EP0368834A1 - Catalyseur de combustion aqueux et combustible - Google Patents

Catalyseur de combustion aqueux et combustible 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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EP
European Patent Office
Prior art keywords
catalyst solution
solution according
alkaline
combustion
compounds
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.)
Granted
Application number
EP89890256A
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German (de)
English (en)
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EP0368834B1 (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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Publication of EP0368834A1 publication Critical patent/EP0368834A1/fr
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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L9/00Treating solid fuels to improve their combustion
    • C10L9/10Treating solid fuels to improve their combustion by using additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/04Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/06Use 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.

Landscapes

  • 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)
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
AT0244188A AT391873B (de) 1988-10-03 1988-10-03 Waessrige katalysatorloesung sowie brennstoffe
AT2441/88 1988-10-03

Publications (2)

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

Family

ID=3534413

Family Applications (1)

Application Number Title Priority Date Filing Date
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)

Cited By (15)

* 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
FR2698346A1 (fr) * 1992-11-25 1994-05-27 Rhone Poulenc Chimie Agrégat de cristallites d'oxyde cérique, procédé d'obtention et son utilisation pour réduire les résidus de combustion.
WO1995011287A1 (fr) * 1993-10-18 1995-04-27 Ica Innoconsult Ag Procede de protection contre la corrosion
DE4417874A1 (de) * 1994-05-24 1995-11-30 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
WO1996026255A1 (fr) * 1995-02-24 1996-08-29 Rhone-Poulenc Chimie Utilisation d'un compose de cerium pour la protection des moteurs a combustion interne
WO1997044414A1 (fr) * 1996-05-20 1997-11-27 Bp Chemicals (Additives) Limited Procede pour moteur diesel marin et carburant correspondant
DE19643866C2 (de) * 1996-10-30 2001-09-20 Gottfried Roessle Wärmetausch- und Reinigungsverfahren für Abgas eines Kraftwerkes
WO2008042089A2 (fr) * 2006-10-03 2008-04-10 Siemens Water Technologies Corp. Oxydation en milieu humide de la suie
US7993588B2 (en) 2006-10-03 2011-08-09 Siemens Industry, Inc. Catalytic wet oxidation systems and methods
WO2012064084A2 (fr) * 2010-11-08 2012-05-18 Oh Mi Hye Composition de catalyseur de combustion liquide incluant un composé ionique complexe métallique mixte
US8501149B2 (en) 2011-02-18 2013-08-06 Siemens Energy, Inc. H2S conversion to sulfur using a regenerated iodine solution
EP2749355A2 (fr) 2012-12-29 2014-07-02 SMF Poland Spolka Z Ograniczona Odpowiedzialnoscia Suspension de catalyseur et son procédé de préparation
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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2235204A1 (en) * 1973-06-26 1975-01-24 Bergmann Borsig Gorlitzer Fouling and corrosion inhibition in combustion units - by adding metal salts to fuel
EP0270719A1 (fr) * 1986-12-12 1988-06-15 TECHNIQUE FRANCAISE DE DETARTRAGE dite T.F.D., Société Anonyme Procédé de réduction des imbrûlés de combustion et agent pour sa mise en oeuvre

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2235204A1 (en) * 1973-06-26 1975-01-24 Bergmann Borsig Gorlitzer Fouling and corrosion inhibition in combustion units - by adding metal salts to fuel
EP0270719A1 (fr) * 1986-12-12 1988-06-15 TECHNIQUE FRANCAISE DE DETARTRAGE dite T.F.D., Société Anonyme Procédé de réduction des imbrûlés de combustion et agent pour sa mise en oeuvre

Cited By (27)

* 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
FR2698346A1 (fr) * 1992-11-25 1994-05-27 Rhone Poulenc Chimie Agrégat de cristallites d'oxyde cérique, procédé d'obtention et son utilisation pour réduire les résidus de combustion.
EP0599717A1 (fr) * 1992-11-25 1994-06-01 Rhone-Poulenc Chimie Agrégat de cristallites d'oxyde cérique, procédé d'obtention et son utilisation pour réduire les résidus de combustion
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 (zh) * 1992-11-25 1999-03-10 罗纳·布朗克化学公司 二氧化铈微晶聚集体,生产方法及应用
WO1995011287A1 (fr) * 1993-10-18 1995-04-27 Ica Innoconsult Ag Procede de protection contre la corrosion
DE4417874C2 (de) * 1994-05-24 1999-02-04 Erc Emissions Reduzierungs Con Verfahren zur Verminderung von Kesselbelägen im Zusammenhang mit NO¶x¶-reduzierenden Maßnahmen
DE4417874A1 (de) * 1994-05-24 1995-11-30 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
WO1996026255A1 (fr) * 1995-02-24 1996-08-29 Rhone-Poulenc Chimie Utilisation d'un compose de cerium pour la protection des moteurs a combustion interne
FR2731009A1 (fr) * 1995-02-24 1996-08-30 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
WO1997044414A1 (fr) * 1996-05-20 1997-11-27 Bp Chemicals (Additives) Limited Procede pour moteur diesel marin et carburant correspondant
DE19643866C2 (de) * 1996-10-30 2001-09-20 Gottfried Roessle Wärmetausch- und Reinigungsverfahren für Abgas eines Kraftwerkes
US9193613B2 (en) 2006-10-03 2015-11-24 Siemens Energy, Inc. pH control to enable homogeneous catalytic wet air oxidation
WO2008042089A2 (fr) * 2006-10-03 2008-04-10 Siemens Water Technologies Corp. Oxydation en milieu humide de la suie
WO2008042089A3 (fr) * 2006-10-03 2008-07-03 Siemens Water Tech Corp Oxydation en milieu humide de la suie
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 (fr) * 2010-11-08 2012-09-20 Oh Mi Hye Composition de catalyseur de combustion liquide incluant un composé ionique complexe métallique mixte
WO2012064084A2 (fr) * 2010-11-08 2012-05-18 Oh Mi Hye Composition de catalyseur de combustion liquide incluant un composé ionique complexe métallique mixte
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 (fr) 2012-12-29 2014-07-02 SMF Poland Spolka Z Ograniczona Odpowiedzialnoscia Suspension de catalyseur et son procédé de préparation
EP2749355A3 (fr) * 2012-12-29 2015-02-18 SMF Poland Spolka Z Ograniczona Odpowiedzialnoscia Suspension de catalyseur et son procédé de préparation

Also Published As

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

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