EP0270719A1 - Process for reducing unburned combustion particles, and agent for carrying out the process - Google Patents
Process for reducing unburned combustion particles, and agent for carrying out the process Download PDFInfo
- Publication number
- EP0270719A1 EP0270719A1 EP86402784A EP86402784A EP0270719A1 EP 0270719 A1 EP0270719 A1 EP 0270719A1 EP 86402784 A EP86402784 A EP 86402784A EP 86402784 A EP86402784 A EP 86402784A EP 0270719 A1 EP0270719 A1 EP 0270719A1
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- Prior art keywords
- cerium
- potassium
- combustion
- liquid
- weight
- 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.)
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- 238000002485 combustion reaction Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000002245 particle Substances 0.000 title abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000004449 solid propellant Substances 0.000 claims abstract description 11
- 239000000446 fuel Substances 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical group 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 230000002195 synergetic effect Effects 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- -1 potassium carboxylates Chemical class 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 3
- 239000011885 synergistic combination Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 12
- 239000002956 ash Substances 0.000 description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 description 11
- 239000011707 mineral Substances 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000011056 potassium acetate Nutrition 0.000 description 6
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 159000000001 potassium salts Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000001464 adherent effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UADULFIZHZKEOP-UHFFFAOYSA-K cerium(3+);triformate Chemical compound [Ce+3].[O-]C=O.[O-]C=O.[O-]C=O UADULFIZHZKEOP-UHFFFAOYSA-K 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000011545 laboratory measurement Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
Definitions
- the present invention relates to a method for reducing the amount and modifying the structure of unburnt deposits which form on the surfaces of heat generators.
- the invention also relates to synergistic combinations of products used for this purpose in heat generators.
- the heat generators concerned can burn liquid fuels such as petroleum derivatives or solid fuels such as coal and / or industrial waste such as black liquors from paper mills or household waste for example.
- the heat generators concerned can be indifferently those whose purpose is the production of hot air, hot water, saturated steam or superheated steam.
- the deposits which generally form on the exchange surfaces in contact with the combustion fumes are composed of unburnt carbon elements generally called "soot", non-combustible mineral ash and products of surface corrosion. mainly sulfates and sulfides.
- compositions Among the most known compositions, one can cite those containing certain metal salts forming part of the series of rare earths, such as the oil-soluble salts of cerium, for example claimed in French patents 2,359,192 and 2,359,199 as combustion adjuvants.
- the subject of the present invention is a treatment method making it possible to obtain a more advantageous result than that obtained with the compositions currently used.
- This process is characterized in that, either on solid fuels before their combustion, or in the enclosures of the generators during the combustion of liquid or solid fuels, a composition, in powder or liquid form, constituted by an association with synergistic effect of water-soluble organic salts of an alkali metal and a metal from the rare earth series.
- the present invention also relates to an unburnt reducing agent for the implementation of the process defined above.
- this reducing agent consists of a pulverulent composition comprising, in combination with a synergistic effect, from 70 to 90% by weight of potassium carboxylates and from 10 to 30% by weight of cerium carboxylates.
- this reducing agent consists of a liquid composition comprising, in a synergistic effect, from 10 to 20% by weight of potassium carboxylates and from 15 to 20% by weight of cerium carboxylates, and 65 to 70% water.
- the treatment method according to the invention therefore provides for the combination of potassium compounds and cerium compounds in order to reduce unburnt deposits and to destroy unburnable deposits on the surfaces of the combustion chambers.
- Another characteristic of the present process consists in associating with them potassium and cerium salts soluble in water and obtained from low molecular weight carboxylic acids of elementary formula: C x O y H z in which the value of x is a even or odd whole number, between 1 and 3 inclusive.
- the salts of lower carboxylic acids of potassium and of cerium such as potassium formate, cerium formate, potassium acetate and cerium acetate have the advantage of being able to be mixed together under their pulverulent forms or in the form of aqueous solutions making it possible to vary the proportions of alkali metal and of metal of the rare earth series in ratios chosen preferably as a function of the optimal activity of the mixtures with respect to the reduction of unburnt carbonaceous and friability of mineral ash constituting the residues of incomplete combustion of liquid or solid fuels.
- salts of the lower series of carboxylic acids has the advantage of causing, by heat decomposition, only the formation of gaseous compounds such as CO2, O2, H2 and H2O not presenting significant risks. of atmospheric pollution nor, in particular, the disadvantages of the formation of compounds of the NO x type.
- the salts of lower carboxylic acids of potassium and cerium can be sprayed beforehand on solid fuels or directly in the combustion flame of liquid or solid fuels.
- the mixing can be carried out using a simple feed hopper depositing the pulverulent composition on the fuel before it enters into combustion.
- a pulverulent composition according to the invention is prepared by intimately mixing 85% of potassium acetate and 15% of cerium acetate.
- the powder mixture thus obtained is injected by any pneumatic means into the flame of a heat generator consuming 10 tonnes of fuel oil per day, in a single injection of 1000 grams per day for 20 days consecutively.
- Example 2 Under experimental conditions identical to those indicated in Example 1, a pulverulent composition according to the invention comprising 70% of potassium acetate and 30% of cerium acetate was sprayed. At the end of the treatment, the carbon content of the remaining unburnt deposits had decreased by 35% and the mineral deposits in the hot zones had become much more brittle while remaining relatively adherent to the metal surfaces.
- an 18-day spraying of a powder mixture according to the invention was carried out under experimental conditions practically identical to those indicated in Example 1.
- a composition according to the invention was prepared by dissolving 9 kg of potassium acetate and 8.5 kg of cerium formate in 32.5 kg of demineralized water, in order to avoid any interference of the salts contained in natural raw water with the results of the experiment.
- the liquid preparation according to the invention was sprayed using a centrifugal pump and via a nozzle, into the flame of a burner of a steam generator consuming 17 to 23 tonnes of heavy fuel oil per 24 hours, for an average of 18.7 tonnes per day.
- a liquid composition according to the invention obtained by dissolving 20% by weight in the flame of a burner of a pressurized hot water generator supplied with domestic fuel oil potassium acetate and 15% by weight of cerium acetate in 65% by weight of water. The treatment was continued for 8 consecutive days.
- the pulverulent compositions according to the invention can be ground finely enough to be sprayed onto solid fuels or in the flame of the generators, they nevertheless retain an irreducible particle size which delays their thermal decomposition speed and somewhat limits their remarkable efficiency.
- compositions according to the invention in the form of aqueous solutions, results in a spraying with a perfectly adjustable particle size up to nebulization, allowing very rapid thermal decomposition and excellent distribution of the resulting dehydrated salts distributed by the molecules of water vapor subjected to this instantaneous vaporization.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
La présente invention concerne un procédé destiné à réduire la quantité et à modifier la structure des dépôts imbrûlés qui se forment sur les surfaces des générateurs de chaleur.The present invention relates to a method for reducing the amount and modifying the structure of unburnt deposits which form on the surfaces of heat generators.
L'invention concerne également les associations synergiques de produits utilisés à cet effet dans les générateurs de chaleur.The invention also relates to synergistic combinations of products used for this purpose in heat generators.
Les générateurs de chaleur concernés peuvent brûler des combustibles liquides tels que les dérivés du pétrole ou des combustibles solides tels que le charbon et/ou les déchets industriels tels que les liqueurs noires de papeteries ou les ordures ménagères par exemple.The heat generators concerned can burn liquid fuels such as petroleum derivatives or solid fuels such as coal and / or industrial waste such as black liquors from paper mills or household waste for example.
Les générateurs de chaleur concernés peuvent être indifféremment ceux qui ont pour finalité la production d'air chaud, d'eau chaude, de vapeur saturée ou de vapeur surchauffée.The heat generators concerned can be indifferently those whose purpose is the production of hot air, hot water, saturated steam or superheated steam.
Dans de tels générateurs, les dépôts qui se forment généralement sur les surfaces d'échange en contact avec les fumées de la combustion sont composés d'éléments carbonés imbrûlés appelés généralement "suie", de cendres minérales incombustibles et de produits de la corrosion des surfaces tels que sulfates et sulfures principalement.In such generators, the deposits which generally form on the exchange surfaces in contact with the combustion fumes are composed of unburnt carbon elements generally called "soot", non-combustible mineral ash and products of surface corrosion. mainly sulfates and sulfides.
Tous ces dépôts, dont les divers composants cités coexistent généralement, contribuent à diminuer les échanges thermiques et, par suite, le rendement des générateurs.All these deposits, of which the various components cited generally coexist, contribute to reducing the heat exchanges and, consequently, the efficiency of the generators.
De plus, la dureté et l'adhérence de ces dépôts peuvent devenir très importantes et rendre difficiles, voire inéfficaces, les ramonages et nettoyages habituels à la vapeur, à l'air comprimé ou mécaniques.In addition, the hardness and adhesion of these deposits can become very important and make it difficult, even ineffective, the usual sweeping and cleaning operations. steam, compressed air or mechanical.
Aussi trouve-t-on sur le marché des produits ou des compositions de produits qui ont pour but soit la destruction de la suie (imbrûlés carbonés) mais qui ne diminuent ni la dureté ni l'adhérence des cendres minérales fondues (oxydes métalliques généralement), soit la friabilisation des concrétions de cendres minérales mais qui ne diminuent pas ou peu les quantités de suie, soit encore à la fois la réduction de la suie et la friabilisation des cendres, comme certains chlorures par exemple mais qui ont le fâcheux inconvénient de contribuer aussi à la destruction progressive des surfaces métalliques et des revêtements réfractaires des générateurs de chaleur, ou encore comme certains nitrates qui ont l'inconvénient de contribuer sensiblement à la pollution atmosphérique en donnant naissance à des composés de la forme NOx dont les législations internationales tendent à limiter au maximum les teneurs dans les gaz résultant de la combustion.Also we find on the market products or product compositions which aim either the destruction of soot (unburnt carbon) but which does not reduce the hardness or adhesion of molten mineral ash (usually metal oxides) , either the friability of the concretions of mineral ash but which do not decrease or little the quantities of soot, or still at the same time the reduction of the soot and the friabilisation of the ashes, like certain chlorides for example but which have the annoying disadvantage of contributing also to the progressive destruction of metallic surfaces and of the refractory coatings of heat generators, or even like certain nitrates which have the disadvantage of contributing appreciably to atmospheric pollution by giving rise to compounds of the NO x form whose international legislations tend limit as much as possible the contents in the gases resulting from combustion.
Dans cette lutte contre les encrassements des générateurs et la pollution atmosphérique, il est également d'usage, en vue de diminuer les quantités résiduelles d'imbrûlés combustibles, de pulvériser des sels alcalins et plus particulièrement des sels de baryum et/ou de potassium tels que nitrates, carbonates, sulfates et acétates. C'est ainsi que, par exemple, le brevet européen No 0 007862 revendique l'utilisation d'une solution aqueuse d'un composé d'acétate de potassium et de nitrate de magnésium.In this fight against fouling of generators and atmospheric pollution, it is also customary, in order to reduce the residual quantities of combustible unburnt materials, to spray alkaline salts and more particularly barium and / or potassium salts such than nitrates, carbonates, sulfates and acetates. Thus, for example, European patent No. 0 007862 claims the use of an aqueous solution of a potassium compound acetate and magnesium nitrate.
Il est également d'usage, dans le but d'élever les points de fusion des cendres minérales et d'améliorer légèrement la combustion des composés carbonés, d'utiliser des adjuvants à base de métaux de la classe des terres rares.It is also customary, in order to raise the melting points of mineral ash and slightly improve the combustion of carbonaceous compounds, to use adjuvants based on metals from the rare earth class.
Parmi les compositions les plus connues, on peut citer celles contenant certains sels de métaux faisant partie de la série des terres rares, tels les sels oléosolubles de cérium, par exemple revendiquées dans les brevets français 2.359.192 et 2.359.199 comme adjuvants de combustion.Among the most known compositions, one can cite those containing certain metal salts forming part of the series of rare earths, such as the oil-soluble salts of cerium, for example claimed in French patents 2,359,192 and 2,359,199 as combustion adjuvants.
La présente invention a pour objet un procédé de traitement permettant d'obtenir un résultat plus avantageux que celui obtenu avec les compositions actuellement utilisés.The subject of the present invention is a treatment method making it possible to obtain a more advantageous result than that obtained with the compositions currently used.
Ce procédé est caractérisé en ce que l'on projette, soit sur les combustibles solides avant leur combustion, soit dans les enceintes des générateurs durant la combustion des combustibles liquides ou solides, une composition, de forme pulvérulente ou liquide, constituée par une association à effet synergique de sels organiques hydrosolubles d'un métal alcalin, et d'un métal de la série des terres rares.This process is characterized in that, either on solid fuels before their combustion, or in the enclosures of the generators during the combustion of liquid or solid fuels, a composition, in powder or liquid form, constituted by an association with synergistic effect of water-soluble organic salts of an alkali metal and a metal from the rare earth series.
Cependant la présente invention a également pour objet un agent réducteur d'imbrûlés pour la mise en oeuvre du procédé défini ci-dessus.However, the present invention also relates to an unburnt reducing agent for the implementation of the process defined above.
Dans une forme particulière de composition, cet agent réducteur consiste en une composition pulvérulente comportant, en association à effet synergique, de 70 à 90% en poids de carboxylates de potassium et de 10 à 30% en poids de carboxylates de cérium.In a particular form of composition, this reducing agent consists of a pulverulent composition comprising, in combination with a synergistic effect, from 70 to 90% by weight of potassium carboxylates and from 10 to 30% by weight of cerium carboxylates.
Dans une autre forme de composition, cet agent réducteur consiste en une composition liquide comportant, en association à effet synergique, de 10 à 20% en poid de carboxylates de potassium et de 15 à 20% en poids de carboxylates de cérium, et 65 à 70% d'eau.In another form of composition, this reducing agent consists of a liquid composition comprising, in a synergistic effect, from 10 to 20% by weight of potassium carboxylates and from 15 to 20% by weight of cerium carboxylates, and 65 to 70% water.
La conception du procédé selon l'invention découle d'une étude systématique de l'évolution des résidus carbonés et minéraux subsistant sur les surfaces des enceintes de combusion en fonction des divers adjuvants à introduire dans les combustibles ou à pulvériser dans la flamme et proposés dans le commerce ou communément utilisés par l'homme de l'art. En effet en procédant à une telle étude le demandeur eut la surprise de constater qu'en associant judicieusement un sel de métal alcalin à un sel de métal de la série des terres rares, il se produisait un accroissement inattendu des effets propres à chacun des composés essayés séparément.The design of the process according to the invention follows from a systematic study of the evolution of carbonaceous and mineral residues remaining on the surfaces of the combustion chambers as a function of the various adjuvants to be introduced into the fuels or to be sprayed into the flame and offered commercially or commonly used by those skilled in the art. Indeed, by carrying out such a study, the applicant was surprised to note that by judiciously combining an alkali metal salt with a metal salt from the rare earth series, there was an unexpected increase in the effects specific to each of the compounds. tried separately.
Les effets recherchés étant d'une part la diminution de la température d'oxydation des imbrûlés carbonés et, d'autre part, l'élévation des points de fusion des cendres incombustibles, effets qui ont généralement pour résultat la réduction des dépôts d'imbrûlés, les essais industriels effectués par le demandeur et complétés par des mesures en laboratoire ont permis de constater que non seulement les sels alcalins et les sels de terre rare agissent bien séparément selon ce qui en est généralement dit, mais encore, et cela de manière tout-à-fait inattendue, que la conjonction simultanée de leurs activités respectives donne des résultats supérieurs à ceux obtenus dans les mêmes conditions à l'aide desdits sels utilisés séparément.The desired effects being on the one hand the reduction in the oxidation temperature of the carbon unburnt products and, on the other hand, the rise in the melting points of the incombustible ash, effects which generally result in the reduction of the unburnt deposits , the industrial tests carried out by the applicant and supplemented by laboratory measurements have shown that not only the alkali and rare earth salts act well separately according to what is generally said, but also, and this in a very - unexpectedly, that the simultaneous conjunction of their respective activities gives results superior to those obtained under the same conditions using the said salts used separately.
On indique dans le tableau I ci-après, les moyennes des mesures obtenues, dans des conditions tout-à-fait reproductibles et constantes, sur les températures d'ignition des imbrûlés carbonés seuls et en présence de sels de potassium et/ou des sels de cérium.
Il est manifeste que l'association POTASSIUM + CERIUM utilisée au dosage total identique de 250 ppm entraine une très sensible diminution de la température d'ignition par rapport aux résultats obtenus à l'aide du POTASSIUM seul ou du CERIUM seul.It is obvious that the POTASSIUM + CERIUM combination used at the identical total dosage of 250 ppm leads to a very significant reduction in the ignition temperature compared to the results obtained using POTASSIUM alone or CERIUM alone.
On indique également dans le tableau II ci-après les moyennes des mesures obtenues dans des conditions constantes d'expérimentation, sur les points de fusion apparents des cendres minérales seules et en présence des sels de potassium et/ou des sels de cérium.
Les résultats consignés dans le tableau II font apparaître de manière surprenante que l'association d'un métal alcalin, tel le potassium, par exemple, et d'un métal de la famille des terres rares, tel le cérium, par exemple, manifeste une activité sur l'augmentation du point de fusion apparent des cendres minérales très nettement supérieure à celle, pratiquement nulle, du potassium seul et à celle, déjà très importante, du cérium seul.The results recorded in Table II surprisingly show that the combination of an alkali metal, such as potassium, for example, and a metal of the rare earth family, such as cerium, for example, exhibits a activity on the increase in the apparent melting point of mineral ash very much higher than that, practically zero, of potassium alone and that, already very important, of cerium alone.
Le procédé de traitement selon l'invention prévoit donc l'association de composés du potassium et de composés du cérium en vue de réduire les dépôts imbrûlés et de destructurer les dépôts imbrûlables sur les surfaces des enceintres de combustion.The treatment method according to the invention therefore provides for the combination of potassium compounds and cerium compounds in order to reduce unburnt deposits and to destroy unburnable deposits on the surfaces of the combustion chambers.
Une autre particularité du présent procédé consiste à associer entre eux des sels de potassium et de cérium solubles dans l'eau et obtenus à partir d'acides carboxyliques à bas poids moléculaires de formule élémentaire : CxOyHz dans laquelle la valeur de x est un nombre entier pair ou impair, compris entre 1 et 3 inclus.Another characteristic of the present process consists in associating with them potassium and cerium salts soluble in water and obtained from low molecular weight carboxylic acids of elementary formula: C x O y H z in which the value of x is a even or odd whole number, between 1 and 3 inclusive.
En effet, les sels d'acides carboxyliques inférieurs de potassium et de cérium tels que le formiate de potassium, le formiate de cerium, l'acétate de potassium et l'acétate de cérium présentent l'avantage de pouvoir être mélangés entre eux sous leurs formes pulvérulentes ou sous forme de solutions aqueuses permettant de faire varier les proportions de métal alcalin et de métal de la série des terres rares dans des rapports choisis de préférence en fonction de l'activité optimale des mélanges vis-à-vis de la réduction des imbrûlés carbonés et de la friabilisation des cendres minérales constituant les résidus de la combustion imcomplète des combustibles liquides ou solides.In fact, the salts of lower carboxylic acids of potassium and of cerium such as potassium formate, cerium formate, potassium acetate and cerium acetate have the advantage of being able to be mixed together under their pulverulent forms or in the form of aqueous solutions making it possible to vary the proportions of alkali metal and of metal of the rare earth series in ratios chosen preferably as a function of the optimal activity of the mixtures with respect to the reduction of unburnt carbonaceous and friability of mineral ash constituting the residues of incomplete combustion of liquid or solid fuels.
De plus, l'utilisation de sels de la série inférieure des acides carboxyliques présente l'avantage de ne provoquer, par décomposition à la chaleur, que la formation de composés gazeux tels que CO₂, O₂, H₂ et H₂O ne présentant pas de risques notables de pollution atmosphérique ni, en particulier, les inconvénients de formation de composés du type NOx.In addition, the use of salts of the lower series of carboxylic acids has the advantage of causing, by heat decomposition, only the formation of gaseous compounds such as CO₂, O₂, H₂ and H₂O not presenting significant risks. of atmospheric pollution nor, in particular, the disadvantages of the formation of compounds of the NO x type.
Suivant les besoins, et grâce à leur forme cristallisée en poudre ou à leur possibilité de mise en solutions aqueuses, les sels d'acides carboxyliques inférieurs de potassium et de cérium peuvent être préalablement pulvérisés sur les combustibles solides ou directement dans la flamme de combustion des combustibles liquides ou solides.Depending on requirements, and thanks to their crystallized powder form or their possibility of being put into aqueous solutions, the salts of lower carboxylic acids of potassium and cerium can be sprayed beforehand on solid fuels or directly in the combustion flame of liquid or solid fuels.
Ces possibilités présentent de nombreux avantages selon la configuration des générateurs à protéger, la nature du combustible, la précision des réglages à effectuer.These possibilities have numerous advantages depending on the configuration of the generators to be protected, the nature of the fuel, the precision of the adjustments to be made.
Dans le cas, par exemple, d'alimentation au charbon de houille, de générateurs possédant des circuits de fumées relativement courts, on peut avoir intérêt à mélanger en association les produits selon l'invention sous leur forme pulvérulente au combustible avant son introduction dans le générateur. Dans ce cas, le mélange peut s'éffectuer à l'aide d'une simple trémie d'alimentation déposant la composition pulvérulente sur le combustible avant son entrée en combustion.In the case, for example, of coal coal supply, of generators having relatively short smoke circuits, it may be advantageous to mix in association the products according to the invention in their pulverulent form with the fuel before its introduction into the generator. In this case, the mixing can be carried out using a simple feed hopper depositing the pulverulent composition on the fuel before it enters into combustion.
Dans d'autres cas, et notamment dans des générateurs de grandes dimensions alimentés en combustibles liquides, on pourra, selon les besoins, pulvériser les produits selon l'invention sous forme de solution aqueuse dans l'enceinte même de conbustion, de telle sorte que, par sa plus faible concentration en métaux, la solution aqueuse, très finement pulvérisable à l'aide d'un système pneumatique, par exemple, s'évapore rapidement en entraînant la dessication des sels dissous et leur meilleure répartition dans toutes les parties parcourues par les fumées chaudes.In other cases, and in particular in generators of large dimensions supplied with liquid fuels, it is possible, as necessary, to spray the products according to the invention in the form of an aqueous solution in the very combustion chamber, so that , by its lower concentration of metals, the aqueous solution, very finely sprayable using a pneumatic system, for example, evaporates quickly causing the desiccation of dissolved salts and their better distribution in all the parts traversed by hot fumes.
Les exemples ci-après, donnés à titre non limitatif, illustrent les avantages et l'originalité du procédé selon l'invention.The examples below, given without limitation, illustrate the advantages and originality of the method according to the invention.
Une composition pulvérulente selon l'invention est préparée en mélangeant intimement 85% d'acétate de potassium et 15% d'acétate de cérium. Le mélange en poudre ainsi obtenu est injecté par un moyen pneumatique quelconque dans la flamme d'un générateur de chaleur consommant 10 tonnes de fioul par jour et ce, en une seule injection de 1 000 grammes par jour durant 20 jours consécutivement.A pulverulent composition according to the invention is prepared by intimately mixing 85% of potassium acetate and 15% of cerium acetate. The powder mixture thus obtained is injected by any pneumatic means into the flame of a heat generator consuming 10 tonnes of fuel oil per day, in a single injection of 1000 grams per day for 20 days consecutively.
A la fin de la période de traitement selon l'invention, on a constaté une diminution de près de 40% de la teneur en imbrûlés carbonés dans les dépôts qui avaient ainsi diminués en quantité et étaient devenus très friables et peu adhérents aux parois métalliques.At the end of the treatment period according to the invention, there was a reduction of almost 40% in the content of carbon unburnt deposits which had thus decreased in quantity and had become very brittle and not very adherent to the metal walls.
En particulier, à poids égaux, les échantillons prélevés occupaient des volumes pratiquement doubles, ce qui indiquait une densité apparente réduite de moitié, une plus grande facilité d'élimination par ramonage.In particular, for equal weights, the samples sampled occupied almost double volumes, indicating an apparent density reduced by half, greater ease of elimination by sweeping.
Dans des conditions expérimentales identiques à celles indiquées dans l'exemple 1, on a pulvérisé une composition pulvérulente selon l'invention comprenant 70% d'acétate de potassium et 30% d'acétate de cérium. A la fin du traitement, la teneur en carbone des dépôts imbrûlés subsistants avait diminué de 35% et les dépôts minéraux des zones chaudes étaient devenus très nettement plus friables tout en demeurant relativement adhérents aux surfaces métalliques.Under experimental conditions identical to those indicated in Example 1, a pulverulent composition according to the invention comprising 70% of potassium acetate and 30% of cerium acetate was sprayed. At the end of the treatment, the carbon content of the remaining unburnt deposits had decreased by 35% and the mineral deposits in the hot zones had become much more brittle while remaining relatively adherent to the metal surfaces.
Sur le même site et après une période de fonctionnement du générateur sans traitement, on a procédé, dans des conditions expérimentales pratiquement identiques à celles indiquées dans l'exemple 1, à la pulvérisation durant 18 jours d'un mélange en poudre selon l'invention composé de 90% d'acétate de potassium et de 10% d'acétate de cérium, et introduit à raison de 800 grammes par jour en deux injections par jour de traitement.On the same site and after a period of operation of the generator without treatment, an 18-day spraying of a powder mixture according to the invention was carried out under experimental conditions practically identical to those indicated in Example 1. composed of 90% potassium acetate and 10% cerium acetate, and introduced at the rate of 800 grams per day in two injections per day of treatment.
A la fin du traitement, les analyses des échantillons de dépôts prélevés dans les parties les moins chaudes montraient une diminution de plus de 55% des teneurs en carbone et, sur les dépôts prélevés dans les zones les plus chaudes, une diminution de 34% de la densité des cendres minérales, démontrant ainsi l'efficacité assez remarquable du procédé et des compositions selon l'invention.At the end of the treatment, analyzes of the samples of deposits taken in the warmest parts showed a decrease of more than 55% in the carbon contents and, on the deposits taken in the hottest areas, a decrease of 34% in the density of mineral ash, thus demonstrating the rather remarkable efficiency of the process and of the compositions according to the invention.
On a préparé une composition selon l'invention en dissolvant 9 kg d'acétae de potassium et 8,5 kg de formate de cérium dans 32,5 kg d'eau déminéralisée, afin d'éviter toute interférence des sels contenus dans une eau brute naturelle sur les résultats de l'expérience.A composition according to the invention was prepared by dissolving 9 kg of potassium acetate and 8.5 kg of cerium formate in 32.5 kg of demineralized water, in order to avoid any interference of the salts contained in natural raw water with the results of the experiment.
La préparation liquide selon l'invention fut pulvérisée à l'aide d'une pompe centrifuge et par l'intermédiaire d'un gicleur, dans la flamme d'un brûleur d'un générateur de vapeur consommant de 17 à 23 tonnes de fioul lourd par 24 heures, pour une moyenne de 18,7 tonnes par jour.The liquid preparation according to the invention was sprayed using a centrifugal pump and via a nozzle, into the flame of a burner of a steam generator consuming 17 to 23 tonnes of heavy fuel oil per 24 hours, for an average of 18.7 tonnes per day.
L'expérience a été poursuivie 28 jours consécutivement à raison de deux injections de 1 000 grammes chacune de la composition ci-dessus et par jour de traitement.The experiment was continued 28 days consecutively at the rate of two injections of 1000 grams each of the above composition and per day of treatment.
Les examens de laboratoire effectués sur les échantillons de dépôts prélevés aux mêmes endroits et dans les mêmes conditions qu'avant le traitement ont permis de constater une diminution de près de 61% de la teneur en imbrûlés carbonés et la disparition presque complète des dépôts structurés dans les zones chaudes où ne subsistait plus qu'une très fine pellicule de poussières blanches, non adhérentes aux surfaces et d'une densité apparente de 25% de celle des échantillons antérieurement prélevés aux mêmes endroits.Laboratory examinations carried out on the samples of deposits taken in the same places and under the same conditions as before the treatment revealed a decrease of almost 61% in the content of unburnt carbon and the almost complete disappearance of the structured deposits in hot areas where only a very thin film of white dust remained, not adhering to surfaces and with an apparent density of 25% of that of samples previously taken from the same places.
Dans la flamme d'un brûleur d'un générateur d'eau chaude surpressée et alimenté en fioul domestique, on a pulvérisé trois fois par jour 250 à 300 grammes d'une composition liquide selon l'invention obtenue en dissolvant 20% en poids d'acétate de potassium et 15% en poids d'acétate de cérium dans 65% en poids d'eau. Le traitement a été poursuivi durant 8 jours consécutifs.250 to 300 grams of a liquid composition according to the invention obtained by dissolving 20% by weight in the flame of a burner of a pressurized hot water generator supplied with domestic fuel oil potassium acetate and 15% by weight of cerium acetate in 65% by weight of water. The treatment was continued for 8 consecutive days.
Les prélèvements effectués à l'issue de l'essai dans des conditions analogues à ceux effectués préalablement, avant un nettoyage périodique du générateur, ont fait apparaître une diminution de plus de 42% de la teneur en carbone imbrûlé.The samples taken at the end of the test under conditions similar to those taken before, before periodic cleaning of the generator, showed a reduction of more than 42% in the content of unburnt carbon.
Les dépôts de cendres minérales subsistant dans les parties chaudes paraissaient n'avoir pas diminués en poids ni s'être accrus en volume. Cependant, l'opération de nettoyage de ce générateur s'est effectuée en trois heures à l'aide d'un simple aspirateur industriel au lieu d'une journée habituellement nécessaire après écouvillonnage, aspiration et lessivage neutralisant.The mineral ash deposits remaining in the hot parts appeared not to have decreased in weight or to have increased in volume. However, the cleaning operation of this generator was carried out in three hours using a simple industrial vacuum cleaner instead of a day usually necessary after swabbing, suction and neutralizing leaching.
Si les exemples 1 à 5 non limitatifs ci-dessus font apparaître des efficacités légèrement supérieures pour les traitements à l'aide des compositions liquides selon l'invention par rapport aux compositions pulvérulentes selon l'invention également, cela tient aux conditions de pulvérisation que permet l'une des originalités de l'invention qui fait appel à des sels solubles dans l'eau de potassium et de cérium.If the nonlimiting examples 1 to 5 above show slightly higher efficiencies for the treatments using the liquid compositions according to the invention compared to the pulverulent compositions according to the invention also, this is due to the spraying conditions which allows one of the original features of the invention which uses water-soluble salts of potassium and cerium.
En effet, si les compositions pulvérulentes selon l'invention peuvent être broyé assez finement pour être projetées sur les combustibles solides ou dans la flamme même des générateurs, elles conservent néanmoins une granulométrie irréductible qui retarde leur vitesse de décomposition thermique et limite quelque peu leur remarquable efficacité.Indeed, if the pulverulent compositions according to the invention can be ground finely enough to be sprayed onto solid fuels or in the flame of the generators, they nevertheless retain an irreducible particle size which delays their thermal decomposition speed and somewhat limits their remarkable efficiency.
En revanche, la possibilité de présenter les compositions selon l'invention sous forme de solutions aqueuses, entraîne une pulvérisation de granulométrie parfaitement réglable jusqu'à la nébulisation, autorisant une décomposition thermique très rapide et une excellente répartition des sels déshydratés résultants et diffusés par les molécules de vapeur d'eau soumises à cette vaporisation instantanée.On the other hand, the possibility of presenting the compositions according to the invention in the form of aqueous solutions, results in a spraying with a perfectly adjustable particle size up to nebulization, allowing very rapid thermal decomposition and excellent distribution of the resulting dehydrated salts distributed by the molecules of water vapor subjected to this instantaneous vaporization.
Claims (5)
CxOyHz
dans laquelle x représente un nombre entier, pair ou impair, compris entre 1 et 3 inclus, alors que y et z représentent les valeurs nécessaires pour satisfaire les formules générales des trois premiers termes des acides carboxylique comportant une fonction - COOH(-) tels que H - COOH, CH₃ - COOH et CH₃ - CH₂ - COOH -3.- A method according to claims 2 characterized in that the organic potassium and cerium salts are water-soluble salts of low molecular weight carboxylic acids corresponding to the elementary formula below:
C x O y H z
in which x represents an integer, even or odd, between 1 and 3 inclusive, while y and z represent the values necessary to satisfy the general formulas of the first three terms of the carboxylic acids comprising a function - COOH (-) such that H - COOH, CH₃ - COOH and CH₃ - CH₂ - COOH -
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8511551A FR2585360B1 (en) | 1985-07-29 | 1985-07-29 | METHOD FOR REDUCING COMBUSTION IMBRULES AND AGENT FOR IMPLEMENTING SAME |
DE8686402784T DE3665074D1 (en) | 1986-12-12 | 1986-12-12 | Process for reducing unburned combustion particles, and agent for carrying out the process |
EP86402784A EP0270719B1 (en) | 1986-12-12 | 1986-12-12 | Process for reducing unburned combustion particles, and agent for carrying out the process |
ES86402784T ES2010670B3 (en) | 1986-12-12 | 1986-12-12 | PROCEDURE FOR THE REDUCTION OF FUELS AND AGENT FOR THEIR START-UP. |
GR89400133T GR3000126T3 (en) | 1986-12-12 | 1989-08-17 | Process for reducing unburned combustion particles, and agent for carrying out the process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP86402784A EP0270719B1 (en) | 1986-12-12 | 1986-12-12 | Process for reducing unburned combustion particles, and agent for carrying out the process |
Publications (2)
Publication Number | Publication Date |
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EP0270719A1 true EP0270719A1 (en) | 1988-06-15 |
EP0270719B1 EP0270719B1 (en) | 1989-08-16 |
Family
ID=8196366
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86402784A Expired EP0270719B1 (en) | 1985-07-29 | 1986-12-12 | Process for reducing unburned combustion particles, and agent for carrying out the process |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0270719B1 (en) |
DE (1) | DE3665074D1 (en) |
ES (1) | ES2010670B3 (en) |
FR (1) | FR2585360B1 (en) |
GR (1) | GR3000126T3 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0368834A1 (en) * | 1988-10-03 | 1990-05-16 | Lang & Co., chemisch-technische Produkte Kommanditgesellschaft | Aqueous combustion catalysts and fuels |
EP0423417A1 (en) * | 1989-09-15 | 1991-04-24 | SAT Chemie G.m.b.H. | Process for the selective, non-catalytic reduction of the emissions from oil-fired boiler plants |
EP0426978A1 (en) * | 1989-09-15 | 1991-05-15 | ERC Emissions-Reduzierungs-Concepte GmbH | Process for the selective, non-catalytic reduction of the emissions from oil fired boiler plants |
DE4032845A1 (en) * | 1989-11-02 | 1991-07-11 | Lang Chem Tech Prod | Hydrophilic catalyst soln. for (hydro)carbon material combustion - contg. lanthanide cpds. in higher oxidation state, iron gp. cpds. and opt. complexing agents |
WO1995011287A1 (en) * | 1993-10-18 | 1995-04-27 | Ica Innoconsult Ag | Corrosion-proofing process |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2585360B1 (en) * | 1985-07-29 | 1987-11-20 | Rosenbluth Germain | METHOD FOR REDUCING COMBUSTION IMBRULES AND AGENT FOR IMPLEMENTING SAME |
DE4424090A1 (en) * | 1994-07-12 | 1996-01-18 | Erc Emissions Reduzierungs Con | Fluid catalyst injection to improve burn-out of solid fuel, reducing fouling and corrosion |
GB9610563D0 (en) * | 1996-05-20 | 1996-07-31 | Bp Chemicals Additives | Marine diesel process and fuel therefor |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2014686A (en) * | 1931-08-27 | 1935-09-17 | Lubovitch | Combustion of fuels |
FR2359199A1 (en) * | 1976-07-22 | 1978-02-17 | Gamlen Naintre Sa | Additives improving combustion of diesel fuel - comprising oil-soluble rare earth metal derivs. |
EP0007862A1 (en) * | 1978-07-25 | 1980-02-06 | Drivex S.A. | Liquid agent for the chemical destruction of soot and method of application |
EP0134146A2 (en) * | 1983-08-17 | 1985-03-13 | Exxon Research And Engineering Company | Residual fuel oil composition |
FR2585360A1 (en) * | 1985-07-29 | 1987-01-30 | Rosenbluth Germain | Process for reducing unburnt materials from combustion and agent for its use |
-
1985
- 1985-07-29 FR FR8511551A patent/FR2585360B1/en not_active Expired
-
1986
- 1986-12-12 ES ES86402784T patent/ES2010670B3/en not_active Expired
- 1986-12-12 EP EP86402784A patent/EP0270719B1/en not_active Expired
- 1986-12-12 DE DE8686402784T patent/DE3665074D1/en not_active Expired
-
1989
- 1989-08-17 GR GR89400133T patent/GR3000126T3/en unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2014686A (en) * | 1931-08-27 | 1935-09-17 | Lubovitch | Combustion of fuels |
FR2359199A1 (en) * | 1976-07-22 | 1978-02-17 | Gamlen Naintre Sa | Additives improving combustion of diesel fuel - comprising oil-soluble rare earth metal derivs. |
EP0007862A1 (en) * | 1978-07-25 | 1980-02-06 | Drivex S.A. | Liquid agent for the chemical destruction of soot and method of application |
EP0134146A2 (en) * | 1983-08-17 | 1985-03-13 | Exxon Research And Engineering Company | Residual fuel oil composition |
FR2585360A1 (en) * | 1985-07-29 | 1987-01-30 | Rosenbluth Germain | Process for reducing unburnt materials from combustion and agent for its use |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0368834A1 (en) * | 1988-10-03 | 1990-05-16 | Lang & Co., chemisch-technische Produkte Kommanditgesellschaft | Aqueous combustion catalysts and fuels |
AT391873B (en) * | 1988-10-03 | 1990-12-10 | Lang Chem Tech Prod | AQUEOUS CATALYST SOLUTION AND FUELS |
EP0423417A1 (en) * | 1989-09-15 | 1991-04-24 | SAT Chemie G.m.b.H. | Process for the selective, non-catalytic reduction of the emissions from oil-fired boiler plants |
EP0426978A1 (en) * | 1989-09-15 | 1991-05-15 | ERC Emissions-Reduzierungs-Concepte GmbH | Process for the selective, non-catalytic reduction of the emissions from oil fired boiler plants |
DE4032845A1 (en) * | 1989-11-02 | 1991-07-11 | Lang Chem Tech Prod | Hydrophilic catalyst soln. for (hydro)carbon material combustion - contg. lanthanide cpds. in higher oxidation state, iron gp. cpds. and opt. complexing agents |
WO1995011287A1 (en) * | 1993-10-18 | 1995-04-27 | Ica Innoconsult Ag | Corrosion-proofing process |
Also Published As
Publication number | Publication date |
---|---|
ES2010670B3 (en) | 1989-12-01 |
FR2585360A1 (en) | 1987-01-30 |
EP0270719B1 (en) | 1989-08-16 |
DE3665074D1 (en) | 1989-09-21 |
FR2585360B1 (en) | 1987-11-20 |
GR3000126T3 (en) | 1990-11-29 |
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