EP0368834B1 - Catalyseur de combustion aqueux et combustible - Google Patents

Catalyseur de combustion aqueux et combustible Download PDF

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Publication number
EP0368834B1
EP0368834B1 EP89890256A EP89890256A EP0368834B1 EP 0368834 B1 EP0368834 B1 EP 0368834B1 EP 89890256 A EP89890256 A EP 89890256A EP 89890256 A EP89890256 A EP 89890256A EP 0368834 B1 EP0368834 B1 EP 0368834B1
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EP
European Patent Office
Prior art keywords
catalyst solution
combustion
alkaline
solution according
aqueous
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.)
Expired - Lifetime
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EP89890256A
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German (de)
English (en)
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EP0368834A1 (fr
Inventor
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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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
    • 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 components in the exhaust gas, as well as causing a significantly increased risk of corrosion on iron materials.
  • Copper is much 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, in order to benefit both from the combustion-catalytic effect of the metal ion and to exploit 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 combination with free alkalis, such as alkali hydroxides, carbonates and silicates, whereby the soot is oxidized by H2O2 and the acid neutralization by the strong aqueous alkali solutions; 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 catalytic converter which is non-toxic, catalytically highly effective for 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 to be 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.
  • cerium compounds for example, Comprehensive Inorganic Chemistry in five Volumes, Volume 4, Lanthanides, Transition Metal Compounds, Pergamon Press, pages 97-101, and further on Chemistry With Inorganic Qualitative Analysis, second edition, Academic Press, page 1033.
  • an alkalinity reserve is present in order to neutralize acids from the burned fuels.
  • This neutralization of inorganic acids, such as sulfuric and sulfurous 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.
  • 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.
  • This solution is applied to sooty and tarred surfaces and improves the combustion of these harmful coatings similar to Example 1.
  • wetting agents 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.
  • the magnesium nitrate is also thermally decomposed and, as a basic oxide / hydroxide, the mineral acids as well, but also organic acids, which are formed when burning sulfur-containing heating oils and coal or in 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). Furthermore, 60 pbw of oxyacetic acid (glycolic acid) are added and adjusted to a pH of 7 with 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.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Claims (14)

  1. Solution aqueuse de catalyseur pour la combustion améliorée de substances contenant du carbone et/ou un hydrocarbure, telles que les fuels de chauffage, les gaz de chauffage et les combustibles solides, et/eu pour éliminer les dépôts de charbon et de goudron des surfaces de la chambre de combustion, la solution catalytique renfermant des sels de cérium, caractérisée en ce que la solution aqueuse de catalyseur présente un pH d'au moins 7 et contient, en une quantité catalytiquement active, du cérium tétravalent (Ce⁴⁺) et des composés de métal alcalin, de métal alcalino-terreux et/ou de magnésium, qui, après leur combustion ou leur décomposition thermique, ont une réaction alcaline, ainsi qu'un agent complexant pour ce Ce⁴⁺.
  2. Solution catalytique selon la revendication 1, caractérisée en ce qu'elle contient, comme composés à réaction alcaline, des sels ou des savons organiques de potassium, de sodium, de lithium.
  3. Solution catalytique selon la revendication 1, caractérisée en ce qu'elle contient, comme composés à réaction alcaline, des composés organiques de calcium, magnésium et/ou baryum.
  4. Solution catalytique selon la revendication 1, caractérisée en ce qu'elle contient, comme composés à réaction alcaline, des nitrates alcalins, alcalino-terreux et/ou magnésium.
  5. Solution catalytique selon la revendication 1, caractérisée en ce qu'elle contient, comme composés à réaction alcaline, des carbonates alcalins, alcalino-terreux et/ou de magnésium.
  6. Solution catalytique selon la revendication 1, caractérisée en ce qu'elle contient, comme composés à réaction alcaline, des polycarboxylates alcalins, alcalino-terreux et/ou de magnésium.
  7. Solution catalytique selon la revendication 1, caractérisée en ce qu'elle contient, comme composés à réaction alcaline, des hydroxycarboxylates alcalins, alcalino-terreux et/ou de magnésium.
  8. Solution catalytique selon une quelconque des revendications précédentes, caractérisée en ce qu'elle contient Ce⁴⁺ à raison de 0,1 à 15 % en poids, par rapport à la quantité totale de solution catalytique, et le composé à réaction alcaline, à raison de 0,1 à 30 % en poids, par rapport à la quantité totale de solution catalytique.
  9. Solution catalytique selon une quelconque des revendications 1 à 8 précédentes, caractérisée en ce qu'elle contient l'agent complexant à raison de 1 à 40 % en poids, par rapport à la quantité totale de solution catalytique.
  10. Solution catalytique selon la revendication 9, caractérisée en ce qu'elle contient l'agent complexant à raison de 2 à 10 % en poids.
  11. Utilisation de la solution aqueuse de catalyseur pour améliorer la combustion de substances contenant du carbone et/ou un hydrocarbure, selon les revendications 1 à 10, caractérisée en ce que ladite solution est introduite en continu ou périodiquement dans la chambre de combustion, de préférence par pulvérisation.
  12. Utilisation de la solution aqueuse de catalyseur pour améliorer la combustion de substances contenant du carbone et/ou un hydrocarbure, selon les revendications 1 à 10, caractérisé en en ce que, avant la combustion, ladite solution est mise en dispersion ou en émulsion dans du combustible liquide.
  13. Utilisation de la solution aqueuse de catalyseur pour améliorer la combustion de substances contenant du carbone et/ou un hydrocarbure, selon les revendications 1 à 10, caractérisée en ce que, avant la combustion, ladite solution est déposée sur du combustible solide.
  14. Combustible liquide ou solide, en particulier fuel de chauffage ou charbon, caractérisé en ce qu'il renferme la solution aqueuse de catalyseur selon une ou plusieurs des revendications 1 à 10 en une proportion telle que la teneur en Ce⁴⁺ vaille entre 1 et 100 ppm, de préférence entre 15 et 35 ppm, par rapport à la quantité de combustible.
EP89890256A 1988-10-03 1989-09-29 Catalyseur de combustion aqueux et combustible Expired - Lifetime EP0368834B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT2441/88 1988-10-03
AT0244188A AT391873B (de) 1988-10-03 1988-10-03 Waessrige katalysatorloesung sowie brennstoffe

Publications (2)

Publication Number Publication Date
EP0368834A1 EP0368834A1 (fr) 1990-05-16
EP0368834B1 true EP0368834B1 (fr) 1993-01-07

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EP89890256A Expired - Lifetime EP0368834B1 (fr) 1988-10-03 1989-09-29 Catalyseur de combustion aqueux et combustible

Country Status (7)

Country Link
EP (1) EP0368834B1 (fr)
AT (1) AT391873B (fr)
CS (1) CS276140B6 (fr)
DD (1) DD290146A5 (fr)
DE (1) DE58903225D1 (fr)
FI (1) FI894658A (fr)
HU (1) HU207671B (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT395383B (de) * 1991-04-25 1992-12-10 Ind Und Bergbaugesellschaft Pr Kombiniertes verfahren zur steigerung des umsetzungsgrades bei der verbrennung von brennstoffen und zur beseitigung von schwefelund stickoxiden aus den abgasen
FR2698346B1 (fr) * 1992-11-25 1995-01-27 Rhone Poulenc Chimie Agrégat de cristallites d'oxyde cérique, procédé d'obtention et son utilisation pour réduire les résidus de combustion.
ATA208793A (de) * 1993-10-18 1998-03-15 Ica Innoconsult Ag Korrosionsschutzverfahren
DE4417874C2 (de) * 1994-05-24 1999-02-04 Erc Emissions Reduzierungs Con Verfahren zur Verminderung von Kesselbelägen im Zusammenhang mit NO¶x¶-reduzierenden Maßnahmen
DE4424090A1 (de) * 1994-07-12 1996-01-18 Erc Emissions Reduzierungs Con Verfahren zur Ausbrandverbesserung von Festbrennstoffen
FR2731009B1 (fr) * 1995-02-24 1997-04-04 Rhone Poulenc Chimie Procede de protection des moteurs a combustion interne et application de compose a base de cerium a la protection des moteurs contre l'usure et l'oxydation
GB9610563D0 (en) * 1996-05-20 1996-07-31 Bp Chemicals Additives Marine diesel process and fuel therefor
DE19643866C2 (de) * 1996-10-30 2001-09-20 Gottfried Roessle Wärmetausch- und Reinigungsverfahren für Abgas eines Kraftwerkes
DE102005031528A1 (de) * 2005-06-29 2007-03-15 Hoffmann Gmbh & Co. Kg Verfahren und Steuerungssystem zur Minderung von Korrosionen und zur Reduzierung von Ablagerungen in einer Verbrennungsanlage
US9193613B2 (en) 2006-10-03 2015-11-24 Siemens Energy, Inc. pH control to enable homogeneous catalytic wet air oxidation
US7993588B2 (en) 2006-10-03 2011-08-09 Siemens Industry, Inc. Catalytic wet oxidation systems and methods
WO2008042089A2 (fr) * 2006-10-03 2008-04-10 Siemens Water Technologies Corp. Oxydation en milieu humide de la suie
US9315401B2 (en) 2007-01-22 2016-04-19 Siemens Energy, Inc. Wet air oxidation process using recycled copper catalyst
KR101246879B1 (ko) * 2010-11-08 2013-03-25 오미혜 복합 금속착이온화합물을 포함하는 액상 연소촉매 조성물
AU2012219374B2 (en) 2011-02-18 2015-07-02 Nexen Energy Ulc H2S conversion to sulfur using a regenerated iodine solution
EP2749355A3 (fr) 2012-12-29 2015-02-18 SMF Poland Spolka Z Ograniczona Odpowiedzialnoscia Suspension de catalyseur et son procédé de préparation

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD112660A1 (fr) * 1973-06-26 1975-04-20
GB2095283B (en) * 1981-02-09 1984-08-01 Polarchem Ltd Method for the prevention of deposits on or the removal ofdeposits from heating and ancillary surfaces
FR2585360B1 (fr) * 1985-07-29 1987-11-20 Rosenbluth Germain Procede de reduction des imbrules de combustion et agent pour sa mise en oeuvre

Also Published As

Publication number Publication date
DE58903225D1 (de) 1993-02-18
FI894658A (fi) 1990-04-04
AT391873B (de) 1990-12-10
ATA244188A (de) 1990-06-15
HU207671B (en) 1993-05-28
CS276140B6 (en) 1992-04-15
DD290146A5 (de) 1991-05-23
EP0368834A1 (fr) 1990-05-16
HUT52711A (en) 1990-08-28
FI894658A0 (fi) 1989-10-02

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