EP0368834A1 - Aqueous combustion catalysts and fuels - Google Patents

Aqueous combustion catalysts and fuels Download PDF

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Publication number
EP0368834A1
EP0368834A1 EP89890256A EP89890256A EP0368834A1 EP 0368834 A1 EP0368834 A1 EP 0368834A1 EP 89890256 A EP89890256 A EP 89890256A EP 89890256 A EP89890256 A EP 89890256A EP 0368834 A1 EP0368834 A1 EP 0368834A1
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catalyst solution
solution according
alkaline
combustion
compounds
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German (de)
French (fr)
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EP0368834B1 (en
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Gertrude Dipl.-Ing. Kaes
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Lang & Co Chemisch-Technische Produkte KG
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Lang & Co Chemisch-Technische Produkte KG
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    • 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
    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal

Definitions

  • the invention relates to aqueous combustion catalysts for improved combustion of carbon and / or hydrocarbon-containing substances, such as heating oils, heating gases and solid fuels and / or for removing soot or tar deposits on surfaces of the combustion chamber.
  • the invention further relates to the use of such catalyst solutions and fuels.
  • Soot formation adversely affects combustion due to the loss of heat generation as well as the reduced heat transfer, since soot has a high thermal insulation effect.
  • Combustion catalysts have therefore been used for a long time in order to both prevent or minimize the formation of soot and to burn off soot and tar deposits that have already formed at the lowest possible temperatures.
  • the improved combustion of tars and soot already formed is most effectively achieved by transition metal compounds, which are known to exist in different valences.
  • metal compounds are those of copper, manganese, cobalt, zinc and chromium (chromates).
  • copper compounds or metallic copper powder significantly reduce the combustion temperature of soot and tars.
  • they have the disadvantage of acting as toxic constituents in the exhaust gas, and of causing a significantly increased risk of corrosion on iron materials.
  • Copper is more positive than iron in the electrochemical voltage series, so that in the case of copper deposits, local elements are formed on the iron materials commonly used in heating technology, which corrode the iron-containing structural parts. This is significantly increased by the presence of sulfuric acid or sulfurous acid, which are formed when burning sulfur-containing fuels.
  • Zinc compounds are less toxic than copper and also pose no significant risk of corrosion for ferrous materials, but are practically hardly effective as a combustion catalyst for soot and tars.
  • Chromium has so far been used for the present purposes mainly in the form of chromates, both to benefit from the combustion-catalytic effect of the metal ion and to utilize the oxidation potential of the chromates on carbon. Due to the carcinogenic effects of some chromium compounds, however, these are eliminated according to today's environmental protection requirements. The same applies to nickel and cobalt compounds, although cobalt in particular is able to have a good combustion catalytic effect.
  • Iron is a non-toxic transition metal, which is often used in oil-soluble form (iron soaps, ferrocene, for example) as a combustion catalyst in liquid fuels.
  • aqueous iron salt solutions such as iron sulfates
  • Hydrogen peroxide was also used as a metal ion-free cleaning agent for fire-side carbon deposits.
  • This oxidizing agent is also recommended in conjunction with free alkalis such as alkali hydroxides, carbonates and silicates, whereby the oxidation of the carbon black by H2O2 and the acid neutralization by the strong aqueous alkali solutions follows; there is no combustion catalytic effect.
  • Examples of published documents are GB-PS 1 252 624 for hydrogen peroxide and strong aqueous alkali solutions, DE-OS 3 023 520 for the addition of calcium compounds (calcium phosphates in powder form), DE-PS 2 413 520 for deblocking agents based on metal compounds containing copper powder , US Pat. No. 4,287,090 for aqueous catalytically active metal salt solutions consisting of manganese acetate, calcium nitrate and copper acetate, DE-OS 2 911 259 as a means of cleaning on the fire side with alkali iodate or alkali periodate solutions together with copper carbonate as oxidation aid and ammonia or alkali carbonates for neutralizing acidic ash components.
  • GB-PS 1 303 552 recommends ammonium nitrate in addition to potassium nitrate and / or sodium nitrate for the binding and condensation of sulfuric acid from the combustion exhaust gases.
  • soot thickness as a deposit of only 1 mm can increase the exhaust gas temperature by approx. 70 ° C and entails additional fuel oil (heating) consumption of 5%.
  • the object of the invention is therefore to provide a combustion catalyst which is non-toxic, catalytically highly effective for the combustion at the lowest possible temperatures of soot and tars due to atmospheric oxygen, and which has a high oxidation potential in its higher-quality form. Furthermore, there should be a neutralization potential after combustion or thermal decomposition.
  • Lanthanides, in particular cerium compounds, in their tetravalent form have been found suitable as such a combustion catalyst.
  • Water-soluble cerium compounds are non-toxic and cerium nitrate hexahydrate has, for example, an LD50 (oral-rat) of 4200 mg / kg, compared to pure table salt LD50 (oral-rat) of only 3000 mg / kg.
  • Tetravalent cerium compounds are strong oxidizing agents, the oxidation potential of Ce (IV) / Ce (III) is approx. 1.6 volts, ie it is only slightly below that of permanganate to manganese dioxide with approx. 1.7 volts and more than twice as much high than for Fe (III) / Fe (II).
  • Oil-soluble cerium compounds have previously been used as fuel oil additives for improved combustion, in accordance with DE-OS 2 729 365 and US Pat. No. 4,462,810. However, these are exclusively oil-soluble and non- aqueous solutions of cerium compounds. In addition, the cerium is there in its trivalent form as an additive and not tetravalent.
  • an alkalinity reserve is present in order to neutralize acids from the burned fuels.
  • This neutralization of inorganic acids, such as sulfuric and sulfuric acid and organic, such as acetic acid, propionic acid, formic acid reduces the deposition of moist and adherent, carbon-containing deposits on the solid surfaces, in particular those for heat transfer, and inhibits the corrosive action of these acids on the Materials.
  • the invention is primarily characterized in that the aqueous catalyst solution has a pH of at least 7 and in a catalytically effective amount of tetravalent cerium (Ce4+) and alkali, alkaline earth and / or magnesium compounds, which after their combustion or thermal decomposition react alkaline, and contains complexing agents for this Ce4+. Further advantageous features of the invention can be found in the claims and the description.
  • Aqueous solutions with a strongly alkaline reaction also offer risks of attack for metallic and in particular mineral building materials, such as chamottes, as well as burns for the user during application.
  • the aforementioned solution can also advantageously be applied to heat transfer surfaces and other soot-endangered surfaces after the respective mechanical cleaning, which is mandatory in many countries, and serves both as corrosion protection and in particular as catalytically effective surface coating, which largely inhibits sooting and taring.
  • the aqueous catalyst solution according to Example 1 is diluted 1:10 with water and periodically applied to heat transfer surfaces and other surfaces to be sooted by means of a mechanical, built-in spray device. It turns out that - depending on the heating load and the degree of sootiness - a periodic spraying in 2- to 24-hour intervals is sufficient to prevent soot deposits and to achieve the best possible heat transfer and thus utilization of the fuels.
  • This method is mainly for large systems, i.e. industrial plants and caloric power plants.
  • the aqueous catalyst solution according to Example 1 is diluted 1:20 with water, which means that the finished dilution contains about 1,000 ppm of tetravalent cerium ions.
  • fine stone spraying into the combustion air of larger heating and boiler systems in the ratio of 1 GT diluted aqueous solution per 50 GT residue heating oil as Ver combustion catalyst introduced. Due to the relatively low proportion of 20 ppm tetravalent cerium in relation to the heavy heating oil, the soot number is reduced by 3 points according to Bacharach.
  • 10 pbw of a tetravalent water-dispersible cerium hydrate are finely distributed in 79 pbw of water.
  • 10 pbw of a sodium polyacrylate with an average molecular weight of 4000 are dissolved, and 1 pbw of nonylphenol with 7 moles of ethylene oxide addition.
  • the cerium hydrate contains 89% CeO2.
  • the particle size is 15 micrometers, the crystal size (XRD) is approximately 9 nanometers.
  • the Ce4+ content is 7.2 wt .-%, based on the dispersion.
  • aqueous dispersion is sprayed onto tar deposits in wood-burning systems and burned off by means of a brief, increased supply of air. It turns out that the catalytic effect of the tetravalent cerium can also be used to almost completely burn off the harmful and fire-hazardous tar residues in this form.
  • 10 pbw of trivalent cerium nitrate are dissolved in 70 pbw of water and converted into the tetravalent form with 3 pbw of 35% hydrogen peroxide (corresponding to about 3.4% by weight of cerium). Furthermore, 10 pbw of magnesium nitrate, 5 pbw of polyacrylates with a molecular weight of 2,000 (on average) are dissolved and brought to a pH of 8 using potassium hydroxide solution or caustic potash.
  • the magnesium nitrate is also thermally decomposed and, as a basic oxide / hydroxide, the mineral acids as well, but also organic acids, which form when burning sulfur-containing heating oils and coals or in the case of wood, straw, etc., accordingly neutralize.
  • Example 5 The solution according to Example 5 is prepared analogously, with magnesium nitrate being replaced by barium nitrate.
  • an alkalinity reserve occurs due to thermal decomposition, as well as the combustion catalysis mentioned.
  • Example 1 A solution according to Example 1 is prepared, the Caustic potash is replaced by lithium hydroxide monohydrate. Lithium hydroxide not only has an acid-neutralizing effect, but also a combustion-catalytic effect which supports the tetravalent cerium.
  • cerium nitrate (Ce (NO3) 2.6H2O are dissolved in 77 pbw of water and converted into the tetravalent cerium form with 2 pbw of hydrogen peroxide (35%) (approx. 1.7% by weight of cerium).
  • EDTA ethylenediaminetetraacetic acid
  • composition according to Example 9 the sodium nitrilotriacetate (NTA) being used instead of EDTA.
  • NTA sodium nitrilotriacetate
  • cerium nitrate 40 pbw of cerium nitrate (trivalent) are dissolved in 60 pbw of water and brought into the tetravalent form with 20 pbw of 35% hydrogen peroxide (about 13.3% by weight of cerium). 60 pbw of oxyacetic acid (glycolic acid) are also added and the pH is adjusted to 7 using potassium hydroxide solution or caustic potash.
  • the solution is used in the sense of the aforementioned examples as an aqueous combustion catalyst for liquid, solid and also gaseous fuels.
  • the content of the cerium ions in the catalyst solution according to the invention is generally between 0.1 and 15% by weight of the amount of catalyst solution and the metal ion content of the alkaline compound is advantageously between 0.1 and 30% by weight, based on the amount of catalyst solution.
  • the Cer4+ ion content is preferably between 1 and 100 ppm, based on the amount of fuel.
  • the catalyst solution according to the invention is at a pH of at least 7 in the neutral or basic range. This takes into account the required corrosion protection.
  • the complexing agent is preferably present in the catalyst solution in such an amount that precipitation of the cerium as a hydroxide is prevented.
  • the quantity range for the complexing agent can be between 1 and 40% by weight, based on the total amount of catalyst, preferably between 2 and 10% by weight.

Abstract

The invention relates to an aqueous catalyst solution for the improved combustion of materials containing carbon and/or hydrocarbon, such as fuel oils, fuel gases and solid fuels, and/or for the removal of deposits of soot or tar on surfaces of the combustion chamber, and it is characterised above all in that the aqueous catalyst solution has a pH of at least 7 and contains, in a catalytically active quantity, tetravalent cerium (Ce<4><+>) and alkali metal, alkali earth metal and/or magnesium compounds which, after combustion or thermal decomposition, show an alkaline reaction, and complexing agents for this Ce<4><+>. The invention also relates to a liquid or solid fuel, in particular fuel oil or coal, which is characterised in that it contains the aqueous catalyst solution in such a quantity that the cerium<4><+> content is between 1 and 100 ppm, preferably about 35 ppm, relative to the fuel quantity.

Description

Die Erfindung betrifft wäßrige Verbrennungskatalysatoren zur verbesserten Verbrennung von Kohlenstoff und/oder Kohlenwas­serstoff enthaltenden Stoffen, wie Heizöle, Heizgase und feste Brennstoffe und/oder zur Entfernung von Ruß- oder Teerablage­rungen auf Oberflächen des Brennraumes. Weiters betrifft die Erfindung die Anwendung derartiger Katalysatorlösungen und Brennstoffe.The invention relates to aqueous combustion catalysts for improved combustion of carbon and / or hydrocarbon-containing substances, such as heating oils, heating gases and solid fuels and / or for removing soot or tar deposits on surfaces of the combustion chamber. The invention further relates to the use of such catalyst solutions and fuels.

Zur Vermeidung von Rußablagerungen auf feuerseitigen festen Oberflächen ist eine möglichst vollständige Verbrennung der eingesetzten kohlenstoff- und kohlenwasserstoffhältigen Brenn­stoffe notwendig. Dies kann durch einen hohen Luftüberschuß erreicht werden, d.h. daß wesentlich mehr Luft den Brennstof­fen zugeführt wird als zu deren stöchiometrischer Verbrennung notwendig ist. Das bringt zwar eine Verbesserung der vollstän­digen Verbrennung, aber auch gleichzeitig den Nachteil eines unwirtschaftlichen Einsatzes der Brennstoffe mit sich, da un­nötig große Mengen an Luft aufgeheizt werden müssen und die Menge heißer Abgase erhöht wird. Man ist daher bemüht, die Verbrennung von kohlenstoff- und kohlenwasserstoffhältigen Brennstoffen ohne Rußbildung bzw. Minimierung derselben bei nahstöchiometrischer Verbrennung zu gestalten, was in der Pra­xis naturgemäß nicht vollständig bzw. nicht immer gelingt. Auch durch eine allmähliche Veränderung der Düseneinspritzung bei flüssigen Brennstoffen wird eine anfänglich perfekte Ver­brennungseinstellung negativ beeinflußt und die Rußbildung verstärkt.In order to avoid soot deposits on solid surfaces on the fire side, the most complete combustion possible of the fuels used containing carbon and hydrocarbons is necessary. This can be achieved by a high excess of air, i.e. that much more air is supplied to the fuels than is necessary for their stoichiometric combustion. Although this brings about an improvement in the complete combustion, it also has the disadvantage of an uneconomical use of the fuels, since unnecessarily large amounts of air have to be heated and the amount of hot exhaust gases is increased. It is therefore endeavored to design the combustion of fuels containing carbon and hydrocarbons without forming soot or minimizing them in the case of near-stoichiometric combustion, which of course in practice is not completely or not always possible. A gradual change in the nozzle injection in the case of liquid fuels also adversely affects an initially perfect combustion setting and increases the formation of soot.

Rußbildung benachteiligt die Verbrennung sowohl durch den Ver­lust an Wärmebildung als auch durch die verringerte Wärmeüber­tragung, da Ruß eine hohe thermische Isolierwirkung aufweist.Soot formation adversely affects combustion due to the loss of heat generation as well as the reduced heat transfer, since soot has a high thermal insulation effect.

Seit langer Zeit wird daher der Einsatz von Verbrennungskata­lysatoren vorgenommen, um sowohl die Bildung von Ruß zu ver­hindern bzw. zu minimieren als auch bereits gebildete Ablage­rungen von Ruß und Teer bei möglichst niedrigen Temperaturen wieder abzubrennen. Die verbesserte Verbrennung von bereits gebildeten Teeren und Ruß wird am wirksamsten durch Übergangs­metallverbindungen erzielt, welche bekanntlich in verschiede­nen Wertigkeiten vorkommen. Bisher hauptsächlich verwendete Metallverbindungen sind solche von Kupfer, Mangan, Kobalt, Zink und Chrom (Chromate). Insbesondere Kupferverbindungen bzw metallische Kupferpulver senken die Verbrennungstemperatur von Ruß und Teeren beträchtlich ab. Sie haben jedoch den Nachteil, als giftige Bestandteile im Abgas zu agieren, sowie eine we­sentlich verstärkte Korrosionsgefahr auf Eisenwerkstoffen zu bewirken. Kupfer ist in der elektrochemischen Spannungsreihe wesentlicher positiver als Eisen, sodaß sich bei Kupfernieder­schlägen auf den in der Wärmetechnik üblicherweise verwende­ten Eisenwerkstoffen Lokalelemente bilden, welche die eisen­hältigen Konstruktionsteile korrodieren. Dies wird durch das Vorhandensein von Schwefelsäure bzw. Schwefeliger Säure, wel­che sich bei der Verbrennung von schwefelhaltigen Brennstof­fen bilden, noch wesentlich verstärkt.Combustion catalysts have therefore been used for a long time in order to both prevent or minimize the formation of soot and to burn off soot and tar deposits that have already formed at the lowest possible temperatures. The improved combustion of tars and soot already formed is most effectively achieved by transition metal compounds, which are known to exist in different valences. So far mainly used metal compounds are those of copper, manganese, cobalt, zinc and chromium (chromates). In particular, copper compounds or metallic copper powder significantly reduce the combustion temperature of soot and tars. However, they have the disadvantage of acting as toxic constituents in the exhaust gas, and of causing a significantly increased risk of corrosion on iron materials. Copper is more positive than iron in the electrochemical voltage series, so that in the case of copper deposits, local elements are formed on the iron materials commonly used in heating technology, which corrode the iron-containing structural parts. This is significantly increased by the presence of sulfuric acid or sulfurous acid, which are formed when burning sulfur-containing fuels.

Zinkverbindungen sind weniger giftig als Kupfer und stellen auch keine wesentliche Korrosionsgefahr für Eisenwerkstoffe dar, sind jedoch als Verbrennungskatalysator für Ruß und Teere praktisch kaum wirksam.Zinc compounds are less toxic than copper and also pose no significant risk of corrosion for ferrous materials, but are practically hardly effective as a combustion catalyst for soot and tars.

Chrom wurde bisher für vorliegende Zwecke hauptsächlich in Form von Chromaten eingesetzt, um sowohl von der verbrennungs­katalytischen Wirkung des Metallions zu profitieren als auch das Oxidationspotential der Chromate auf Kohlenstoff auszu­nützen. Infolge der krebserregenden Wirkung einiger Chromver­bindungen scheiden diese jedoch nach den heutigen Umwelt­schutzanforderungen aus. Dasselbe gilt für Nickel- und Kobalt­verbindungen, obwohl insbesondere Kobalt in der Lage ist, eine gute verbrennungskatalytische Wirkung auszuüben.Chromium has so far been used for the present purposes mainly in the form of chromates, both to benefit from the combustion-catalytic effect of the metal ion and to utilize the oxidation potential of the chromates on carbon. Due to the carcinogenic effects of some chromium compounds, however, these are eliminated according to today's environmental protection requirements. The same applies to nickel and cobalt compounds, although cobalt in particular is able to have a good combustion catalytic effect.

Auch Mangan, insbesondere als Permanganat, hat gute verbren­nungskatalytische Eigenschaften und mit -1,70 Volt als MnO₂ + 2H₂O=MnO₄⁻ + 4 H⁺ + 3e⁻ ein hohes Oxidationspotential, jedoch sind Manganverbindungen ebenfalls giftig und sogar als kanzero­genverdächtig eingestuft worden.Manganese, in particular as permanganate, has good combustion-catalytic properties and, with -1.70 volts as MnO₂ + 2H₂O = MnO₄⁻ + 4 H⁺ + 3e⁻, a high oxidation potential, but manganese compounds are also toxic and have even been classified as carcinogenic.

Ein ungiftiges Übergangsmetall stellt Eisen dar, welches in öllöslicher Form (Eisenseifen, Ferrocen z.B.) als Verbrennungs­katalysator bei flüssigen Brennstoffen häufig eingesetzt wird. Auch die Einspritzung von wäßrigen Eisensalzlösungen, wie Eisensulfate, in die Flamme wurde vorgeschlagen bzw. gehand­habt. Trotz dieser positiven Eigenschaften für die Verbren­nungskatalyse stellten Eisenverbindungen ein ungenügendes Werk­zeug dar, um bereits gebildeten Ruß und Teere zu verbrennen. Der Grund liegt in dem relativ niedrigen Oxidationspotential von 3-wertigen Eisenverbindungen, nämlich -0,77 Volt Fe⁺⁺ = Fe⁺⁺⁺ + e⁻.Iron is a non-toxic transition metal, which is often used in oil-soluble form (iron soaps, ferrocene, for example) as a combustion catalyst in liquid fuels. The injection of aqueous iron salt solutions, such as iron sulfates, into the flame has also been proposed or handled. Despite these positive properties for combustion catalysis, iron compounds were an insufficient tool to burn soot and tars that had already formed. The reason lies in the relatively low oxidation potential of trivalent iron compounds, namely -0.77 volt Fe⁺⁺ = Fe⁺⁺⁺ + e⁻.

Auch Calziumverbindungen - wobei Calzium als Erdalkali bekannt­lich kein Übergangsmetall darstellt - wurden zur Beseitigung von Rußablagerungen empfohlen. Calzium hat eine nur geringfü­gige verbrennungskatalytische Wirkung und dürfte eine solche überhaupt nur bei hohen Verbrennungstemperaturen durch Bildung von Hydroxylionen in der Flamme ausüben. Als Erdalkali weist es jedoch eine Neutralisationswirkung auf Schwefel- und Schwe­feliger Säure auf, soweit es nicht an thermisch stabile und unverbrennbare Anionen gebunden ist.Calcium compounds - although calcium as an alkaline earth is not known to be a transition metal - have also been recommended for removing soot deposits. Calcium has only a slight combustion catalytic effect and is only likely to exert this effect at high combustion temperatures due to the formation of hydroxyl ions in the flame. However, as alkaline earth, it has a neutralizing effect on sulfuric and sulfuric acid, provided that it is not bound to thermally stable and non-combustible anions.

Als metallionenfreies Reinigungsmittel für feuerseitige Koh­lenstoffbeläge wurde weiters Wasserstoffperoxid verwendet. Dieses Oxidationsmittel wird auch in Verbindung mit freien Alkalien, wie Alkalihydroxide, -carbonate und -silikate empfoh­len, wobei die Oxidation des Russes durch H₂O₂ und die Säure­neutralisierung durch die starken wäßrigen Alkalilösungen er­ folgt; eine verbrennungskatalytische Wirkung tritt nicht auf.Hydrogen peroxide was also used as a metal ion-free cleaning agent for fire-side carbon deposits. This oxidizing agent is also recommended in conjunction with free alkalis such as alkali hydroxides, carbonates and silicates, whereby the oxidation of the carbon black by H₂O₂ and the acid neutralization by the strong aqueous alkali solutions follows; there is no combustion catalytic effect.

Beispiele für veröffentlichte Druckschriften sind die GB-PS 1 252 624 für Wasserstoffperoxid und starke wäßrige Alkali­lösungen, DE-OS 3 023 520 für die Zugabe von Calziumverbindun­gen (Calziumphosphate in Pulverform), DE-PS 2 413 520 für Ent­rußungsmittel auf Basis von Metallverbindungen enthaltend Kup­ferpulver, US-PS 4 287 090 für wäßrige katalytisch aktive Me­tallsalzlösungen bestehend aus Manganacetat, Calziumnitrat und Kupferacetat, DE-OS 2 911 259 als Mittel zur feuerseitigen Rei­nigung mit Alkalijodat oder Alkaliperjodatlösungen zusammen mit Kupfercarbonat als Oxidationshilfe und Ammoniak oder Al­kalicarbonate zur Neutralisierung saurer Aschebestandteile.Examples of published documents are GB-PS 1 252 624 for hydrogen peroxide and strong aqueous alkali solutions, DE-OS 3 023 520 for the addition of calcium compounds (calcium phosphates in powder form), DE-PS 2 413 520 for deblocking agents based on metal compounds containing copper powder , US Pat. No. 4,287,090 for aqueous catalytically active metal salt solutions consisting of manganese acetate, calcium nitrate and copper acetate, DE-OS 2 911 259 as a means of cleaning on the fire side with alkali iodate or alkali periodate solutions together with copper carbonate as oxidation aid and ammonia or alkali carbonates for neutralizing acidic ash components.

Als chemische Rußvernichter wurden Kaliumnitrat und Ammonium­nitrat in der DE-OS 2 228 467 (ohne katalytische Verbrennungs­wirkung) genannt. In der GB-PS 1 303 552 werden Ammoniumnitrat neben Kaliumnitrat und/oder Natriumnitrat zur Bindung und Kon­densierung von Schwefelsäure aus den Verbrennungsabgasen empfohlen.Potassium nitrate and ammonium nitrate were mentioned as chemical soot killers in DE-OS 2 228 467 (without a catalytic combustion effect). GB-PS 1 303 552 recommends ammonium nitrate in addition to potassium nitrate and / or sodium nitrate for the binding and condensation of sulfuric acid from the combustion exhaust gases.

Auch in einer Reihe anderer feuerseitiger Reiniger von Heiz­flächen werden zur Beseitigung der Ruß- und Teeranteile unter­stützende Oxidationsmittel bzw. katalytische Verbrennungshil­fen wie Ammoniumnitrat, Ammoniumchromat bzw. Zink- und Kupfer­salze (DE-OS 1 810 424) genannt.In a number of other fire-side cleaners of heating surfaces, supporting oxidants or catalytic combustion aids such as ammonium nitrate, ammonium chromate or zinc and copper salts (DE-OS 1 810 424) are mentioned to remove the soot and tar fractions.

Die schwedischen Nobel-Werke haben bereits vor Jahren, zur Reinhaltung von Heizflächen unter der Marke SP-SOTIN ein Mit­tel herausgebracht, das als Hauptbestandteil laut eigenen An­gaben Alkalinitrate enthält (kein Verbrennungskatalysator).Years ago, the Swedish Nobel works brought out an agent for keeping heating surfaces clean under the brand SP-SOTIN, which, according to its own statements, contains alkali nitrates (no combustion catalyst).

Alle genannten Mittel haben die Beseitigung von Ruß und Teeren zum Ziele, können jedoch die heutigen Anforderungen an eine umweltfreundliche und möglichst ohne größere Verluste erfol­gende Wärmeübertragung nur ungenügend erfüllen. Die katalyti­ sche Verbrennung durch geeignete Metalle hat bei guter Wirk­samkeit den Nachteil von Giftstoffen im Abgas (Cu, Ni, Co, Cr, Mn), während das Oxidationspotential bei den umweltfreund­lichen Metallen, wie Fe, Ca ungenügend ist. Beim Einsatz von Oxidationsmitteln, wie Nitraten, Jodaten oder Peroxiden ist nur eine einmalige Wirkung vorhanden und kann sich Ruß und Teer nach Verbrauch des aktiven Sauerstoffes aus diesen Substanzen wieder unbehindert ablagern und die Wärmebilanz verschlechtern sowie durch Rußausstoß die Umwelt belasten.All of the means mentioned aim at the removal of soot and tars, but can only insufficiently meet today's requirements for environmentally friendly heat transfer, which if possible takes place without major losses. The catalytic With good effectiveness, combustion by suitable metals has the disadvantage of toxins in the exhaust gas (Cu, Ni, Co, Cr, Mn), while the oxidation potential of environmentally friendly metals, such as Fe, Ca, is insufficient. When using oxidizing agents such as nitrates, iodates or peroxides there is only a one-off effect and soot and tar can be deposited again without hindrance after consumption of the active oxygen from these substances and worsen the heat balance and pollute the environment due to soot emissions.

Es ist hiebei zu beachten, daß z.B. eine Rußdicke als Abla­gerung von nur 1 mm die Abgastemperatur um ca. 70°C erhöhen kann und einen Heizöl-(Heizstoff)-Mehrverbrauch von 5 % nach sich zieht.It should be noted that e.g. a soot thickness as a deposit of only 1 mm can increase the exhaust gas temperature by approx. 70 ° C and entails additional fuel oil (heating) consumption of 5%.

Aufgabe der Erfindung ist es daher, einen Verbrennungskata­lysator zu schaffen, der ungiftig, katalytisch für die Ver­brennung bei möglichst niedrigen Temperaturen von Ruß und Teeren durch Luftsauerstoff hochwirksam ist, sowie in seiner höherwertigen Form ein hohes Oxidationspotential aufweist. Weiters soll nach erfolgter Verbrennung bzw. thermischer Zersetzung ein Neutralisationspotential gegeben sein.The object of the invention is therefore to provide a combustion catalyst which is non-toxic, catalytically highly effective for the combustion at the lowest possible temperatures of soot and tars due to atmospheric oxygen, and which has a high oxidation potential in its higher-quality form. Furthermore, there should be a neutralization potential after combustion or thermal decomposition.

Als solcher Verbrennungskatalysator wurden Lanthanide, ins­besondere Cerverbindungen in ihrer vierwertigen Form als geeignet gefunden. Wasserlösliche Cerverbindungen sind un­giftig und Cernitrat-Hexahydrat weist z.B. eine LD50(oral-rat) von 4200 mg/kg auf, im Vergleich zu reinem Kochsalz LD50(oral-rat) von lediglich 3000 mg/kg.Lanthanides, in particular cerium compounds, in their tetravalent form have been found suitable as such a combustion catalyst. Water-soluble cerium compounds are non-toxic and cerium nitrate hexahydrate has, for example, an LD50 (oral-rat) of 4200 mg / kg, compared to pure table salt LD50 (oral-rat) of only 3000 mg / kg.

Vierwertige Cerverbindungen stellen starke Oxidationsmittel dar, das Oxidationspotential von Ce(IV)/Ce(III) beträgt ca. 1,6 Volt, d.h. es liegt nur geringfügig unter dem vorgenann­ten von Permanganat zu Mangandioxid mit ca. 1,7 Volt und über doppelt so hoch als beim Fe(III)/Fe(II).Tetravalent cerium compounds are strong oxidizing agents, the oxidation potential of Ce (IV) / Ce (III) is approx. 1.6 volts, ie it is only slightly below that of permanganate to manganese dioxide with approx. 1.7 volts and more than twice as much high than for Fe (III) / Fe (II).

Öllösliche Cerverbindungen wurden bereits früher als Heizölzusätze zur verbesserten Verbrennung eingesetzt, gemäß der DE-OS 2 729 365 und der US-PS 4 462 810. Es handelt sich hiebei aber um ausschließlich öllösliche und nicht wäßrige Lösun­gen von Cerverbindungen. Überdies ist das Cer dort in seiner dreiwertigen Form als Zusatz vorhanden und nicht vierwertig.Oil-soluble cerium compounds have previously been used as fuel oil additives for improved combustion, in accordance with DE-OS 2 729 365 and US Pat. No. 4,462,810. However, these are exclusively oil-soluble and non- aqueous solutions of cerium compounds. In addition, the cerium is there in its trivalent form as an additive and not tetravalent.

Beide bekannten Anwendungen sind somit für die feuerseitige Reinigung von Ruß und Teeren nicht vorgesehen und auch nicht geeignet.Both known applications are therefore not intended for the fire-side cleaning of soot and tars and are also not suitable.

Für die feuerseitige Reinigung hat sich weiters als vorteil­haft erwiesen, wenn nach Verbrennung des Rußes oder Teeres bzw. nach thermischer Zersetzung der aufgebrachten vierwer­tigen wäßrigen Cerlösung eine Alkalitätsreserve vorhanden ist, um Säuren aus den verbrannten Heizstoffen zu neutrali­sieren. Diese Neutralisierung von anorganischen Säuren, wie Schwefel- und Schwefelige Säure und organischen, wie Essig­säure, Propionsäure, Ameisensäure vermindert die Ablagerung feuchter und haftender, Kohlenstoff enthaltender Beläge auf den festen Oberflächen, wie insbesondere solche zur Wärmeüber­tragung und inhibiert die korrodierende Wirkung dieser Säuren auf die Werkstoffe. Die Verwendung wäßriger vierwertiger Cerlösungen bei Vorhandensein obiger Alkalitätsreserve bietet den Vorteil, daß diese verbrennungskatalytisch wirksamen Lösungen auch um den Neutralpunkt (pH = 7) eingestellt werden können bzw. in schwach sauren oder mild alkalisch reagieren­den wäßrigen Lösungen vorliegen können.For cleaning on the fire side, it has also proven to be advantageous if, after burning the soot or tar or after thermal decomposition of the tetravalent aqueous cerium solution applied, an alkalinity reserve is present in order to neutralize acids from the burned fuels. This neutralization of inorganic acids, such as sulfuric and sulfuric acid and organic, such as acetic acid, propionic acid, formic acid, reduces the deposition of moist and adherent, carbon-containing deposits on the solid surfaces, in particular those for heat transfer, and inhibits the corrosive action of these acids on the Materials. The use of aqueous tetravalent cerium solutions in the presence of the above-mentioned alkalinity reserve offers the advantage that these combustion-catalytically active solutions can also be adjusted around the neutral point (pH = 7) or can be present in weakly acidic or mildly alkaline aqueous solutions.

Die Erfindung ist in erster Linie dadurch gekennzeichnet, daß die wäßrige Katalysatorlösung einen pH-Wert von mindestens 7 aufweist und in katalytisch wirksamer Menge vierwertiges Cer (Ce⁴⁺) und Alkali-, Erdalkali- und/oder Magnesiumverbindungen, die nach ihrer Verbrennung oder thermischen Zersetzung alka­lisch reagieren, sowie Komplexierungsmittel für dieses Ce⁴⁺ enthält. Weitere vorteilhafte Merkmale der Erfindung sind den Ansprüchen und der Beschreibung zu entnehmen.The invention is primarily characterized in that the aqueous catalyst solution has a pH of at least 7 and in a catalytically effective amount of tetravalent cerium (Ce⁴⁺) and alkali, alkaline earth and / or magnesium compounds, which after their combustion or thermal decomposition react alkaline, and contains complexing agents for this Ce⁴⁺. Further advantageous features of the invention can be found in the claims and the description.

Gegenüber den stark sauren Lösungen z.B. von Cernitrat bringt dies entsprechenden Korrosionsschutz für die damit behandelten metallischen Oberflächen. Auch stark alkalisch reagierende wäßrige Lösungen bieten Angriffsgefahren für metallische und insbesondere mineralische Baustoffe, wie Schamotten, sowie Verätzungsgefahren für den Anwender bei der Aufbringung.Compared to the strongly acidic solutions e.g. from Cernitrat this provides appropriate corrosion protection for the metallic surfaces treated with it. Aqueous solutions with a strongly alkaline reaction also offer risks of attack for metallic and in particular mineral building materials, such as chamottes, as well as burns for the user during application.

Die nachfolgenden Beispiele sollen die vorliegende Erfindung näher erläutern.The following examples are intended to explain the present invention in more detail.

Beispiel 1example 1

In 77,4 Gewichtsteilen (GT) Wasser werden 6 GT dreiwertiges Cernitrat = Ce(NO₃)₃.6H₂O gelöst und mit 2,2 GT 35%igem Wasser­stoffperoxid in die vierwertige Form überführt, entsprechend etwa 2 Gew.-% Cer⁴⁺ in der fertigen Lösung. Weiters wurden 3 GT Citronensäure und 2 GT eines Natriumsalzes von Malein­säure-Acryl-Copolymer mit einem Molekulargewicht von durch­schnittlich 70.000 als Komplexierungsmittel obiger Lösung zugeführt und mit 4,4 GT Ätzkali (KOH) auf einen pH-Wert von ca. 9 gebracht. Zur verbesserten Netzung auf den verrußten und verteerten festen Oberflächen werden dieser wäßrigen Lösung noch 2 GT eines synthetischen Alkohols mit 13 Kohlen­stoffatomen und 9 Molen Äthylenoxidanlagerung zugefügt. Es entsteht eine stabile, klare Lösung von rotbrauner Farbe.In 77.4 parts by weight (GT) of water 6 GT trivalent cerium nitrate = Ce (NO₃) ₃.6H₂O are dissolved and converted into the tetravalent form with 2.2 GT 35% hydrogen peroxide, corresponding to about 2 wt .-% Cer⁴⁺ in the finished solution. Furthermore, 3 pbw of citric acid and 2 pbw of a sodium salt of maleic acid / acrylic copolymer with an average molecular weight of 70,000 were added as a complexing agent to the above solution and brought to a pH of approx. 9 with 4.4 pbw of caustic potash (KOH). For improved wetting on the sooty and tarred solid surfaces, 2 parts by weight of a synthetic alcohol with 13 carbon atoms and 9 moles of ethylene oxide addition are added to this aqueous solution. A stable, clear solution of red-brown color is created.

Diese Lösung wird auf verrußte und teerige Oberflächen aufge­sprüht. Durch nachfolgende Beheizung dieser Oberflächen im normalen Gebrauch tritt ein Abbrennen der kohlenstoff- und kohlenwasserstoffhältigen Beläge (Ruß, Teer) katalytisch begünstigt ein.This solution is sprayed onto sooty and tarred surfaces. Subsequent heating of these surfaces in normal use leads to a catalytically favored burning off of the carbon and hydrocarbon-containing deposits (soot, tar).

Die vorgenannte Lösung kann auch vorteilhafterweise nach der jeweiligen, in vielen Ländern obligatorisch vorgeschrie­benen, mechanischen Reinigung auf Wärmeübertragungsflächen und andere rußgefährdete Oberflächen aufgetragen werden und dient sowohl als Korrosionsschutz als auch insbesondere als katalytisch wirksamer Oberflächenüberzug, welcher die erneute Verrußung und Verteerung weitgehend inhibiert.The aforementioned solution can also advantageously be applied to heat transfer surfaces and other soot-endangered surfaces after the respective mechanical cleaning, which is mandatory in many countries, and serves both as corrosion protection and in particular as catalytically effective surface coating, which largely inhibits sooting and taring.

Nach Abbrennen der organischen Substanzen (auch der Citronen­säure und des Malein-Acryl-Copolymers) verbleiben ca. 1,9 % vierwertiges Cer, vorwiegend als CeO₂, sowie ca. 5 % Ätzal­kalien (aus 4,4 % KOH und dem Natriumsalz des Copolymers) aus 100 % der vorgenannten Lösung zum Zwecke der katalyti­schen Verbrennung von Ruß und Teeren sowie zur Neutralisie­rung von Mineralsäuren, vorwiegend Schwefel und Schwefeliger Säure sowie organischer Säuren, wie insbesondere Essigsäure (aus der Holzverbrennung).After burning off the organic substances (also the citric acid and the maleic acrylic copolymer), approx. 1.9% tetravalent cerium remains, predominantly as CeO₂, and approx. 5% caustic alkalis (from 4.4% KOH and the sodium salt of the copolymer) from 100% of the aforementioned solution for the purpose of the catalytic combustion of soot and tars and for the neutralization of mineral acids, mainly sulfur and sulfuric acid as well as organic acids, such as acetic acid (from wood burning).

Beispiel 2Example 2

Die wäßrige Katalysatorlösung laut Beispiel 1 wird 1:10 mit Wasser verdünnt und periodisch auf Wärmeübertragungsflächen und andere zu entrußende Oberflächen mittels einer mechani­schen, eingebauten Sprühvorrichtung aufgebracht. Es zeigt sich, daß - je nach Heizbelastung und Verrußungsgrad - eine periodische Aufsprühung in 2- bis 24-stündigen Intervallen ausreicht, um Rußbeläge zu verhindern und einen bestmöglichen Wärmeübergang und damit Ausnützung der Brennstoffe zu errei­chen. Diese Methode ist vor allem für Großanlagen, d.h. in­dustrielle Anlagen und kalorische Kraftwerke geeignet.The aqueous catalyst solution according to Example 1 is diluted 1:10 with water and periodically applied to heat transfer surfaces and other surfaces to be sooted by means of a mechanical, built-in spray device. It turns out that - depending on the heating load and the degree of sootiness - a periodic spraying in 2- to 24-hour intervals is sufficient to prevent soot deposits and to achieve the best possible heat transfer and thus utilization of the fuels. This method is mainly for large systems, i.e. industrial plants and caloric power plants.

Beispiel 3Example 3

Die wäßrige Katalysatorlösung laut Beispiel 1 wird 1:20 mit Wasser verdünnt, was bedeutet, daß in der fertigen Verdünnung etwa 1.000 ppm vierwertige Cerionen enthalten sind. Davon werden durch Feinsteinsprühung in die Verbrennungsluft von größeren Heiz- und Kesselanlagen im Verhältnis von 1 GT ver­dünnter wäßriger Lösung per 50 GT Rückstandsheizöl als Ver­ brennungskatalysator eingebracht. Durch den relativ geringen Anteil von 20 ppm vierwertigem Cer im Verhältnis zum schweren Heizöl wird eine Reduktion der Rußzahl um 3 Punkte nach Bacharach erreicht.The aqueous catalyst solution according to Example 1 is diluted 1:20 with water, which means that the finished dilution contains about 1,000 ppm of tetravalent cerium ions. Of these, fine stone spraying into the combustion air of larger heating and boiler systems in the ratio of 1 GT diluted aqueous solution per 50 GT residue heating oil as Ver combustion catalyst introduced. Due to the relatively low proportion of 20 ppm tetravalent cerium in relation to the heavy heating oil, the soot number is reduced by 3 points according to Bacharach.

Beispiel 4Example 4

10 GT eines vierwertigen wasserdispergierbaren Cer-Hydrates werden in 79 GT Wasser feinst verteilt. Hiezu werden 10 GT eines Natriumpolyacrylates mit Molekulargewicht von durch­schnittlich 4000 gelöst sowie 1 GT von Nonylphenol mit 7 Mo­len Äthylenoxidanlagerung.10 pbw of a tetravalent water-dispersible cerium hydrate are finely distributed in 79 pbw of water. To this end, 10 pbw of a sodium polyacrylate with an average molecular weight of 4000 are dissolved, and 1 pbw of nonylphenol with 7 moles of ethylene oxide addition.

Das Cer-Hydrat enthält 89 % CeO₂. Die Teilchengröße beträgt 15 Mikrometer, die Kristallgröße (XRD) ca. 9 Nanometer. Der Ce⁴⁺-Gehalt liegt bei 7,2 Gew.-%, bezogen auf die Dispersion.The cerium hydrate contains 89% CeO₂. The particle size is 15 micrometers, the crystal size (XRD) is approximately 9 nanometers. The Ce⁴⁺ content is 7.2 wt .-%, based on the dispersion.

Die oben genannte wäßrige Dispersion wird auf Teerablagerun­gen bei Holzfeuerungen aufgesprüht und durch kurze, verstärk­te Luftzufuhr abgebrannt. Es zeigt sich, daß durch die kata­lytische Wirkung des vierwertigen Cers auch in dieser Form die gesundheitsschädlichen und auch brandgefährlichen Teer­rückstände fast vollständig abgebrannt werden können.The above-mentioned aqueous dispersion is sprayed onto tar deposits in wood-burning systems and burned off by means of a brief, increased supply of air. It turns out that the catalytic effect of the tetravalent cerium can also be used to almost completely burn off the harmful and fire-hazardous tar residues in this form.

Beispiel 5Example 5

In 70 GT Wasser werden 10 GT dreiwertiges Cernitrat gelöst und mit 3 GT 35%igem Wasserstoffperoxid in die vierwertige Form überführt (entsprechend etwa 3,4 Gew.-% Cer⁴⁺). Weiters werden 10 GT Magnesiumnitrat, 5 GT Polyacrylate mit Molekular­gewicht 2.000 (im Durchschnitt) gelöst und mit Kalilauge oder Ätzkali auf einen pH-Wert von 8 gebracht.10 pbw of trivalent cerium nitrate are dissolved in 70 pbw of water and converted into the tetravalent form with 3 pbw of 35% hydrogen peroxide (corresponding to about 3.4% by weight of cerium). Furthermore, 10 pbw of magnesium nitrate, 5 pbw of polyacrylates with a molecular weight of 2,000 (on average) are dissolved and brought to a pH of 8 using potassium hydroxide solution or caustic potash.

Diese Lösung wird auf rußige und teerige Oberflächen aufge­ bracht und verbessert die Verbrennung dieser schädlichen Beläge ähnlich Beispiel 1. Für ölige und fettige Rußbeläge empfiehlt sich noch der Zusatz von Netzmitteln. Vorteilhaf­terweise werden nichtionische oder anionaktive oberflächen­aktive Substanzen verwendet, wie Ähtylenoxidanlagerungspro­dukte, Alkansulfonate, Alkylarylsulfonate. Kationaktive wasch­aktive Substanzen sind zwar ebenfalls geeignet, erniedrigen aber häufig die Grenzenflächenspannung zwischen der wäßrigen Katalysatorlösung und den öligen/teerigen Rückständen in geringerem Ausmaße und sind auch wirtschaftlich ungünstiger.This solution is applied to sooty and tarry surfaces brings and improves the combustion of these harmful coatings similar to Example 1. For oily and greasy soot coatings, the addition of wetting agents is recommended. Nonionic or anionic surface-active substances are advantageously used, such as ethylene oxide addition products, alkanesulfonates, alkylarylsulfonates. Cationactive wash-active substances are also suitable, but they often lower the interfacial tension between the aqueous catalyst solution and the oily / tarry residues to a lesser extent and are also less economical.

Bei der Abbrennung von Ruß und Teeren wird auch das Magne­siumnitrat thermisch zersetzt und kann als basisches Oxid/­Hydroxid ebenfalls die Mineralsäuren, aber auch organische Säuren, welche sich bei der Verbrennung von schwefelhältigen Heizölen und Kohlen bzw. bei Holz, Stroh etc. bilden, entspre­chend neutralisieren.When soot and tars are burned off, the magnesium nitrate is also thermally decomposed and, as a basic oxide / hydroxide, the mineral acids as well, but also organic acids, which form when burning sulfur-containing heating oils and coals or in the case of wood, straw, etc., accordingly neutralize.

Beispiel 6Example 6

Die Lösung gemäß Beispiel 5 wird analog angesetzt, wobei Magnesiumnitrat durch Bariumnitrat ersetzt wird. Auch hier tritt durch thermische Zersetzung eine Alkalitätsreserve, sowie die genannte Verbrennungskatalyse ein.The solution according to Example 5 is prepared analogously, with magnesium nitrate being replaced by barium nitrate. Here too, an alkalinity reserve occurs due to thermal decomposition, as well as the combustion catalysis mentioned.

Beispiel 7Example 7

Analog den Beispielen 5 und 6, wobei statt Magnesiumnitrat Calziumnitrat eingesetzt wird.Analogous to Examples 5 and 6, with calcium nitrate being used instead of magnesium nitrate.

Beispiel 8Example 8

Es wird eine Lösung gemäß Beispiel 1 angesetzt, wobei das Ätzkali durch Lithiumhydroxid-Monohydrat ersetzt wird. Lithium­hydroxid weist nicht nur eine Säure neutralisierende Wirkung auf, sondern auch eine das vierwertige Cer unterstützende verbrennungskatalytische Wirkung.A solution according to Example 1 is prepared, the Caustic potash is replaced by lithium hydroxide monohydrate. Lithium hydroxide not only has an acid-neutralizing effect, but also a combustion-catalytic effect which supports the tetravalent cerium.

Beispiel 9Example 9

In 77 GT Wasser werden 5 GT Cernitrat (Ce(NO₃)₂.6H₂O gelöst und mit 2 GT Wasserstoffperoxid (35 %) in die vierwertige Cerform überführt (etwa 1,7 Gew.-% Cer⁴⁺). Weiters werden 25 GT einer 40%igen Lösung des Tetranatriumsalzes von Äthylen­diamintetraessigsäure (EDTA) und 1 GT Netzmittel zugefügt. Diese Lösung wird analog den vorgenannten Beispielen als wäßriger Verbrennungskatalysator eingesetzt.5 pbw of cerium nitrate (Ce (NO₃) ₂.6H₂O are dissolved in 77 pbw of water and converted into the tetravalent cerium form with 2 pbw of hydrogen peroxide (35%) (approx. 1.7% by weight of cerium). 25 pbw of a 40th % solution of the tetrasodium salt of ethylenediaminetetraacetic acid (EDTA) and 1 part by weight of wetting agent, which is used as an aqueous combustion catalyst analogously to the abovementioned examples.

Beispiel 10Example 10

Zusammensetzung gemäß Beispiel 9, wobei statt EDTA das Natrium­nitrilotriacetat (NTA) Verwendung findet.Composition according to Example 9, the sodium nitrilotriacetate (NTA) being used instead of EDTA.

Beispiel 11Example 11

40 GT Cernitrat (3-wertig) werden in 60 GT Wasser gelöst und mit 20 GT 35%igem Wasserstoffperoxid in die vierwertige Form gebracht (etwa 13,3 Gew.-% Cer⁴⁺). Weiters werden 60 GT der Oxyessigsäure (Glykolsäure) zugefügt und mit Kalilauge oder Ätzkali auf einen pH-Wert von 7 eingestellt. Die Lösung wird im Sinne der vorgenanntne Beispiele als wäßriger Ver­brennungskatalysator für flüssige, feste und auch gasförmige Brennstoffe eingesetzt.40 pbw of cerium nitrate (trivalent) are dissolved in 60 pbw of water and brought into the tetravalent form with 20 pbw of 35% hydrogen peroxide (about 13.3% by weight of cerium). 60 pbw of oxyacetic acid (glycolic acid) are also added and the pH is adjusted to 7 using potassium hydroxide solution or caustic potash. The solution is used in the sense of the aforementioned examples as an aqueous combustion catalyst for liquid, solid and also gaseous fuels.

Beispiel 12Example 12

10 GT Cernitrat (3-wertig) werden in 60 GT Wasser gelöst und mit 3 GT 35%igem Wasserstoffperoxid in die vierwertige Form gebracht (etwa 3,3 Gew.-% Cer⁴⁺). Weiters werden 7 GT Kaliumcarbonat und 20 GT einer 40%igen Lösung von Tetra­kalium-EDTA zugeführt. Diese Lösung wird im Verhältnis 1:1000 Gewichtsteile Heizölen mechanisch in feinster Teil­chengröße eindispergiert. Die W/O-Emulsion wird zur Verbren­nung gebracht, wobei Rußbildungen weitgehend vermieden werden können. SO₃ bzw. H₂SO₄ wird durch die Neutralisationswirkung des KOH zum Großteil bevorzugt gebunden, sodaß auch bei der Verbrennung schwefelreicher Heizöle vorwiegend das schwächer saure und damit weniger aggressive und korrosive SO₂ bzw. Schwefelige Säure im Abgas vorhanden sind.10 pbw of cerium nitrate (trivalent) are dissolved in 60 pbw of water and brought into the tetravalent form with 3 pbw of 35% hydrogen peroxide (about 3.3% by weight of cerium). Furthermore, 7 pbw of potassium carbonate and 20 pbw of a 40% solution of tetrapotassium EDTA are added. This solution is mechanically dispersed in the finest particle size in a ratio of 1: 1000 parts by weight of heating oils. The W / O emulsion is burned, soot formation can be largely avoided. SO₃ or H₂SO₄ is largely bound by the neutralizing effect of KOH, so that even when burning sulfur-rich heating oils, the weakly acidic and thus less aggressive and corrosive SO₂ or sulfuric acid are mainly present in the exhaust gas.

In vorteilhafter Weise liegt allgemein der Gehalt der Cer⁴⁺-­Ionen in der erfindungsgemäßen Katalysatorlösung zwischen 0,1 und 15 Gew.-% der Katalysatorlösungsmenge und der Metall­ionengehalt der alkalisch reagierenden Verbindung liegt vorteilhaft zwischen 0,1 und 30 Gew.-%, bezogen auf die Katalysatorlösungsmenge. Im flüssigen oder festen Brennstoff liegt der Cer⁴⁺-Ionengehalt bevorzugt zwischen 1 und 100 ppm, bezogen auf die Brennstoffmenge.Advantageously, the content of the cerium ions in the catalyst solution according to the invention is generally between 0.1 and 15% by weight of the amount of catalyst solution and the metal ion content of the alkaline compound is advantageously between 0.1 and 30% by weight, based on the amount of catalyst solution. In the liquid or solid fuel, the Cer⁴⁺ ion content is preferably between 1 and 100 ppm, based on the amount of fuel.

Die erfindungsgemäße Katalysatorlösung liegt bei einem pH-­Wert von mindestens 7 im neutralen oder basischen Bereich. Damit wird dem erforderlichen Korrosionsschutz Rechnung ge­tragen. Das Komplexierungsmittel ist in der Katalysatorlösung bevorzugt in einer solchen Menge vorhanden, daß das Ausfallen des Cers als Hydroxid verhindert ist. Der Mengenbereich für das Komplexierungsmittel kann zwischen 1 und 40 Gew.-%, be­zogen auf die gesamte Katalysatormenge, bevorzugt zwischen 2 und 10 Gew.-% liegen.The catalyst solution according to the invention is at a pH of at least 7 in the neutral or basic range. This takes into account the required corrosion protection. The complexing agent is preferably present in the catalyst solution in such an amount that precipitation of the cerium as a hydroxide is prevented. The quantity range for the complexing agent can be between 1 and 40% by weight, based on the total amount of catalyst, preferably between 2 and 10% by weight.

Claims (14)

1. Wäßrige Katalysatorlösung zur verbesserten Verbrennung von Kohlen­stoff und/oder Kohlenwasserstoff enthaltenden Stoffen, wie Heizöle, Heiz­gase und feste Brennstoffe und/oder zur Entfernung von Ruß- oder Teer­ablagerungen auf Oberflächen des Brennraumes, wobei die Katalysatorlösung Cersalze enthält, dadurch gekennzeichnet, daß die wäßrige Katalysatorlö­sung eine pH-Wert von mindestens 7 aufweist und in katalytisch wirksamer Menge vierwertiges Cer (Ce⁴⁺) und Alkali-, Erdalkali- und/od. Magnesiumver­bindungen, die nach ihrer Verbrennung oder thermischen Zersetzung alka­lisch reagieren, sowie Komplexierungsmittel für dieses Ce⁴⁺ enthält.1. Aqueous catalyst solution for improved combustion of carbon and / or hydrocarbon-containing substances, such as heating oils, heating gases and solid fuels and / or for removing soot or tar deposits on surfaces of the combustion chamber, the catalyst solution containing cerium salts, characterized in that the aqueous Catalyst solution has a pH of at least 7 and in a catalytically effective amount tetravalent cerium (Ce⁴⁺) and alkali, alkaline earth and / or. Magnesium compounds that react alkaline after their combustion or thermal decomposition, and contains complexing agents for this Ce⁴⁺. 2. Katalysatorlösung nach Anspruch 1, dadurch gekennzeichnet, daß als alkalisch reagierende Verbindungen organische Kalium-, Natrium-, Lithium­salze bzw. Seifen enthalten sind.2. Catalyst solution according to claim 1, characterized in that organic potassium, sodium, lithium salts or soaps are contained as alkaline compounds. 3. Katalysatorlösung nach Anspruch 1, dadurch gekennzeichnet, daß als alkalisch reagierende Verbindungen organische Calzium, Magnesium- und/oder Bariumverbindungen enthalten sind.3. Catalyst solution according to claim 1, characterized in that organic calcium, magnesium and / or barium compounds are present as alkaline compounds. 4. Katalysatorlösung nach Anspruch 1, dadurch gekennzeichnet, daß als alkalisch reagierende Verbindungen Nitrate von Alkalien, Erdalkalien und/oder Magnesium enthalten sind.4. Catalyst solution according to claim 1, characterized in that nitrates of alkalis, alkaline earths and / or magnesium are contained as alkaline compounds. 5. Katalysatorlösung nach Anspruch 1, dadurch gekennzeichnet, daß als alkalisch reagierende Verbindungen Carbonate von Alkalien, Erdalkalien und/oder Magnesium enthalten sind.5. Catalyst solution according to claim 1, characterized in that carbonates of alkalis, alkaline earths and / or magnesium are contained as alkaline reacting compounds. 6. Katalysatorlösung nach Anspruch 1, dadurch gekennzeichnet, daß als alkalisch reagierende Verbindungen Polycarboxylate von Alkalien, Erd­alkalien und/oder Magnesium enthalten sind.6. Catalyst solution according to claim 1, characterized in that polycarboxylates of alkalis, alkaline earths and / or magnesium are contained as alkaline reacting compounds. 7. Katalysatorlösung nach Anspruch 1, dadurch gekennzeichnet, daß als alkalisch reagierende Verbindungen Hydroxycarboxylate von Alkalien, Erd­alkalien und/oder Magnesium enthalten sind.7. Catalyst solution according to claim 1, characterized in that the alkali-reacting compounds contain hydroxycarboxylates of alkalis, alkaline earths and / or magnesium. 8. Katalysatorlösung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Katalysatorlösung Cer⁴⁺ in Mengen zwischen 0,1 und 15 Gew.-%, bezogen auf die gesamte Katalysatorlösungsmenge, enthält, und daß die alkalisch reagierende Verbindung in Mengen zwischen 0,1 und 30 Gew.-%, bezogen auf den Metallionengehalt und die gesamte Katalysa­torlösungsmenge, enthalten ist.8. Catalyst solution according to one of the preceding claims, characterized in that the catalyst solution Cer⁴⁺ in amounts between 0.1 and 15 wt .-%, based on the total amount of catalyst solution, and that the alkaline compound in amounts between 0.1 and 30 wt .-%, based on the metal ion content and the total amount of catalyst solution is included. 9. Katalysatorlösung nach einem der vorhergehenden Ansprüche 1 bis 8, dadurch gekennzeichnet, daß das Komplexierungsmittel in Mengen von 1 - 40 Gew.-%, bezogen auf die gesamte Katalysatorlösungsmenge, enthalten ist.9. Catalyst solution according to one of the preceding claims 1 to 8, characterized in that the complexing agent is contained in amounts of 1 - 40 wt .-%, based on the total amount of catalyst solution. 10. Katalysatorlösung nach Anspruch 9, dadurch gekennzeichnet, daß das Komplexierungsmittel in Mengen von 2 - 10 Gew.-% enthalten ist.10. Catalyst solution according to claim 9, characterized in that the complexing agent is contained in amounts of 2 - 10 wt .-%. 11. Verwendung der wäßrigen Katalysatorlösung gemäß den Ansprüchen 1 bis 10, dadurch gekennzeichnet, daß sie kontinuierlich oder periodisch in den Brennraum eingebracht, vorzugsweise eingesprüht wird.11. Use of the aqueous catalyst solution according to claims 1 to 10, characterized in that it is introduced continuously or periodically into the combustion chamber, preferably sprayed. 12. Verwendung der wäßrigen Katalysatorlösung gemäß den Ansprüchen 1 bis 10, dadurch gekennzeichnet, daß sie vor der Verbrennung in flüssi­gen Brennstoff dispergiert oder emulgiert wird.12. Use of the aqueous catalyst solution according to claims 1 to 10, characterized in that it is dispersed or emulsified in liquid fuel before combustion. 13. Verwendung der wäßrigen Katalysatorlösung gemäß den Ansprüchen 1 bis 10, dadurch gekennzeichnet, daß sie vor der Verbrennung auf festen Brennstoff aufgebracht wird.13. Use of the aqueous catalyst solution according to claims 1 to 10, characterized in that it is applied to solid fuel before combustion. 14. Flüssiger oder fester Brennstoff, insbesondere Heizöl oder Kohle, dadurch gekennzeichnet, daß er die wäßrige Katalysatorlösung gemäß einem oder mehreren der Ansprüche 1 bis 10 in einer Menge enthält, daß der Cer⁴⁺-Gehalt zwischen 1 und 100 ppm, bevorzugt zwischen 15 und 35 ppm, bezogen auf die Brennstoffmenge, liegt.14. Liquid or solid fuel, in particular heating oil or coal, characterized in that it contains the aqueous catalyst solution according to one or more of claims 1 to 10 in an amount that the cerium content between 1 and 100 ppm, preferably between 15 and 35 ppm, based on the amount of fuel.
EP89890256A 1988-10-03 1989-09-29 Aqueous combustion catalysts and fuels Expired - Lifetime EP0368834B1 (en)

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AT0244188A AT391873B (en) 1988-10-03 1988-10-03 AQUEOUS CATALYST SOLUTION AND FUELS

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AT395383B (en) * 1991-04-25 1992-12-10 Ind Und Bergbaugesellschaft Pr COMBINED METHOD FOR INCREASING THE LEVEL OF REALIZATION IN THE COMBUSTION OF FUELS AND FOR THE REMOVAL OF SULFUR AND NITROGEN OXIDS FROM THE EXHAUST GAS
FR2698346A1 (en) * 1992-11-25 1994-05-27 Rhone Poulenc Chimie Ceric oxide crystallite aggregate, process for obtaining it and its use for reducing combustion residues.
WO1995011287A1 (en) * 1993-10-18 1995-04-27 Ica Innoconsult Ag Corrosion-proofing process
DE4417874A1 (en) * 1994-05-24 1995-11-30 Erc Emissions Reduzierungs Con Reducing boiler deposits in combustion plants
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
WO1996026255A1 (en) * 1995-02-24 1996-08-29 Rhone-Poulenc Chimie Use of a cerium compound for protecting internal combustion engines
WO1997044414A1 (en) * 1996-05-20 1997-11-27 Bp Chemicals (Additives) Limited Marine diesel process and fuel therefor
DE19643866C2 (en) * 1996-10-30 2001-09-20 Gottfried Roessle Heat exchange and cleaning processes for exhaust gas from a power plant
WO2008042089A2 (en) * 2006-10-03 2008-04-10 Siemens Water Technologies Corp. Wet oxidation of soot
US7993588B2 (en) 2006-10-03 2011-08-09 Siemens Industry, Inc. Catalytic wet oxidation systems and methods
WO2012064084A2 (en) * 2010-11-08 2012-05-18 Oh Mi Hye Liquid-combustion catalyst composition including mixed metal-complex ionic compound
US8501149B2 (en) 2011-02-18 2013-08-06 Siemens Energy, Inc. H2S conversion to sulfur using a regenerated iodine solution
EP2749355A2 (en) 2012-12-29 2014-07-02 SMF Poland Spolka Z Ograniczona Odpowiedzialnoscia The catalyst suspension and method for preparing thereof
US9193613B2 (en) 2006-10-03 2015-11-24 Siemens Energy, Inc. pH control to enable homogeneous catalytic wet air oxidation
US9315401B2 (en) 2007-01-22 2016-04-19 Siemens Energy, Inc. Wet air oxidation process using recycled copper catalyst

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Cited By (27)

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AT395383B (en) * 1991-04-25 1992-12-10 Ind Und Bergbaugesellschaft Pr COMBINED METHOD FOR INCREASING THE LEVEL OF REALIZATION IN THE COMBUSTION OF FUELS AND FOR THE REMOVAL OF SULFUR AND NITROGEN OXIDS FROM THE EXHAUST GAS
FR2698346A1 (en) * 1992-11-25 1994-05-27 Rhone Poulenc Chimie Ceric oxide crystallite aggregate, process for obtaining it and its use for reducing combustion residues.
EP0599717A1 (en) * 1992-11-25 1994-06-01 Rhone-Poulenc Chimie Aggregate of cristallites of cerium oxide, process for obtaining it and use in the reduction of combustion residues
US6093223A (en) * 1992-11-25 2000-07-25 Rhone-Poulenc Chimie Aggregates of ceric oxide crystallites and reduction of vehicular emissions therewith
AU672834B2 (en) * 1992-11-25 1996-10-17 Rhone-Poulenc Chimie Ceric oxide crystallite aggregate, process of production and its use in reducing combustion residues
CN1042442C (en) * 1992-11-25 1999-03-10 罗纳·布朗克化学公司 Ceric oxide crystallite aggregate, process of production and its use in reducing combustion residues
WO1995011287A1 (en) * 1993-10-18 1995-04-27 Ica Innoconsult Ag Corrosion-proofing process
DE4417874C2 (en) * 1994-05-24 1999-02-04 Erc Emissions Reduzierungs Con Process for the reduction of boiler deposits in connection with measures to reduce NO¶x¶
DE4417874A1 (en) * 1994-05-24 1995-11-30 Erc Emissions Reduzierungs Con Reducing boiler deposits in combustion plants
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
WO1996026255A1 (en) * 1995-02-24 1996-08-29 Rhone-Poulenc Chimie Use of a cerium compound for protecting internal combustion engines
FR2731009A1 (en) * 1995-02-24 1996-08-30 Rhone Poulenc Chimie METHOD OF PROTECTING INTERNAL COMBUSTION ENGINES AND APPLICATION OF CERIUM-BASED COMPOUND TO THE PROTECTION OF ENGINES AGAINST WEAR AND OXIDATION
WO1997044414A1 (en) * 1996-05-20 1997-11-27 Bp Chemicals (Additives) Limited Marine diesel process and fuel therefor
DE19643866C2 (en) * 1996-10-30 2001-09-20 Gottfried Roessle Heat exchange and cleaning processes for exhaust gas from a power plant
US9193613B2 (en) 2006-10-03 2015-11-24 Siemens Energy, Inc. pH control to enable homogeneous catalytic wet air oxidation
WO2008042089A2 (en) * 2006-10-03 2008-04-10 Siemens Water Technologies Corp. Wet oxidation of soot
WO2008042089A3 (en) * 2006-10-03 2008-07-03 Siemens Water Tech Corp Wet oxidation of soot
US7993588B2 (en) 2006-10-03 2011-08-09 Siemens Industry, Inc. Catalytic wet oxidation systems and methods
US8114297B2 (en) 2006-10-03 2012-02-14 Siemens Industry, Inc. Wet oxidation of soot
US8460557B2 (en) 2006-10-03 2013-06-11 Siemens Energy, Inc. Catalytic wet oxidation systems and methods
US9315401B2 (en) 2007-01-22 2016-04-19 Siemens Energy, Inc. Wet air oxidation process using recycled copper catalyst
WO2012064084A3 (en) * 2010-11-08 2012-09-20 Oh Mi Hye Liquid-combustion catalyst composition including mixed metal-complex ionic compound
WO2012064084A2 (en) * 2010-11-08 2012-05-18 Oh Mi Hye Liquid-combustion catalyst composition including mixed metal-complex ionic compound
US8828351B2 (en) 2011-02-18 2014-09-09 Siemens Energy, Inc. H2S conversion to sulfur using a regenerated iodine solution
US8501149B2 (en) 2011-02-18 2013-08-06 Siemens Energy, Inc. H2S conversion to sulfur using a regenerated iodine solution
EP2749355A2 (en) 2012-12-29 2014-07-02 SMF Poland Spolka Z Ograniczona Odpowiedzialnoscia The catalyst suspension and method for preparing thereof
EP2749355A3 (en) * 2012-12-29 2015-02-18 SMF Poland Spolka Z Ograniczona Odpowiedzialnoscia The catalyst suspension and method for preparing thereof

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ATA244188A (en) 1990-06-15
CS276140B6 (en) 1992-04-15
HU207671B (en) 1993-05-28
HUT52711A (en) 1990-08-28
FI894658A0 (en) 1989-10-02
AT391873B (en) 1990-12-10
EP0368834B1 (en) 1993-01-07
DD290146A5 (en) 1991-05-23
DE58903225D1 (en) 1993-02-18
FI894658A (en) 1990-04-04

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