EP0270719A1 - Verfahren zur Reduzierung von nichtverbrannten Anteilen bei der Verbrennung und Agens zu dessen Durchführung - Google Patents

Verfahren zur Reduzierung von nichtverbrannten Anteilen bei der Verbrennung und Agens zu dessen Durchführung Download PDF

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Publication number
EP0270719A1
EP0270719A1 EP86402784A EP86402784A EP0270719A1 EP 0270719 A1 EP0270719 A1 EP 0270719A1 EP 86402784 A EP86402784 A EP 86402784A EP 86402784 A EP86402784 A EP 86402784A EP 0270719 A1 EP0270719 A1 EP 0270719A1
Authority
EP
European Patent Office
Prior art keywords
cerium
potassium
combustion
liquid
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP86402784A
Other languages
English (en)
French (fr)
Other versions
EP0270719B1 (de
Inventor
Germain Rosenbluth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Technique Francaise De Detartrage Dite Tfd SA
Original Assignee
Technique Francaise De Detartrage Dite Tfd SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to FR8511551A priority Critical patent/FR2585360B1/fr
Application filed by Technique Francaise De Detartrage Dite Tfd SA filed Critical Technique Francaise De Detartrage Dite Tfd SA
Priority to EP86402784A priority patent/EP0270719B1/de
Priority to ES86402784T priority patent/ES2010670B3/es
Priority to DE8686402784T priority patent/DE3665074D1/de
Publication of EP0270719A1 publication Critical patent/EP0270719A1/de
Application granted granted Critical
Publication of EP0270719B1 publication Critical patent/EP0270719B1/de
Priority to GR89400133T priority patent/GR3000126T3/el
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/10—Treating solid fuels to improve their combustion by using additives

Definitions

  • the present invention relates to a method for reducing the amount and modifying the structure of unburnt deposits which form on the surfaces of heat generators.
  • the invention also relates to synergistic combinations of products used for this purpose in heat generators.
  • the heat generators concerned can burn liquid fuels such as petroleum derivatives or solid fuels such as coal and / or industrial waste such as black liquors from paper mills or household waste for example.
  • the heat generators concerned can be indifferently those whose purpose is the production of hot air, hot water, saturated steam or superheated steam.
  • the deposits which generally form on the exchange surfaces in contact with the combustion fumes are composed of unburnt carbon elements generally called "soot", non-combustible mineral ash and products of surface corrosion. mainly sulfates and sulfides.
  • compositions Among the most known compositions, one can cite those containing certain metal salts forming part of the series of rare earths, such as the oil-soluble salts of cerium, for example claimed in French patents 2,359,192 and 2,359,199 as combustion adjuvants.
  • the subject of the present invention is a treatment method making it possible to obtain a more advantageous result than that obtained with the compositions currently used.
  • This process is characterized in that, either on solid fuels before their combustion, or in the enclosures of the generators during the combustion of liquid or solid fuels, a composition, in powder or liquid form, constituted by an association with synergistic effect of water-soluble organic salts of an alkali metal and a metal from the rare earth series.
  • the present invention also relates to an unburnt reducing agent for the implementation of the process defined above.
  • this reducing agent consists of a pulverulent composition comprising, in combination with a synergistic effect, from 70 to 90% by weight of potassium carboxylates and from 10 to 30% by weight of cerium carboxylates.
  • this reducing agent consists of a liquid composition comprising, in a synergistic effect, from 10 to 20% by weight of potassium carboxylates and from 15 to 20% by weight of cerium carboxylates, and 65 to 70% water.
  • the treatment method according to the invention therefore provides for the combination of potassium compounds and cerium compounds in order to reduce unburnt deposits and to destroy unburnable deposits on the surfaces of the combustion chambers.
  • Another characteristic of the present process consists in associating with them potassium and cerium salts soluble in water and obtained from low molecular weight carboxylic acids of elementary formula: C x O y H z in which the value of x is a even or odd whole number, between 1 and 3 inclusive.
  • the salts of lower carboxylic acids of potassium and of cerium such as potassium formate, cerium formate, potassium acetate and cerium acetate have the advantage of being able to be mixed together under their pulverulent forms or in the form of aqueous solutions making it possible to vary the proportions of alkali metal and of metal of the rare earth series in ratios chosen preferably as a function of the optimal activity of the mixtures with respect to the reduction of unburnt carbonaceous and friability of mineral ash constituting the residues of incomplete combustion of liquid or solid fuels.
  • salts of the lower series of carboxylic acids has the advantage of causing, by heat decomposition, only the formation of gaseous compounds such as CO2, O2, H2 and H2O not presenting significant risks. of atmospheric pollution nor, in particular, the disadvantages of the formation of compounds of the NO x type.
  • the salts of lower carboxylic acids of potassium and cerium can be sprayed beforehand on solid fuels or directly in the combustion flame of liquid or solid fuels.
  • the mixing can be carried out using a simple feed hopper depositing the pulverulent composition on the fuel before it enters into combustion.
  • a pulverulent composition according to the invention is prepared by intimately mixing 85% of potassium acetate and 15% of cerium acetate.
  • the powder mixture thus obtained is injected by any pneumatic means into the flame of a heat generator consuming 10 tonnes of fuel oil per day, in a single injection of 1000 grams per day for 20 days consecutively.
  • Example 2 Under experimental conditions identical to those indicated in Example 1, a pulverulent composition according to the invention comprising 70% of potassium acetate and 30% of cerium acetate was sprayed. At the end of the treatment, the carbon content of the remaining unburnt deposits had decreased by 35% and the mineral deposits in the hot zones had become much more brittle while remaining relatively adherent to the metal surfaces.
  • an 18-day spraying of a powder mixture according to the invention was carried out under experimental conditions practically identical to those indicated in Example 1.
  • a composition according to the invention was prepared by dissolving 9 kg of potassium acetate and 8.5 kg of cerium formate in 32.5 kg of demineralized water, in order to avoid any interference of the salts contained in natural raw water with the results of the experiment.
  • the liquid preparation according to the invention was sprayed using a centrifugal pump and via a nozzle, into the flame of a burner of a steam generator consuming 17 to 23 tonnes of heavy fuel oil per 24 hours, for an average of 18.7 tonnes per day.
  • a liquid composition according to the invention obtained by dissolving 20% by weight in the flame of a burner of a pressurized hot water generator supplied with domestic fuel oil potassium acetate and 15% by weight of cerium acetate in 65% by weight of water. The treatment was continued for 8 consecutive days.
  • the pulverulent compositions according to the invention can be ground finely enough to be sprayed onto solid fuels or in the flame of the generators, they nevertheless retain an irreducible particle size which delays their thermal decomposition speed and somewhat limits their remarkable efficiency.
  • compositions according to the invention in the form of aqueous solutions, results in a spraying with a perfectly adjustable particle size up to nebulization, allowing very rapid thermal decomposition and excellent distribution of the resulting dehydrated salts distributed by the molecules of water vapor subjected to this instantaneous vaporization.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP86402784A 1985-07-29 1986-12-12 Verfahren zur Reduzierung von nichtverbrannten Anteilen bei der Verbrennung und Agens zu dessen Durchführung Expired EP0270719B1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
FR8511551A FR2585360B1 (fr) 1985-07-29 1985-07-29 Procede de reduction des imbrules de combustion et agent pour sa mise en oeuvre
EP86402784A EP0270719B1 (de) 1986-12-12 1986-12-12 Verfahren zur Reduzierung von nichtverbrannten Anteilen bei der Verbrennung und Agens zu dessen Durchführung
ES86402784T ES2010670B3 (es) 1986-12-12 1986-12-12 Procedimiento de reduccion de combustidores y agente para su puesta en marcha.
DE8686402784T DE3665074D1 (en) 1986-12-12 1986-12-12 Process for reducing unburned combustion particles, and agent for carrying out the process
GR89400133T GR3000126T3 (en) 1986-12-12 1989-08-17 Process for reducing unburned combustion particles, and agent for carrying out the process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP86402784A EP0270719B1 (de) 1986-12-12 1986-12-12 Verfahren zur Reduzierung von nichtverbrannten Anteilen bei der Verbrennung und Agens zu dessen Durchführung

Publications (2)

Publication Number Publication Date
EP0270719A1 true EP0270719A1 (de) 1988-06-15
EP0270719B1 EP0270719B1 (de) 1989-08-16

Family

ID=8196366

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86402784A Expired EP0270719B1 (de) 1985-07-29 1986-12-12 Verfahren zur Reduzierung von nichtverbrannten Anteilen bei der Verbrennung und Agens zu dessen Durchführung

Country Status (5)

Country Link
EP (1) EP0270719B1 (de)
DE (1) DE3665074D1 (de)
ES (1) ES2010670B3 (de)
FR (1) FR2585360B1 (de)
GR (1) GR3000126T3 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0368834A1 (de) * 1988-10-03 1990-05-16 Lang & Co., chemisch-technische Produkte Kommanditgesellschaft Wässrige Verbrennungskatalysatoren sowie Brennstoffe
EP0423417A1 (de) * 1989-09-15 1991-04-24 SAT Chemie G.m.b.H. Verfahren zur selektiven nichtkatalytischen Reduktion der Emission von Schadstoffen aus ölbefeuerten Kesselanlagen
EP0426978A1 (de) * 1989-09-15 1991-05-15 ERC Emissions-Reduzierungs-Concepte GmbH Verfahren zur selektiven nicht-katalytischen Reduktion der Emission von Schadstoffen aus ölbefeuerten Kesselanlagen
DE4032845A1 (de) * 1989-11-02 1991-07-11 Lang Chem Tech Prod Hydrophile katalysatorloesung zur verbesserten verbrennung von kohlenstoff- und kohlenwasserstoffhaltigen stoffen
WO1995011287A1 (de) * 1993-10-18 1995-04-27 Ica Innoconsult Ag Korrosionsschutzverfahren

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2585360B1 (fr) * 1985-07-29 1987-11-20 Rosenbluth Germain Procede de reduction des imbrules de combustion et agent pour sa mise en oeuvre
DE4424090A1 (de) * 1994-07-12 1996-01-18 Erc Emissions Reduzierungs Con Verfahren zur Ausbrandverbesserung von Festbrennstoffen
GB9610563D0 (en) * 1996-05-20 1996-07-31 Bp Chemicals Additives Marine diesel process and fuel therefor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2014686A (en) * 1931-08-27 1935-09-17 Lubovitch Combustion of fuels
FR2359199A1 (fr) * 1976-07-22 1978-02-17 Gamlen Naintre Sa Derives oleosolubles de metaux de terres rares utiles comme adjuvants de combustion dans les moteurs diesel
EP0007862A1 (de) * 1978-07-25 1980-02-06 Drivex S.A. Flüssiges Mittel zur chemischen Vernichtung von Russ und Verfahren zu seiner Anwendung
EP0134146A2 (de) * 1983-08-17 1985-03-13 Exxon Research And Engineering Company Zusammensetzungen aus Rückständen von Kraftstoff
FR2585360A1 (fr) * 1985-07-29 1987-01-30 Rosenbluth Germain Procede de reduction des imbrules de combustion et agent pour sa mise en oeuvre

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2014686A (en) * 1931-08-27 1935-09-17 Lubovitch Combustion of fuels
FR2359199A1 (fr) * 1976-07-22 1978-02-17 Gamlen Naintre Sa Derives oleosolubles de metaux de terres rares utiles comme adjuvants de combustion dans les moteurs diesel
EP0007862A1 (de) * 1978-07-25 1980-02-06 Drivex S.A. Flüssiges Mittel zur chemischen Vernichtung von Russ und Verfahren zu seiner Anwendung
EP0134146A2 (de) * 1983-08-17 1985-03-13 Exxon Research And Engineering Company Zusammensetzungen aus Rückständen von Kraftstoff
FR2585360A1 (fr) * 1985-07-29 1987-01-30 Rosenbluth Germain Procede de reduction des imbrules de combustion et agent pour sa mise en oeuvre

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0368834A1 (de) * 1988-10-03 1990-05-16 Lang & Co., chemisch-technische Produkte Kommanditgesellschaft Wässrige Verbrennungskatalysatoren sowie Brennstoffe
AT391873B (de) * 1988-10-03 1990-12-10 Lang Chem Tech Prod Waessrige katalysatorloesung sowie brennstoffe
EP0423417A1 (de) * 1989-09-15 1991-04-24 SAT Chemie G.m.b.H. Verfahren zur selektiven nichtkatalytischen Reduktion der Emission von Schadstoffen aus ölbefeuerten Kesselanlagen
EP0426978A1 (de) * 1989-09-15 1991-05-15 ERC Emissions-Reduzierungs-Concepte GmbH Verfahren zur selektiven nicht-katalytischen Reduktion der Emission von Schadstoffen aus ölbefeuerten Kesselanlagen
DE4032845A1 (de) * 1989-11-02 1991-07-11 Lang Chem Tech Prod Hydrophile katalysatorloesung zur verbesserten verbrennung von kohlenstoff- und kohlenwasserstoffhaltigen stoffen
WO1995011287A1 (de) * 1993-10-18 1995-04-27 Ica Innoconsult Ag Korrosionsschutzverfahren

Also Published As

Publication number Publication date
FR2585360A1 (fr) 1987-01-30
ES2010670B3 (es) 1989-12-01
DE3665074D1 (en) 1989-09-21
GR3000126T3 (en) 1990-11-29
EP0270719B1 (de) 1989-08-16
FR2585360B1 (fr) 1987-11-20

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