression. Comme la pureté de l'oxygène peut atteindre environ 94 % et l'argon peut être présent jusqu'à 5 % en volume, cette voie peut être utilisée à la fois comme source d'oxygène et d'argon. Selon un mode de réalisation de la présente invention (Figure 1 ), le procédé peut être mis en œuvre dans un réacteur à plasma froid muni au moins d'une entrée (1 ) pour l'oxygène et l'argon, d'une entrée (2) pour la vapeur d'eau et éventuellement d'une entrée pour l'hydrogène et d'une sortie. L'effluent à la sortie (3) du réacteur est ensuite soumis à une étape de condensation pour donner une solution aqueuse de peroxyde d'hydrogène (4) et un flux gazeux comprenant de l'oxygène, de l'argon et éventuellement de l'hydrogène qui est totalement ou partiellement recyclé (6) au réacteur plasma froid après une éventuelle purge d'argon (5).However, it is preferred to use gaseous oxygen generators of the type VSA (Vacuum Swing Adsorption) which use a non-cryogenic technology based on the adsorption of nitrogen through a molecular sieve under pressure variations. Since the purity of oxygen can reach about 94% and argon can be present up to 5% by volume, this route can be used both as a source of oxygen and argon. According to one embodiment of the present invention (FIG. 1), the process can be implemented in a cold plasma reactor equipped with at least one inlet (1) for oxygen and argon, an inlet (2) for steam and possibly an inlet for hydrogen and an outlet. The effluent at the outlet (3) of the reactor is then subjected to a condensation step to give an aqueous solution of hydrogen peroxide (4) and a gaseous flow comprising oxygen, argon and optionally hydrogen which is totally or partially recycled (6) to the cold plasma reactor after a possible purge of argon (5).
Le réacteur à plasma froid peut comprendre un catalyseur. Lorsque la décharge électrique s'obtient entre deux électrodes, le catalyseur peut être déposé directement sur les électrodes, par exemple par technique d'imprégnation et de dépôt.The cold plasma reactor may comprise a catalyst. When the electric discharge is obtained between two electrodes, the catalyst can be deposited directly on the electrodes, for example by impregnation and deposition technique.
Selon une autre variante du procédé, le catalyseur éventuellement sous forme de poudre ou de grain, peut être placé en lit fixe ou fluidisé entre les électrodes.
Lorsque la décharge électrique s'obtient entre une électrode annulaire externe et une électrode centrale, l'électrode centrale peut comporter plusieurs plateaux sur lesquels le catalyseur peut être déposé (Figure 2).According to another variant of the process, the catalyst, optionally in the form of powder or grain, can be placed in a fixed or fluidized bed between the electrodes. When the electric discharge is obtained between an outer annular electrode and a central electrode, the central electrode may comprise several trays on which the catalyst may be deposited (Figure 2).
Le procédé selon la présente invention permet d'obtenir des solutions aqueuses de peroxyde d'hydrogène concentrées avec une très bonne productivité.
The process according to the present invention makes it possible to obtain concentrated aqueous solutions of hydrogen peroxide with very good productivity.
Claims
REVENDICATIONS
1 ) Procédé de fabrication du peroxyde d'hydrogène comprenant (i) une étape au cours de laquelle un mélange gazeux constitué de vapeur d'eau, d'oxygène et d'argon est activé par plasma froid caractérisé en ce qu'à l'issue de cette étape, l'effluent gazeux est soumis à (ii) une étape de condensation pour donner d'une part une solution aqueuse de peroxyde d'hydrogène et d'autre part un mélange de gaz résiduaires qui est ensuite recyclé à l'étape d'activation par plasma froid. 2 ) Procédé selon la revendication 1 caractérisé en ce que l'argon est présent à plus de 50 % en volume dans le mélange gazeux de l'étape d'activation.1) Process for producing hydrogen peroxide, comprising (i) a step in which a gaseous mixture consisting of water vapor, oxygen and argon is activated by cold plasma, characterized in that after this step, the gaseous effluent is subjected to (ii) a condensation step to give on the one hand an aqueous solution of hydrogen peroxide and on the other hand a waste gas mixture which is then recycled to the cold plasma activation step. 2) Process according to claim 1 characterized in that the argon is present at more than 50% by volume in the gaseous mixture of the activation step.
3) Procédé selon la revendication 1 ou 2 caractérisé en ce que le mélange gazeux peut comprendre de l'hydrogène. 4) Procédé selon la revendication 3 caractérisé en ce que la composition du mélange de l'étape d'activation est constituée d'une teneur en hydrogène inférieure à 3,2 % en volume.3) Process according to claim 1 or 2 characterized in that the gaseous mixture may comprise hydrogen. 4) Process according to claim 3 characterized in that the composition of the mixture of the activation step consists of a hydrogen content of less than 3.2% by volume.
5) Procédé selon la revendication 3 caractérisé en ce que la composition du mélange de l'étape d'activation est constituée d'une teneur en oxygène inférieure à 5 % en volume.5) Process according to claim 3 characterized in that the composition of the mixture of the activation step consists of an oxygen content of less than 5% by volume.
6) Procédé selon la revendication 3 caractérisé en ce que la composition du mélange de l'étape d'activation est constituée d'une teneur en hydrogène inférieure à 3,2 % en volume et une teneur en oxygène inférieure à 21 % en volume. 7) Procédé selon la revendication 3 caractérisé en ce que la composition du mélange de l'étape d'activation est constituée d'une teneur en hydrogène supérieure à 76,5 % en volume et une teneur en oxygène inférieure à 5 % en volume.6) Process according to claim 3 characterized in that the composition of the mixture of the activation step consists of a hydrogen content of less than 3.2% by volume and an oxygen content of less than 21% by volume. 7) Process according to claim 3 characterized in that the composition of the mixture of the activation step consists of a hydrogen content greater than 76.5% by volume and an oxygen content of less than 5% by volume.
8) Procédé selon l'une quelconque des revendications précédentes caractérisé en ce l'étape d'activation est mise en oeuve en présence d'un catalyseur.8) Process according to any one of the preceding claims characterized in that the activation step is implemented in the presence of a catalyst.
9) Procédé selon la revendication 8 caractérisé en ce que catalyseur est un solide acide ayant une acidité de Hammett inférieure à +2.
9) The method of claim 8 characterized in that catalyst is an acid solid having a Hammett acidity less than +2.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0653528 | 2006-08-31 | ||
FR0653528A FR2905370B1 (en) | 2006-08-31 | 2006-08-31 | PROCESS FOR PRODUCING HYDROGEN PEROXIDE |
Publications (2)
Publication Number | Publication Date |
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WO2008025917A2 true WO2008025917A2 (en) | 2008-03-06 |
WO2008025917A3 WO2008025917A3 (en) | 2008-04-17 |
Family
ID=37882182
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/FR2007/051803 WO2008025917A2 (en) | 2006-08-31 | 2007-08-09 | Method of manufacturing hydrogen peroxide |
Country Status (2)
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FR (1) | FR2905370B1 (en) |
WO (1) | WO2008025917A2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8956508B2 (en) | 2008-10-28 | 2015-02-17 | Arkema France | Method for producing hydrogen peroxide |
RU2802017C1 (en) * | 2022-12-15 | 2023-08-22 | Федеральное государственное бюджетное учреждение науки Институт химии нефти Сибирского отделения Российской академии наук | Method for producing hydrogen peroxide in barrier discharge |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4106980A1 (en) * | 1990-03-06 | 1991-09-12 | Mitsubishi Electric Corp | Hydrogen peroxide prodn. - by electric discharge in mixed gas with control of oxygen supply |
WO1999037581A2 (en) * | 1998-01-22 | 1999-07-29 | Moeny William M | High efficiency glow discharge gaseous processing system for hydrogen peroxide production and other chemical processing of gases |
-
2006
- 2006-08-31 FR FR0653528A patent/FR2905370B1/en not_active Expired - Fee Related
-
2007
- 2007-08-09 WO PCT/FR2007/051803 patent/WO2008025917A2/en active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4106980A1 (en) * | 1990-03-06 | 1991-09-12 | Mitsubishi Electric Corp | Hydrogen peroxide prodn. - by electric discharge in mixed gas with control of oxygen supply |
WO1999037581A2 (en) * | 1998-01-22 | 1999-07-29 | Moeny William M | High efficiency glow discharge gaseous processing system for hydrogen peroxide production and other chemical processing of gases |
Non-Patent Citations (1)
Title |
---|
B. DODET, E. ODIC, A. GOLMAN, M. GOLMAN, D. RENARD: "Hydrogen peroxide formation by discharges in argon/water vapor mixtures at atmospheric pressure." JOURNAL OF ADVANCED OXIDATION TECHNOLOGIES, vol. 8, no. 1, 31 janvier 2005 (2005-01-31), pages 91-97, XP009081470 cité dans la demande * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8956508B2 (en) | 2008-10-28 | 2015-02-17 | Arkema France | Method for producing hydrogen peroxide |
RU2802017C1 (en) * | 2022-12-15 | 2023-08-22 | Федеральное государственное бюджетное учреждение науки Институт химии нефти Сибирского отделения Российской академии наук | Method for producing hydrogen peroxide in barrier discharge |
Also Published As
Publication number | Publication date |
---|---|
FR2905370B1 (en) | 2009-02-20 |
WO2008025917A3 (en) | 2008-04-17 |
FR2905370A1 (en) | 2008-03-07 |
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