EP0812298A1 - Apparatus for feeding hydrogen peroxide to a processing unit in an industrial facility - Google Patents

Apparatus for feeding hydrogen peroxide to a processing unit in an industrial facility

Info

Publication number
EP0812298A1
EP0812298A1 EP96904142A EP96904142A EP0812298A1 EP 0812298 A1 EP0812298 A1 EP 0812298A1 EP 96904142 A EP96904142 A EP 96904142A EP 96904142 A EP96904142 A EP 96904142A EP 0812298 A1 EP0812298 A1 EP 0812298A1
Authority
EP
European Patent Office
Prior art keywords
hydrogen peroxide
installation
concentration
processing unit
reserve
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Withdrawn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
EP96904142A
Other languages
German (de)
French (fr)
Inventor
Henry Ledon
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
Chemoxal SA
Atofina SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemoxal SA, Atofina SA filed Critical Chemoxal SA
Publication of EP0812298A1 publication Critical patent/EP0812298A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
    • 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
    • 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
    • C01B15/022—Preparation from organic compounds
    • C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process

Definitions

  • the present invention relates to an installation for supplying hydrogen peroxide to a processing unit at an industrial site.
  • the hydrogen peroxide used is always delivered to the treatment unit, in the form of a concentrated aqueous solution, for example from 50 to 70% by weight, by tank or by container.
  • This method of supplying hydrogen peroxide has many drawbacks, in particular security problems linked to the numerous unloading operations for concentrated hydrogen peroxide solutions and the costs associated with transporting it and diluting it to the concentration d on the processing unit.
  • the Applicant has envisaged the production of hydrogen peroxide in a slightly concentrated aqueous solution in the processing unit of the industrial site itself. However, most sites operate almost continuously throughout the year, frequently at least 360 days a year and do not allow the interruption of supply of hydrogen peroxide. Such an interruption is likely to occur, for example during maintenance operations of the installation of production of hydrogen peroxide.
  • the invention aims to allow an uninterrupted supply of the hydrogen peroxide treatment unit, while allowing the usual maintenance operations of the supply installation.
  • the subject of the invention is an installation for supplying hydrogen peroxide to a treatment unit of an industrial site, characterized in that it comprises a main installation for the production of hydrogen peroxide at a concentration of use, arranged on the site of the treatment unit, and an emergency installation , intended to supply the processing unit in the event of a shutdown of the main installation, comprising an emergency reserve of hydrogen peroxide at a storage concentration greater than the use concentration and means for diluting the stored hydrogen peroxide connected between the reserve and the treatment unit and making it possible to reduce the concentration of stored hydrogen peroxide up to the concentration of use.
  • the emergency installation also comprises means for injecting a stabilizer into the diluted hydrogen peroxide;
  • the use concentration of hydrogen peroxide is between 5 and 15% by weight;
  • the concentration of hydrogen peroxide in reserve is between 50 and 70% by weight;
  • the weight of the volume of hydrogen peroxide in reserve is between 100 and 200 tonnes;
  • the main production installation is of the type implementing a process for the production of hydrogen peroxide with anthraquinone
  • the processing unit is a unit for bleaching paper pulp in a paper production site.
  • the invention will be better understood on reading the description which follows given solely by way of example for the understanding of which reference is made to the drawings, in which: - Figure 1 is a block diagram of a hydrogen peroxide feed installation according to the invention;
  • FIG. 2 is a schematic view of a main installation for the production of hydrogen peroxide, integrated into the installation of Figure 1, according to a preferred embodiment.
  • FIG. 1 shows an installation 10 for supplying hydrogen peroxide to a processing unit 12 of an industrial site.
  • This processing unit 12 is for example a pulp bleaching unit from a paper production plant or site.
  • the installation 10 comprises a main installation 14 for producing hydrogen peroxide arranged on the site of the treatment unit 12.
  • the main installation 14 is intended to produce hydrogen peroxide at a relatively low use concentration preferably between 5 and 15% by weight.
  • the installation 10 for supplying hydrogen peroxide also comprises an emergency installation 16 intended to supply the treatment unit 12 in the event of the main installation being stopped.
  • the emergency installation 16 comprises a reserve of emergency hydrogen peroxide 18 and means 20 for diluting stored hydrogen peroxide of known type. These dilution means 20 are connected between the reserve 18 and the processing unit 12 via an upstream conduit 22 and a downstream conduit 24.
  • the hydrogen peroxide stored in reserve 18 is of the type usually supplied on the market.
  • the hydrogen peroxide in reserve has a concentration greater than the use concentration, preferably between 50 and 70% by weight, and a volume of which the weight is preferably between 100 and 200 tonnes, so as to be able to supply, for example, a conventional pulp bleaching unit for approximately one week.
  • the main installation 14 is connected to the processing unit 12 via a conduit 26.
  • conduit 24 downstream of the reserve 18 and the conduit 26 downstream of the installation 14 are connected to the same conduit 28 supplying the processing unit 12.
  • Valves 30, 32 make it possible to isolate the main installation 14 and the emergency installation 18 respectively from the processing unit 12.
  • the hydrogen peroxide at the desired use concentration is supplied directly to the treatment unit by the main production installation 14.
  • this latter installation is connected to the production unit. treatment 12 by opening the valve 30 while the reserve 18 is isolated from the treatment unit 12 by closing the valve 32.
  • the emergency installation 16 comprises means 34 for injecting into the diluted hydrogen peroxide a stabilizer of known type, chosen by example among the carboxylic, aminomethylene-carboxylic, phosphonic and aminomethylenephosphonic compounds, in particular ethylenediamine tetraacetic acid (EDTA) or its salts, diethylenetriamine-pentaacetic acid (DTPA) or its salts, polyacryli acids - ques, diethylenetriaminepentamethylenephosphonic acid or its salts, diamino-1,2NNN'N 'tetramethylenphosphonic acid or its salts, hydroxyethylbismethethylene phosphonic acid or its salts.
  • EDTA ethylenediamine tetraacetic acid
  • DTPA diethylenetriamine-pentaacetic acid
  • polyacryli acids - ques diethylenetriaminepentamethylenephosphonic acid or its salts, diamino-1,2NNN'N 'tetramethylenphosphonic acid or its salts,
  • the main installation 14 for producing hydrogen peroxide is preferably of the type implementing an anthraquinone process. An installation of this type is shown in Figure 2.
  • the production installation 14 in FIG. 2 comprises three main devices in the form of columns: a catalytic hydrogenator 101, a counter-current oxidizer 102, and a water extractor 103. It also includes numerous equipment associated with these three devices , only some of which have been represented: a booster-condenser assembly 104 for recirculating the gaseous mixture containing hydrogen, associated with the hydro ⁇ generator; a filter 106, a pump 107, a heat exchanger 108, a water cooler 109, a head condenser 110 and an air compressor 111 associated with 1 * oxy ⁇ deur; a pipe 112, as short as possible, connecting the base of the oxidizer 102 to that of the extractor 103; and a coalescer 114 and a pump 115 for recycling the working solution.
  • a booster-condenser assembly 104 for recirculating the gaseous mixture containing hydrogen, associated with the hydro ⁇ generator
  • FIG. 2 also shows a line 116 for supplying the hydrogenator with make-up hydrogen, a line 117 for supplying air to the compressor 111, a line 118 for supplying the extractor 103 with demineralized water, a pipe 119 for producing hydrogen peroxide, which leaves from the base of the extractor 103 and ends at the treatment unit 12 consuming hydrogen peroxide at the same concentration, and a pipe 121 for recycling the working solution.
  • Line 119 is connected to line 26.
  • the hydrogen peroxide production installation includes many other pieces of equipment well known in the art and not shown, such as means for regenerating degraded products of the working solution, for using the catalyst, for recovering solvent, etc.
  • the working solution consisting of at least one anthraquinone derivative and at least one organic solvent
  • a stream of hydrogen-containing gas is also introduced at the base of the hydrogenator.
  • This gas stream consists on the one hand of the gas stream drawn off at the top of the hydrogenerator, recirculated by the booster-condenser assembly 104, and on the other hand of make-up hydrogen arriving via line 116 .
  • the working solution is thus partially reduced.
  • the reduced solution drawn off from the base of the hydrogenator by the pump 107 via the filter 106, therefore contains hydroquinone derivatives (for example 80% tetrahydroanthrahydroquinone and 20% anthrahydroquinone).
  • the anthraquinonine derivative constituting the working solution is preferably chosen from the 2 alkyl 9.10 anthraquinones in which the alkyl substituent comprises from 1 to 5 carbon atoms, such as the methyl, ethyl, sec-butyl, tert-butyl radicals , tertio-amyl, as well as the corresponding tetrahydro-5,6,7,8 derivatives, or among the dialkyl 9,10 anthraquinones in which the identical or different alkyl substituents comprise from 1 to 5 carbon atoms, such as methyl radicals , ethyl, tertiobutyl, for example 1.3 dimethyl, 1.4 dimethyl, 2.3 dimethyl, 2.7 dimethyl, 1.3 diethyl, 2.7 ditertiobutyl, 2 ethyl 6 tertiobutyl and the tetrahydro-5,6 derivatives, 7.8 corresponding.
  • the alkyl substituent comprises from 1
  • the organic solvent constituting the working solution is preferably a mixture of a non-polar compound and a polar compound.
  • the non-polar compound is preferably chosen from petroleum fractions with a boiling point above 140 ° C. containing predominantly aromatic hydrocarbons containing at least 9 carbon atoms, such as the isomers of trimethylbenzene, the isomers of tetramethylbenzene , tert-butylbenzene, the isomers of methylnaphthalene, the isoers of dimethylnaphthalene.
  • the polar compound is preferably chosen from saturated alcohols preferably containing from 7 to 11 carbon atoms, such as diisobutylcarbinol, 3,5,5-trimethyl hexanol, isoheptanol, esters of carboxylic acids such as as methyl cyclohexyl acetate sold under the name of "Sextate", heptyl acetate, butyl benzoate, ethyl heptanoate, esters of phosphoric acid such as tributyl phosphate , tri (2 ethyl butyl) phosphate, tri (2 ethyl hexyl) phosphate, tri (n-octyl) phosphate, tetrasubstituted ureas such as tetra (n-butyl urea).
  • saturated alcohols preferably containing from 7 to 11 carbon atoms, such as diisobutylcarbinol, 3,5,5-trimethyl hexan
  • hydrogen peroxide equivalent is understood below to mean the quantity of hydrogen peroxide, expressed in grams, that a liter of working solution is capable of supplying at the end of the oxidization step. tion if the yield of this step in the oxidizer 102 is 100%.
  • This potential mass concentration of peroxide corresponds to a molar concentration which is equal to the molar concentration of all the rehydratable anthrahydroquinone forms in the working solution. It depends on the one hand on the concentration in anthraquinone forms of the starting working solution, and on the other hand on the hydrogenation conditions at 101.
  • the hydrogenation is carried out at a temperature of between 50 and 70 ° C., with a pressure in the gaseous sky of the hydrogenator (pressure which regulates the flow of hydrogen) from 0.8 to 1.5 bar approximately, and the hydrogen peroxide equivalent is adjusted to a value of between 7 and 9 g / 1 approximately, by adjusting the residence time in the hydrogenator, for a given concentration in anthraquinone forms.
  • the reduced working solution withdrawn from the hydrogenator is filtered at 106 to remove all traces of catalyst, then cooled at 108 and then at 109 to a temperature of the order of 35 to 40 "C.
  • the pressure of the gaseous sky of the oxidizer is maintained at a value of between 2 and 4 bars.
  • the reduced working solution is thus oxidized at 102, the head fluid of the oxidizer being partially condensed at 110.
  • the hydrogen peroxide formed by the oxidation reaction is withdrawn from the base of the oxidizer, in an amount equal to the product of the hydrogen peroxide equivalent mentioned above by the yield of the oxidizer, as a mixture. with the oxidized working solution again.
  • This liquid is sent directly via line 112, thanks to the difference in driving pressure at the base of the extractor 103, which operates a little above atmospheric pressure.
  • the extractor is carried out a liquid-liquid extraction by means of demineralized water introduced at the top of the extractor.
  • a water-hydrogen peroxide solution is drawn from the base of the latter, the hydrogen peroxide concentration of which is adjusted to the value necessary for its direct use in the treatment unit 12.
  • the working solution separated from the hydrogen peroxide is withdrawn from the top of the extractor 103, freed from the droplets of aqueous phase which it has entrained in the coalescer 114, then sent by the pump 115 to the heat exchanger 108, in which it heats up, and, from there, recycled to the base of the hydrogé ⁇ nator 101.
  • the oxidizer 102 comprises an outer casing containing an organized lining, or simple resfo trays or trays of the type distillation trays, that is to say each with a liquid guard, bubbling orifices for gas rising through this guard, and means for lowering liquid from one tray to the next, or a combination of 'an organized packing and such trays.
  • the invention has many advantages.
  • the installation according to the invention enables a hydrogen peroxide treatment unit to be supplied without interruption, while allowing maintenance operations to be carried out on the installation.
  • the emergency installation supplies the processing unit in place of the main installation.
  • the dimensions of the reserve 18 are relatively small given the high concentration of hydrogen peroxide stored therein.
  • the installation according to the invention overcomes the drawbacks due to the supply of hydrogen peroxide, in the form of a concentrated aqueous solution, in particular the risks associated with unloading operations.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Storage Of Fruits Or Vegetables (AREA)
  • Paper (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)

Abstract

An apparatus (10) including a main apparatus (14) provided in situ in the processing unit (12) for producing hydrogen peroxide at a working concentration, and a back-up apparatus (16) for supplying the processing unit (12) in the event of a failure of the main apparatus (14). The back-up apparatus comprises a supply (18) of hydrogen peroxide at a storage concentration higher than the working concentration, and means (20) for diluting the stored hydrogen peroxide, arranged between the supply (18) and the processing unit (12) for lowering the storage concentration of the hydrogen peroxide to the working concentration.

Description

Installation pour l'alimentation en peroxyde d'hydrogène d'une unité de traitement d'un site industriel . Installation for the supply of hydrogen peroxide to a processing unit on an industrial site.
La présente invention concerne une installation pour 1 'alimentation en peroxyde d'hydrogène d*une unité de traitement d'un site industriel.The present invention relates to an installation for supplying hydrogen peroxide to a processing unit at an industrial site.
Elle s'applique en particulier à l'alimentation en peroxyde d'hydrogène d'une unité de blanchiment de pâte à papier dans un site de production de papier.It applies in particular to the supply of hydrogen peroxide to a pulp bleaching unit in a paper production site.
De nombreux sites industriels sont consommateurs de grandes quantités de peroxyde d'hydrogène, en particu¬ lier, les sites de production de pâte à papier. Dans la pratique, le peroxyde d'hydrogène utilisé est toujours livré à l'unité de traitement, sous forme de solution acqueuse concentrée, par exemple de 50 à 70% en poids, par citerne ou par conteneur. Ce mode de fourniture de peroxyde d'hydrogène présente de nombreux inconvénients, notamment des problèmes de sécurité liés aux nombreuses opérations de déchargement des solutions concentrées de peroxyde d'hydrogène et des coûts associés à son trans¬ port et à sa dilution à la concentration d'emploi sur l'unité de traitement. La demanderesse a envisagé la production de peroxyde d'hydrogène en solution acqueuse plus faiblement concentrée sur l'unité de traitement du site industriel lui même. Toutefois, la plupart des sites fonctionnement quasiment en continu sur toute l'année, fréquemment au moins 360 jours par an et n'autorisent pas l'interruption de fourniture en peroxyde d'hydrogène. Une telle inter¬ ruption est susceptible d'intervenir, par exemple lors des opérations d'entretien de l'installation de produc¬ tion de peroxyde d*hydrogène. L'invention a pour but de permettre une alimenta¬ tion ininterrompue de l'unité de traitement en peroxyde d'hydrogène, tout en permettant les opérations d'entre¬ tien usuel de l'installation d'alimentation.Many industrial sites consume large quantities of hydrogen peroxide, in particular, pulp production sites. In practice, the hydrogen peroxide used is always delivered to the treatment unit, in the form of a concentrated aqueous solution, for example from 50 to 70% by weight, by tank or by container. This method of supplying hydrogen peroxide has many drawbacks, in particular security problems linked to the numerous unloading operations for concentrated hydrogen peroxide solutions and the costs associated with transporting it and diluting it to the concentration d on the processing unit. The Applicant has envisaged the production of hydrogen peroxide in a slightly concentrated aqueous solution in the processing unit of the industrial site itself. However, most sites operate almost continuously throughout the year, frequently at least 360 days a year and do not allow the interruption of supply of hydrogen peroxide. Such an interruption is likely to occur, for example during maintenance operations of the installation of production of hydrogen peroxide. The invention aims to allow an uninterrupted supply of the hydrogen peroxide treatment unit, while allowing the usual maintenance operations of the supply installation.
A cet effet l'invention a pour objet une instal- lation pour l'alimentation en peroxyde d'hydrogène d'une unité de traitement d'un site industriel, caractérisée en ce qu'elle comprend une installation principale de production de peroxyde d'hydrogène à une concentration d'utilisation, agencée sur le site même de l'unité de traitement, et une installation de secours, destinée à alimenter l'unité de traitement en cas d'arrêt de l'ins¬ tallation principale, comportant une réserve de secours de peroxyde d'hydrogène à une concentration de stockage supérieure à la concentration d'utilisation et des moyens de dilution du peroxyde d'hydrogène stocké raccordés entre la réserve et l'unité de traitement et permettant de réduire la concentration de peroxyde d'hydrogène stocké jusqu'à la concentration d'utilisation.To this end, the subject of the invention is an installation for supplying hydrogen peroxide to a treatment unit of an industrial site, characterized in that it comprises a main installation for the production of hydrogen peroxide at a concentration of use, arranged on the site of the treatment unit, and an emergency installation , intended to supply the processing unit in the event of a shutdown of the main installation, comprising an emergency reserve of hydrogen peroxide at a storage concentration greater than the use concentration and means for diluting the stored hydrogen peroxide connected between the reserve and the treatment unit and making it possible to reduce the concentration of stored hydrogen peroxide up to the concentration of use.
Suivant d'autres caractéristiques de l'invention: - l'installation de secours comporte de plus des moyens d'injection d'un stabilisant dans le peroxyde d'hydrogène dilué ; la concentration d'utilisation du peroxyde d'hydrogène est comprise entre 5 et 15% en poids ; - la concentration du peroxyde d'hydrogène en réserve est comprise entre 50 et 70% en poids ;According to other characteristics of the invention: - the emergency installation also comprises means for injecting a stabilizer into the diluted hydrogen peroxide; the use concentration of hydrogen peroxide is between 5 and 15% by weight; - The concentration of hydrogen peroxide in reserve is between 50 and 70% by weight;
- le poids du volume du peroxyde d'hydrogène en réserve est compris entre 100 et 200 tonnes ;- the weight of the volume of hydrogen peroxide in reserve is between 100 and 200 tonnes;
- l'installation principale de production est du type mettant en oeuvre un procédé de production de peroxyde d'hydrogène à 1 'anthraquinone ;the main production installation is of the type implementing a process for the production of hydrogen peroxide with anthraquinone;
- l'unité de traitement est une unité de blanchi¬ ment de pâte à papier dans un site de production de papier. L'invention sera mieux comprise à la lecture de la description qui va suivre donnée uniquement à titre d'exemple pour la compréhension de laquelle on se référe¬ ra aux dessins, dans lesquels : - la figure 1 est un schéma synoptique d'une installation d'alimentation en peroxyde d'hydrogène selon 1'invention ;- The processing unit is a unit for bleaching paper pulp in a paper production site. The invention will be better understood on reading the description which follows given solely by way of example for the understanding of which reference is made to the drawings, in which: - Figure 1 is a block diagram of a hydrogen peroxide feed installation according to the invention;
- la figure 2 est une vue schématique d'une ins- tallation principale de production de peroxyde d'hydrogè¬ ne, intégré à l'installation de la figure 1, selon un mode de réalisation préféré.- Figure 2 is a schematic view of a main installation for the production of hydrogen peroxide, integrated into the installation of Figure 1, according to a preferred embodiment.
On a représenté sur la figure 1 une installation 10 pour l'alimentation en peroxyde d'hydrogène d'une unité de traitement 12 d'un site industriel.FIG. 1 shows an installation 10 for supplying hydrogen peroxide to a processing unit 12 of an industrial site.
Cette unité de traitement 12 est par exemple une unité de blanchiment de pâte à papier d'une usine ou site de production de papier.This processing unit 12 is for example a pulp bleaching unit from a paper production plant or site.
L'installation 10 comprend une installation principale 14 de production de peroxyde d'hydrogène agencée sur le site même de l'unité de traitement 12.The installation 10 comprises a main installation 14 for producing hydrogen peroxide arranged on the site of the treatment unit 12.
L'installation principale 14 est destinée à produire du peroxyde d'hydrogène a une concentration d'utilisation relativement faible comprise de préférence entre 5 et 15% en poids.The main installation 14 is intended to produce hydrogen peroxide at a relatively low use concentration preferably between 5 and 15% by weight.
L'installation 10 d'alimentation en peroxyde d'hydrogène comporte également une installation de secours 16 destinée à alimenter l'unité de traitement 12 en cas d'arrêt de l'installation principale 14. L'installation de secours 16 comporte une réserve de peroxyde d'hydrogène de secours 18 et des moyens 20 de dilution de peroxyde d'hydrogène stocké de type connu. Ces moyens de dilution 20 sont raccordés entre la réserve 18 et l'unité de traitement 12 par l'intermédiaire d'un conduit amont 22 et d'un conduit aval 24.The installation 10 for supplying hydrogen peroxide also comprises an emergency installation 16 intended to supply the treatment unit 12 in the event of the main installation being stopped. The emergency installation 16 comprises a reserve of emergency hydrogen peroxide 18 and means 20 for diluting stored hydrogen peroxide of known type. These dilution means 20 are connected between the reserve 18 and the processing unit 12 via an upstream conduit 22 and a downstream conduit 24.
Le peroxyde d'hydrogène stocké dans la réserve 18 est du type habituellement fourni sur le marché. Le peroxyde d'hydrogène en réserve a une concentration supérieure à la concentration d'utilisation, comprise de préférence entre 50 et 70% en poids, et un volume dont le poids est compris, de préférence, entre 100 et 200 tonnes, de manière à pouvoir approvisionner par exemple une unité de blanchiment de pâte à papier classique pendant environ une semaine. L'installation principale 14 est reliée à l'unité de traitement 12 par l'intermédiaire d'un conduit 26.The hydrogen peroxide stored in reserve 18 is of the type usually supplied on the market. The hydrogen peroxide in reserve has a concentration greater than the use concentration, preferably between 50 and 70% by weight, and a volume of which the weight is preferably between 100 and 200 tonnes, so as to be able to supply, for example, a conventional pulp bleaching unit for approximately one week. The main installation 14 is connected to the processing unit 12 via a conduit 26.
Le conduit 24 en aval de la réserve 18 et le conduit 26 en aval de l'installation 14 sont raccordés à un même conduit 28 d'alimentation de l'unité de traite- ment 12.The conduit 24 downstream of the reserve 18 and the conduit 26 downstream of the installation 14 are connected to the same conduit 28 supplying the processing unit 12.
Des vannes 30,32 permettent d'isoler respective¬ ment l'installation principale 14 et l'installation de secours 18 de l'unité de traitement 12.Valves 30, 32 make it possible to isolate the main installation 14 and the emergency installation 18 respectively from the processing unit 12.
Le sens d'écoulement général des fluides est indiqué par des flèches sur la figure 1.The general direction of flow of the fluids is indicated by arrows in FIG. 1.
Le fonctionnement de l'installation d'alimenta¬ tion en peroxyde d'hydrogène selon l'invention peut être réalisé selon la manière décrite ci-dessous.The operation of the hydrogen peroxide supply system according to the invention can be carried out in the manner described below.
Habituellement, le peroxyde d'hydrogène a la concentration d'utilisation souhaitée est fourni directe¬ ment à l'unité de traitement par l'installation princi¬ pale de production 14. Dans ce cas, cette dernière installation est reliée à l'unité de traitement 12 par ouverture de la vanne 30 alors que la réserve 18 est isolée de l'unité de traitement 12 par fermeture de la vanne 32.Usually, the hydrogen peroxide at the desired use concentration is supplied directly to the treatment unit by the main production installation 14. In this case, this latter installation is connected to the production unit. treatment 12 by opening the valve 30 while the reserve 18 is isolated from the treatment unit 12 by closing the valve 32.
Lorsque l'installation principale 14 est arrêtée, notamment pour y effectuer des opérations d'entretien, cette installation est isolée de l'unité de traitement 32 par fermeture de la vanne 30, l'alimentation en peroxyde d'hydrogène de l'unité 12 se faisant par la réserve 18 après ouverture de la vanne 32.When the main installation 14 is stopped, in particular to carry out maintenance operations there, this installation is isolated from the treatment unit 32 by closing the valve 30, the supply of hydrogen peroxide to the unit 12 through the reserve 18 after opening the valve 32.
La concentration du peroxyde d'hydrogène stocké est réduite grâce aux moyens de dilution 20 jusqu'à obtenir la concentration d'utilisation normalement fournie par l'installation principale de production 14. De préférence, l'installation de secours 16 comporte des moyens 34 d'injection dans le peroxyde d'hydrogène dilué d'un stabilisant de type connu, choisi par exemple parmi les composés carboxyliques, aminométhy- lène-carboxyliques, phosphoniques et aminométhylènephos- phoniques, en particulier l'acide éthylènediamine tétraa- cétique (EDTA) ou ses sels, l'acide diéthylènetriamine- pentaacétique (DTPA) ou ses sels, les acides polyacryli- ques, l'acide diéthylènetriaminepentaméthylènephosphoni- que ou ses sels, l'acide diamino-1,2NNN'N' tétraméthy- lènephosphonique ou ses sels, l'acide hydroxyéthylbismé- thylènephosphonique ou ses sels. Le stabilisant permet d'éviter la décomposition du peroxyde d'hydrogène à concentration relativement faible jusqu'à l'injection de ce peroxyde d'hydrogène dans l'unité de traitement 12.The concentration of stored hydrogen peroxide is reduced thanks to the dilution means 20 up to obtaining the concentration of use normally provided by the main production installation 14. Preferably, the emergency installation 16 comprises means 34 for injecting into the diluted hydrogen peroxide a stabilizer of known type, chosen by example among the carboxylic, aminomethylene-carboxylic, phosphonic and aminomethylenephosphonic compounds, in particular ethylenediamine tetraacetic acid (EDTA) or its salts, diethylenetriamine-pentaacetic acid (DTPA) or its salts, polyacryli acids - ques, diethylenetriaminepentamethylenephosphonic acid or its salts, diamino-1,2NNN'N 'tetramethylenphosphonic acid or its salts, hydroxyethylbismethethylene phosphonic acid or its salts. The stabilizer makes it possible to avoid the decomposition of hydrogen peroxide at a relatively low concentration until the injection of this hydrogen peroxide into the treatment unit 12.
L'installation principale 14 de production de peroxyde d'hydrogène est de préférence du type mettant en oeuvre un procédé à l'anthraquinone. Une installation de ce type est représentée à la figure 2.The main installation 14 for producing hydrogen peroxide is preferably of the type implementing an anthraquinone process. An installation of this type is shown in Figure 2.
L'installation de production 14 à la figure 2 comprend trois appareils principaux en forme de colonnes: un hydrogénateur catalytique 101, un oxydeur à contre- courant 102, et un extracteur à eau 103. Elle comporte également de nombreux équipements associés à ces trois appareils, dont seuls certains ont été représentés : un ensemble surpresseur-condenseur 104 de recirculation du mélange gazeux contenant l'hydrogène, associé à l'hydro¬ génateur ; un filtre 106, une pompe 107, un échangeur de chaleur 108, un réfrigérant à eau 109, un condenseur de tête 110 et un compresseur d'air 111 associés à 1*oxy¬ deur; une conduite 112, aussi courte que possible, reliant la base de 1*oxydeur 102 à celle de l'extracteur 103 ; et un coalesceur 114 et une pompe 115 pour le recyclage de la solution de travail.The production installation 14 in FIG. 2 comprises three main devices in the form of columns: a catalytic hydrogenator 101, a counter-current oxidizer 102, and a water extractor 103. It also includes numerous equipment associated with these three devices , only some of which have been represented: a booster-condenser assembly 104 for recirculating the gaseous mixture containing hydrogen, associated with the hydro¬ generator; a filter 106, a pump 107, a heat exchanger 108, a water cooler 109, a head condenser 110 and an air compressor 111 associated with 1 * oxy¬ deur; a pipe 112, as short as possible, connecting the base of the oxidizer 102 to that of the extractor 103; and a coalescer 114 and a pump 115 for recycling the working solution.
On a également représenté sur la figure 2 une conduite 116 d'alimentation de l'hydrogénateur en hydro- gène d'appoint, une conduite 117 d'alimentation en air du compresseur 111, une conduite 118 d'alimentation de l'extracteur 103 en eau déminéralisée, une conduite 119 de production de peroxyde d'hydrogène, qui part de la base de l'extracteur 103 et aboutit à l'unité de traite- ment 12 consommatrice de peroxyde d'hydrogène sous la même concentration, et une conduite 121 de recyclage de la solution de travail. La conduite 119 est reliée au conduit 26.FIG. 2 also shows a line 116 for supplying the hydrogenator with make-up hydrogen, a line 117 for supplying air to the compressor 111, a line 118 for supplying the extractor 103 with demineralized water, a pipe 119 for producing hydrogen peroxide, which leaves from the base of the extractor 103 and ends at the treatment unit 12 consuming hydrogen peroxide at the same concentration, and a pipe 121 for recycling the working solution. Line 119 is connected to line 26.
L'installation de production de peroxyde d'hydro- gène comprend de nombreux autres équipements bien connus dans la technique et non représentés, tels que des moyens de régénération de produits dégradés de la solution de travail, de mise en oeuvre du catalyseur, de récupération de solvant, etc. En fonctionnement, la solution de travail, constituée d'au moins un dérivé anthraquinonique et d'au moins un solvant organique, est introduite à la base de 1'hydrogénateur 101 via la conduite de recyclage 121 reliée au refoulement de la pompe 115, et un courant de gaz contenant de l'hydrogène est également introduit à la base de l'hydrogénateur. Ce courant gazeux est constitué d'une part du courant gazeux soutiré au sommet de l'hy¬ drogénateur, recirculé par l'ensemble surpresseur-conden- seur 104, et d'autre part d'hydrogène d'appoint arrivant via la conduite 116.The hydrogen peroxide production installation includes many other pieces of equipment well known in the art and not shown, such as means for regenerating degraded products of the working solution, for using the catalyst, for recovering solvent, etc. In operation, the working solution, consisting of at least one anthraquinone derivative and at least one organic solvent, is introduced at the base of the hydrogenator 101 via the recycling line 121 connected to the discharge of the pump 115, and a stream of hydrogen-containing gas is also introduced at the base of the hydrogenator. This gas stream consists on the one hand of the gas stream drawn off at the top of the hydrogenerator, recirculated by the booster-condenser assembly 104, and on the other hand of make-up hydrogen arriving via line 116 .
La solution de travail est ainsi partiellement réduite. La solution réduite, soutirée de la base de l'hydrogénateur par la pompe 107 via le filtre 106, contient donc des dérivés hydroquinoniques (par exemple 80% de tétrahydroanthrahydroquinone et 20% d*anthrahydro- quinone) .The working solution is thus partially reduced. The reduced solution, drawn off from the base of the hydrogenator by the pump 107 via the filter 106, therefore contains hydroquinone derivatives (for example 80% tetrahydroanthrahydroquinone and 20% anthrahydroquinone).
Le dérivé anthraquinonine constitutif de la solution de travail est choisi de préférence parmi les 2 alkyl 9,10 anthraquinones dans lesquelles le substituant alkyle comprend de 1 à 5 atomes de carbone, tel que les radicaux méthyle, éthyle, sec-butyle, tertio-butyle, tertio-amyle, ainsi que les dérivés tétrahydro-5,6,7,8 correspondants, ou parmi les dialkyl 9,10 anthraquinones dans lesquelles les substituants alkyle identiques ou différents comprennent de 1 à 5 atomes de carbone, tel que les radicaux méthyle, éthyle, tertiobutyle, par exemple 1,3 diméthyle, 1,4 diméthyle, 2,3 diméthyle, 2,7 diméthyle, 1,3 diéthyle, 2,7 ditertiobutyle, 2 éthyle 6 tertiobutyle et les dérivés tétrahydro-5, 6,7,8 correspon¬ dants. Le solvant organique constitutif de la solution de travail est de préférence un mélange d'un composé non polaire et d'un composé polaire. Le composé non polaire est choisi de préférence parmi les coupes pétrolières à point d'ébullition supérieur à 140°C contenant majoritai¬ rement des hydrocarbures aromatiques comportant au moins 9 atomes de carbone, tel que les isomères du triméthyl- benzene, les isomères du tétraméthylbenzène, le tertiobu- tylbenzène, les isomères du méthylnaphtalène, les iso è- res du diméthylnaphtalène. Le composé polaire est choisi de préférence parmi les alcools saturés comportant de préférence de 7 à 11 atomes de carbone, tels que le diisobutylcarbinol, le triméthyl-3,5,5 hexanol, l'isohep- tanol, les esters d'acides carboxyliques tels que l'acé- tate de méthyle cyclohexyl commercialisé sous le nom de "Sextate", l'acétate d'heptyle, le benzoate de butyle, l'heptanoate d*éthyle, les esters de l'acide phosphorique tels que le phosphate de tributyle, le phosphate de tri (2 éthyl butyle), le phosphate de tri (2 éthyle hexyle), le phosphate de tri (n-octyle), les urées tétrasubsti- tuées telle que la tétra (n-butyl urée).The anthraquinonine derivative constituting the working solution is preferably chosen from the 2 alkyl 9.10 anthraquinones in which the alkyl substituent comprises from 1 to 5 carbon atoms, such as the methyl, ethyl, sec-butyl, tert-butyl radicals , tertio-amyl, as well as the corresponding tetrahydro-5,6,7,8 derivatives, or among the dialkyl 9,10 anthraquinones in which the identical or different alkyl substituents comprise from 1 to 5 carbon atoms, such as methyl radicals , ethyl, tertiobutyl, for example 1.3 dimethyl, 1.4 dimethyl, 2.3 dimethyl, 2.7 dimethyl, 1.3 diethyl, 2.7 ditertiobutyl, 2 ethyl 6 tertiobutyl and the tetrahydro-5,6 derivatives, 7.8 corresponding. The organic solvent constituting the working solution is preferably a mixture of a non-polar compound and a polar compound. The non-polar compound is preferably chosen from petroleum fractions with a boiling point above 140 ° C. containing predominantly aromatic hydrocarbons containing at least 9 carbon atoms, such as the isomers of trimethylbenzene, the isomers of tetramethylbenzene , tert-butylbenzene, the isomers of methylnaphthalene, the isoers of dimethylnaphthalene. The polar compound is preferably chosen from saturated alcohols preferably containing from 7 to 11 carbon atoms, such as diisobutylcarbinol, 3,5,5-trimethyl hexanol, isoheptanol, esters of carboxylic acids such as as methyl cyclohexyl acetate sold under the name of "Sextate", heptyl acetate, butyl benzoate, ethyl heptanoate, esters of phosphoric acid such as tributyl phosphate , tri (2 ethyl butyl) phosphate, tri (2 ethyl hexyl) phosphate, tri (n-octyl) phosphate, tetrasubstituted ureas such as tetra (n-butyl urea).
On entendra ci-dessous par "équivalent peroxyde d'hydrogène", la quantité de peroxyde d'hydrogène, exprimée en gramme, qu'un litre de solution de travail est susceptible de fournir à l'issue de l'étape d'oxyda¬ tion si le rendement de cette étape dans l'oxydeur 102 est de 100%. Cette concentration massique potentielle en peroxyde correspond à une concentration molaire qui est égale à la concentration molaire de l'ensemble des formes anthrahydroquinoniques réoxydables dans la solution de travail. Elle dépend d'une part de la concentration en formes anthraquinoniques de la solution de travail de départ, et d'autre part des conditions d'hydrogénation en 101.The expression “hydrogen peroxide equivalent” is understood below to mean the quantity of hydrogen peroxide, expressed in grams, that a liter of working solution is capable of supplying at the end of the oxidization step. tion if the yield of this step in the oxidizer 102 is 100%. This potential mass concentration of peroxide corresponds to a molar concentration which is equal to the molar concentration of all the rehydratable anthrahydroquinone forms in the working solution. It depends on the one hand on the concentration in anthraquinone forms of the starting working solution, and on the other hand on the hydrogenation conditions at 101.
Dans le cas présent, on effectue l'hydrogénation à une température comprise entre 50 et 70°C, avec une pression dans le ciel gazeux de l'hydrogénateur (pression qui régule le débit d'hydrogène) de 0,8 à 1,5 bar envi- ron, et on règle l'équivalent peroxyde d'hydrogène à une valeur comprise entre 7 et 9 g/1 environ, par ajustement du temps de séjour dans l'hydrogénateur, pour une concen¬ tration donnée en formes anthraquinoniques.In the present case, the hydrogenation is carried out at a temperature of between 50 and 70 ° C., with a pressure in the gaseous sky of the hydrogenator (pressure which regulates the flow of hydrogen) from 0.8 to 1.5 bar approximately, and the hydrogen peroxide equivalent is adjusted to a value of between 7 and 9 g / 1 approximately, by adjusting the residence time in the hydrogenator, for a given concentration in anthraquinone forms.
La solution de travail réduite soutirée de 1'hydrogénateur est filtrée en 106 pour éliminer toute trace de catalyseur, puis refroidie en 108 puis en 109 jusqu'à une température de l'ordre de 35 à 40"C. La pression du ciel gazeux de l'oxydeur est maintenue à une valeur comprise entre 2 et 4 bars. La solution de travail réduite est ainsi oxydée en 102, le fluide de tête de 1'oxydeur étant partiellement condensé en 110.The reduced working solution withdrawn from the hydrogenator is filtered at 106 to remove all traces of catalyst, then cooled at 108 and then at 109 to a temperature of the order of 35 to 40 "C. The pressure of the gaseous sky of the oxidizer is maintained at a value of between 2 and 4 bars. The reduced working solution is thus oxidized at 102, the head fluid of the oxidizer being partially condensed at 110.
Le peroxyde d'hydrogène formé par la réaction d'oxydation est soutiré de la base de 1Oxydeur, dans une quantité égale au produit de l'équivalent peroxyde d'hy- drogène précité par le rendement de 1Oxydeur, en mélange avec la solution de travail de nouveau oxydée. Ce liquide est envoyé directement via la conduite 112, grâce à la différence de pression motrice à la base de l'extracteur 103, lequel fonctionne un peu au-dessus de la pression atmosphérique. Dans l'extracteur s'effectue une extrac¬ tion liquide-liquide au moyen de l'eau déminéralisée introduite au sommet de l'extracteur.The hydrogen peroxide formed by the oxidation reaction is withdrawn from the base of the oxidizer, in an amount equal to the product of the hydrogen peroxide equivalent mentioned above by the yield of the oxidizer, as a mixture. with the oxidized working solution again. This liquid is sent directly via line 112, thanks to the difference in driving pressure at the base of the extractor 103, which operates a little above atmospheric pressure. In the extractor is carried out a liquid-liquid extraction by means of demineralized water introduced at the top of the extractor.
On soutire de la base de ce dernier une solution eau-peroxyde d'hydrogène, dont la concentration en peroxyde d'hydrogène est réglée sur la valeur nécessaire pour son utilisation directe dans l'unité de traitement 12.A water-hydrogen peroxide solution is drawn from the base of the latter, the hydrogen peroxide concentration of which is adjusted to the value necessary for its direct use in the treatment unit 12.
La solution de travail séparée du peroxyde d'hy¬ drogène est soutirée du sommet de l'extracteur 103, débarrassée des gouttelettes de phase aqueuse qu'elle a entraînées dans le coalesceur 114, puis envoyée par la pompe 115 à l'échangeur de chaleur 108, dans lequel elle se réchauffe, et, de là, recyclée à la base de l'hydrogé¬ nateur 101. L'oxydeur 102 comporte une enveloppe extérieure contenant un garnissage organisé, ou des plateaux perfo¬ rés simples ou des plateaux du type des plateaux de distillation, c'est-à-dire avec chacun une garde de liquide, des orifices de bullage du gaz montant à travers cette garde, et des moyens de descente de liquide d'un plateau au suivant, ou encore une combinaison d'un garnissage organisé et de tels plateaux.The working solution separated from the hydrogen peroxide is withdrawn from the top of the extractor 103, freed from the droplets of aqueous phase which it has entrained in the coalescer 114, then sent by the pump 115 to the heat exchanger 108, in which it heats up, and, from there, recycled to the base of the hydrogé¬ nator 101. The oxidizer 102 comprises an outer casing containing an organized lining, or simple resfo trays or trays of the type distillation trays, that is to say each with a liquid guard, bubbling orifices for gas rising through this guard, and means for lowering liquid from one tray to the next, or a combination of 'an organized packing and such trays.
L' invention comporte de nombreux avantages. L'installation selon l'invention permet d'alimen- ter de façon ininterrompue une unité de traitement en peroxyde d'hydrogène, tout en permettant des opérations d'entretien de l'installation. Ainsi, lorsque l'installa¬ tion principale de production de peroxyde d'hydrogène est arrêtée, l'installation de secours alimente l'unité de traitement à la place de l'installation principale. Les dimensions de la réserve 18 sont relativement faibles étant donné la concentration élevée du peroxyde d'hydrogène qui y est stocké.The invention has many advantages. The installation according to the invention enables a hydrogen peroxide treatment unit to be supplied without interruption, while allowing maintenance operations to be carried out on the installation. Thus, when the main installation for producing hydrogen peroxide is stopped, the emergency installation supplies the processing unit in place of the main installation. The dimensions of the reserve 18 are relatively small given the high concentration of hydrogen peroxide stored therein.
L'installation selon l'invention permet d'obvier les inconvénients dus à la fourniture de peroxyde d'hy¬ drogène, sous forme de solution aqueuse concentrée, en particulier les risques associés aux opérations de déchargement. The installation according to the invention overcomes the drawbacks due to the supply of hydrogen peroxide, in the form of a concentrated aqueous solution, in particular the risks associated with unloading operations.

Claims

REVENDICATIONS
1. Installation pour l'alimentation en peroxyde d'hydrogène d'une unité de traitement (12) d'un site industriel, caractérisée en ce qu'elle comprend une installation principale (14) de production de peroxyde d'hydrogène à une concentration d'utilisation, agencée sur le site même de l'unité de traitement (12), et une installation de secours (16), destinée à alimenter l'unité de traitement (12) en cas d'arrêt de l'installa- tion principale ( 14 ) , comportant une réserve de secours (18) de peroxyde d'hydrogène à une concentration de stockage supérieure à la concentration d'utilisation et des moyens de dilution du peroxyde d'hydrogène stocké raccordés entre la réserve (18) et l'unité de traitement (12) et permettant de réduire la concentration de pe¬ roxyde d'hydrogène stocké jusqu'à la concentration d'utilisation.1. Installation for supplying hydrogen peroxide to a treatment unit (12) of an industrial site, characterized in that it comprises a main installation (14) for producing hydrogen peroxide at a concentration of use, arranged on the site of the processing unit (12), and an emergency installation (16), intended to supply the processing unit (12) in the event of installation shutdown main (14), comprising an emergency reserve (18) of hydrogen peroxide at a storage concentration greater than the use concentration and means for diluting the stored hydrogen peroxide connected between the reserve (18) and l treatment unit (12) and making it possible to reduce the concentration of stored hydrogen peroxide up to the concentration of use.
2. Installation selon la revendication 1, carac¬ térisée en ce que l'installation de secours (16) comporte de plus des moyens (34) d'injection d'un stabilisant dans le peroxyde d'hydrogène dilué.2. Installation according to claim 1, carac¬ terized in that the emergency installation (16) further comprises means (34) for injecting a stabilizer in dilute hydrogen peroxide.
3. Installation selon la revendication 1 ou 2, caractérisée en ce que la concentration d'utilisation du peroxyde d'hydrogène est comprise entre 5 et 15% en poids.3. Installation according to claim 1 or 2, characterized in that the concentration of use of hydrogen peroxide is between 5 and 15% by weight.
4. Installation selon l'une quelconque des revendications précédentes, caractérisée en ce que la concentration du peroxyde d'hydrogène en réserve est comprise entre 50 et 70% en poids. 4. Installation according to any one of the preceding claims, characterized in that the concentration of hydrogen peroxide in reserve is between 50 and 70% by weight.
5. Installation selon l'une quelconque des revendications précédentes, caractérisée en ce que le poids du volume du peroxyde d'hydrogène en réserve est compris entre 100 et 200 tonnes.5. Installation according to any one of the preceding claims, characterized in that the volume weight of the hydrogen peroxide in reserve is between 100 and 200 tonnes.
6. Installation selon l'une quelconque des revendications précédentes, caractérisée en ce que 12 l'installation principale de production (14) est du type mettant en oeuvre un procédé de production de peroxyde d'hydrogène à l'anthraquinone.6. Installation according to any one of the preceding claims, characterized in that 12 the main production installation (14) is of the type implementing a process for producing hydrogen peroxide with anthraquinone.
7. Installation selon l'une quelconque des revendications précédentes, caractérisée en ce que l'unité de traitement (12) est une unité de blanchiment de pâte à papier dans un site de production de papier. 7. Installation according to any one of the preceding claims, characterized in that the processing unit (12) is a pulp bleaching unit in a paper production site.
EP96904142A 1995-02-28 1996-02-14 Apparatus for feeding hydrogen peroxide to a processing unit in an industrial facility Withdrawn EP0812298A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9502319A FR2730984B1 (en) 1995-02-28 1995-02-28 INSTALLATION FOR SUPPLYING HYDROGEN PEROXIDE TO A TREATMENT UNIT OF AN INDUSTRIAL SITE
FR9502319 1995-02-28
PCT/FR1996/000244 WO1996026897A1 (en) 1995-02-28 1996-02-14 Apparatus for feeding hydrogen peroxide to a processing unit in an industrial facility

Publications (1)

Publication Number Publication Date
EP0812298A1 true EP0812298A1 (en) 1997-12-17

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EP (1) EP0812298A1 (en)
JP (1) JPH11500996A (en)
CN (1) CN1176629A (en)
AU (1) AU4834996A (en)
BR (1) BR9607432A (en)
CA (1) CA2214049A1 (en)
CO (1) CO4560352A1 (en)
FI (1) FI973511A (en)
FR (1) FR2730984B1 (en)
MY (1) MY132346A (en)
TW (1) TW302410B (en)
WO (1) WO1996026897A1 (en)

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AU3892493A (en) * 1992-04-15 1993-11-18 A. Ahlstrom Corporation Production of bleaching chemicals on site at a pulp mill
SE9301940L (en) * 1992-06-10 1993-12-11 Ahlstroem Oy Preparation of bleaching chemicals for cellulose pulp

Non-Patent Citations (1)

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Title
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AU4834996A (en) 1996-09-18
CN1176629A (en) 1998-03-18
MY132346A (en) 2007-10-31
FR2730984A1 (en) 1996-08-30
FR2730984B1 (en) 1997-05-23
FI973511A0 (en) 1997-08-27
CO4560352A1 (en) 1998-02-10
FI973511A (en) 1997-10-16
TW302410B (en) 1997-04-11
WO1996026897A1 (en) 1996-09-06
JPH11500996A (en) 1999-01-26
CA2214049A1 (en) 1996-09-06

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