EP0007862A1 - Flüssiges Mittel zur chemischen Vernichtung von Russ und Verfahren zu seiner Anwendung - Google Patents

Flüssiges Mittel zur chemischen Vernichtung von Russ und Verfahren zu seiner Anwendung Download PDF

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Publication number
EP0007862A1
EP0007862A1 EP79400514A EP79400514A EP0007862A1 EP 0007862 A1 EP0007862 A1 EP 0007862A1 EP 79400514 A EP79400514 A EP 79400514A EP 79400514 A EP79400514 A EP 79400514A EP 0007862 A1 EP0007862 A1 EP 0007862A1
Authority
EP
European Patent Office
Prior art keywords
magnesium
potassium
acetate
atoms
agent
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
EP79400514A
Other languages
English (en)
French (fr)
Other versions
EP0007862B1 (de
Inventor
Jean-Claude Palumbo
Jean Rousseau
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.)
DRIVEX SA
Original Assignee
DRIVEX 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 claimed from FR7821901A external-priority patent/FR2432041A1/fr
Priority claimed from FR7917117A external-priority patent/FR2460318A2/fr
Application filed by DRIVEX SA filed Critical DRIVEX SA
Publication of EP0007862A1 publication Critical patent/EP0007862A1/de
Application granted granted Critical
Publication of EP0007862B1 publication Critical patent/EP0007862B1/de
Expired legal-status Critical Current

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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
    • 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J7/00—Arrangement of devices for supplying chemicals to fire

Definitions

  • the present invention relates to the chemical sweeping of ovens and boilers of all types and flues.
  • soot designates unburnt carbon and that the term “deposits” as used below designates a mixture deposited on the surfaces and consisting of soot, fuel ash containing in particular iron sulphates and oxides of metals, corrosion products, etc.
  • Chloride-based products have been used, for example, which lower the ignition point of carbon, but which present a fire risk and above all a risk of corrosion by the hydrochloric acid which is released as a result of the reaction of chlorides with sulfuric anhydride retained in soot and coming from the sulfur which the majority of the fuels contain.
  • U.S. Patent 2,949,008 relates to a chemical agent containing a magnesium compound and an alkali metal compound and which can be applied in the form of an aqueous solution, but this agent is intended not to chemically destroy the soot, but to reduce corrosion of the soot.
  • a known chemical chimney sweeping age is a mixture, in powder form, of potassium nitrate in high proportion and of sulfur and charcoal in low proportion.
  • the pulverulent mixture is injected with compressed air and burned in the flame of the burner of the oven or of the boiler at a temperature above 450 ° C., the combustion of this mixture causing, with a significant release of heat, the formation of 'A complex gas, containing in particular carbon dioxide and sulfuric anhydride, and very fine solid particles consisting essentially of potassium carbonate, but also potassium sulfate and potassium oxide, among others.
  • the potassium carbonate has an effect of lowering the ignition point of the carbon of the soot and an oxidation effect of this carbon, which is destroyed from 130 ° C by transformation into carbonic gas (it is a combustion slow catalytic), while potassium oxide partially neutralizes the acidic sulfur derivatives retained in the deposits.
  • Chimney sweeps and blowing become unnecessary and it suffices to periodically remove by suction the deposits, which are no longer made up of powdery and poorly adherent ash, containing in particular iron sulphates and metal oxides from the fuel.
  • this chimney sweeping agent presents several difficulties: in fact, the powder of said mixture melts at 140 ° C.
  • the object of the present invention is to remedy the great difficulty of applying, in practice, this chemical agent chimney sweep.
  • This agent which is an aqueous solution of an alkali metal compound and a magnesium compound, is characterized in that the alkali metal compound is potassium acetate, CH 3 Co 2 K, in that the compound of magnesium is magnesium nitrate, (N0 3 ) 2 Mg, or a mixture of magnesium nitrate and magnesium acetate, (CH 3 C0 2 ) 2 M g , and in that the relative proportions of potassium and magnesium in the agent are 40 to 60 atoms of the first for 60 to 40 atoms of the second.
  • said solution can contain 56 potassium atoms for 44 magnesium atoms.
  • the proportion of water is variable, the most suitable dilution being able to be easily determined experimentally in each particular case of use.
  • the solution initially prepared and delivered to users is a saturated solution, to reduce congestion during storage and transport.
  • potassium acetate it is possible to replace potassium acetate with a chemical equivalent in the form of a water-soluble salt of an alkaline earth metal in place of potassium and / or an organic acid other than acid acetic, but, like the latter, usual and inexpensive, such as formic acid or butyric acid.
  • alkali and / or alkaline earth silicates can be added to the liquid agent in question, for example in the form of a saturated aqueous solution added to the saturated aqueous solution of the agent.
  • a saturated aqueous solution added to the saturated aqueous solution of the agent.
  • silicates makes it possible to raise the melting point of these ashes, consequently, to make them "dry", non-adherent and therefore easily removable, and less corrosive, when they contain corrosive substances such as vanadium. , which may be the case when they result from the combustion of fuel oil.
  • the proportion of silicates can be from 5 to 10% by weight relative to the weight of the agent.
  • the liquid chemical sweeping agent according to the invention is easy to spray into the flame of the burner of an oven or a boiler by means of compressed air, or better still by means of an electric vibrator. There is no exothermic reaction which may cause an explosion.
  • the water evaporates as soon as the solution reaches 100 ° C, a temperature which it is useless to exceed.
  • the dry extract then ignites very quickly, it is broken down into its elements, and the free potassium and magnesium ions generate, in the oxidizing atmosphere of the flame reinforced by the oxidizing nitrate ions, on the one hand, potassium oxide (R20), which transforms into powdered potassium carbonate (CO 3 K 2 ), in the presence of the carbon dioxide of the combustion gases, to which is added that resulting from the subsequent oxidation of the soot by this carbonate, and, on the other hand, magnesium oxide (MgO) also in the pulverulent state.
  • the potassium carbonate ensures the catalytic combustion of the soot present in the combustion gases and on the surfaces, in the manner indicated above, by lowering the ignition point of carbon and by an effect of carbon oxidation.
  • the powdery potassium carbonate which is added to the deposits, does not adhere to the walls and is easily removable.
  • magnesium oxide it neutralizes the sulfur oxidation products retained by the deposits as well as the sulfuric acid condensed in the cold areas of the furnace or the boiler, whereas with the previous chemical xamonage agents, it was generally necessary to carry out a complementary treatment, consisting in spraying in these cold areas very fine magnesium oxide, in particular of a size less than 10 microns, which was not an easy operation; with the new chemical sweeping agent, MgO is formed in situ. Since potassium carbonate is basic, it cooperates with MgO for the neutralizing action.
  • the magnesium sulphate and potassium sulphate formed are powdery, non-adherent, easily removable products.
  • the ratio between the number of potassium atoms and the number of nitrate ions (NO 3 - ) in the present agent is 1.87, this which corresponds to 56 potassium atoms for 30 nitrate ions.
  • this preferred K / NO 3 ratio of 1.87 is to optimize the combustion of the dry extract obtained after evaporation of the water, when said agent is used.
  • NO 3 ion content is greater than 30 ions, there is a risk of formation of toxic nitrogen oxides, NO x , as well as products such as nitrites which can be found on the surfaces of the oven or the boiler and flues, in the molten state and inactive, also resulting in a loss of agent efficiency.
  • magnesium can no longer, in this case, be present in the agent only in the form of nitrate, if the ratio is to be maintained preferential K / Mg of 56 atoms of the first for 44 atoms of the second.
  • the magnesium supplement is then provided in the form of magnesium acetate.
  • the improved liquid agent according to the present invention is characterized in that the magnesium compound which it contains is a mixture of magnesium nitrate, (N0 3 ) 2 Mg, and magnesium acetate, (CH 3 C0 2 ) 2 Mg, in the preferred proportions of 15 molecules of nitrate for 29 molecules of acetate.
  • the subject of the invention is also the method of applying said agent, consisting in spraying it into the flame by means of an electric vibrator, which makes it much better than air. tablet, control the injection.
  • an electric vibrator which makes it much better than air. tablet, control the injection.
  • the latter can be either a solid fuel (coal, wood, shale, lignite, for example), liquid (oil), or gas.
  • the liquid form of the agent and its spraying ensure optimum fine distribution and maximum effectiveness of the agent.
  • the sulfur dioxide content (SO 3 ) of the deposits is usually analyzed when chemical sweeping is carried out; this anhydride having to be currently neutralized by magnesium oxide, account is taken of the results of said analysis to introduce magnesium nitrate and optionally magnesium acetate in greater or lesser proportions into the chemical sweeping agent considered, and the agent injection rate or the frequency of its injection are also determined by this analysis as well as, of course, by the extent of the deposits.
  • the injections were periodic, with the new liquid agent, spraying in the flame can be carried out continuously and it has an anti-pollution effect continuously of the atmosphere and anti-corrosion of the equipment.
  • Another object of the invention is the process for the preparation of the new chemical chimney sweeping agent considered.
  • This process consists in preparing a saturated aqueous solution of potassium acetate and optionally magnesium acetate, from acetic acid and, respectively, potassium carbonate and magnesium carbonate, in stoichiometric proportions, then preparing a saturated aqueous solution of magnesium nitrate, starting from nitric acid and magnesium carbonate in stoichiometric proportions, all these preparations being carried out individually under cooling, after which the saturated solutions are mixed so that the ratio of potassium to magnesium in the mixture of 40 to 60 atoms of the first for 60 to 40 atoms of the second and diluted with water in a variable manner, at the time of use, the concentrated intermediate mixture thus obtained, the most favorable dilution being determined experimentally in each case of use of the final solution.
  • the mixing is preferably carried out so that it contains 56 potassium atoms for 44 magnesium atoms and, when we want to obtain the optimal ratio of 1.87 between the number of potassium atoms and the number of nitrate ions, so that it contains, for 56 molecules of potassium acetate, 15 molecules of magnesium nitrate and 29 molecules of magnesium acetate.
  • silicates can be added to the solution, as indicated above.
  • potassium acetate could be replaced by an acetate of an alkaline earth metal, in which case the raw material potassium carbonate is replaced by the corresponding carbonate, and that the acetate anion could be replaced by a another anion, in which case the raw material acetic acid is replaced by another organic acid which is easy to obtain and inexpensive.
  • potassium magnesium acetates and magnesium nitrate potassium hydroxide, KOH, and magnesia, MgO, can also be used instead of potassium carbonate and magnesium carbonate, respectively. Stoichiometric proportions of these bases and of acetic and nitric acids are also used.
  • the agent according to the invention can be prepared in the following manner: under cooling, successively and in stoichiometric proportions are poured into the total amount of water necessary to obtain a saturated solution in the desired amounts of the various constituents, acetic acid, potassium carbonate or potash necessary to form potassium acetate, magnesium carbonate or magnesia necessary to form magnesium acetate, nitric acid, magnesium carbonate or magnesia necessary to form magnesium nitrate, then dilute with water, at the time of use, the concentrated solution obtained, the most favorable dilution being determined experimentally in each case of use of the final solution.
  • the necessary cooling during the preparation of the agent can be obtained by circulating cold water in the reaction medium (for example by means of an immersed coil), or around this medium; for example, the preparation can be carried out in a jacketed container and a circulation of cooling water can be established in the container jacket.
  • composition of the agent according to the invention is given below, but it is in no way limiting
  • the preparation of the product can be carried out according to the method indicated above as an alternative, that is to say by successively adding and under cooling, in the 69.5 parts of water, the quantity of acetic acid necessary to form 14.5 parts of potassium acetate and 10.1 parts of magnesium acetate, the amount of potassium carbonate required to form 14.5 parts of potassium acetate, the amount of magnesium carbonate required to form 10.1 parts of magnesium acetate, the amount of nitric acid required to form 5.9 parts of magnesium nitrate, and the amount of magnesium carbonate required to form 5.9 parts of magnesium nitrate.
  • This concentrated solution will be diluted variably at the time of use and depending on the use.
  • potassium carbonate and the magnesium carbonate can be replaced, as mentioned above, by potash and magnesia.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Incineration Of Waste (AREA)
EP79400514A 1978-07-25 1979-07-20 Flüssiges Mittel zur chemischen Vernichtung von Russ und Verfahren zu seiner Anwendung Expired EP0007862B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR7821901 1978-07-25
FR7821901A FR2432041A1 (fr) 1978-07-25 1978-07-25 Agent de destruction chimique de la suie et son procede d'application et de preparation
FR7917117 1979-07-02
FR7917117A FR2460318A2 (fr) 1979-07-02 1979-07-02 Agent liquide de destruction chimique de la suie et son procede d'application et de preparation

Publications (2)

Publication Number Publication Date
EP0007862A1 true EP0007862A1 (de) 1980-02-06
EP0007862B1 EP0007862B1 (de) 1982-01-27

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EP79400514A Expired EP0007862B1 (de) 1978-07-25 1979-07-20 Flüssiges Mittel zur chemischen Vernichtung von Russ und Verfahren zu seiner Anwendung

Country Status (4)

Country Link
EP (1) EP0007862B1 (de)
DE (1) DE2961969D1 (de)
IT (1) IT1121017B (de)
LU (1) LU81539A1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0042367A2 (de) * 1980-06-16 1981-12-23 Peter M. Scocca Methode für die Reduktion des Schwefelgehalts in Abgasen
FR2585360A1 (fr) * 1985-07-29 1987-01-30 Rosenbluth Germain Procede de reduction des imbrules de combustion et agent pour sa mise en oeuvre

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2949008A (en) * 1958-01-29 1960-08-16 Gulf Research Development Co Residual fuels
FR1326720A (fr) * 1962-05-11 1963-05-10 Maxwell Chemicals Pty Ltd Procédé et préparation pour le traitement de foyers
GB1378882A (en) * 1972-05-16 1974-12-27 Polar Chemicals Ltd Method for the removal of soot and other deposits formed as a result of the combustion of gaseous liquid and solid fuels
FR2235204A1 (en) * 1973-06-26 1975-01-24 Bergmann Borsig Gorlitzer Fouling and corrosion inhibition in combustion units - by adding metal salts to fuel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2949008A (en) * 1958-01-29 1960-08-16 Gulf Research Development Co Residual fuels
FR1326720A (fr) * 1962-05-11 1963-05-10 Maxwell Chemicals Pty Ltd Procédé et préparation pour le traitement de foyers
GB1378882A (en) * 1972-05-16 1974-12-27 Polar Chemicals Ltd Method for the removal of soot and other deposits formed as a result of the combustion of gaseous liquid and solid fuels
FR2235204A1 (en) * 1973-06-26 1975-01-24 Bergmann Borsig Gorlitzer Fouling and corrosion inhibition in combustion units - by adding metal salts to fuel

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0042367A2 (de) * 1980-06-16 1981-12-23 Peter M. Scocca Methode für die Reduktion des Schwefelgehalts in Abgasen
EP0042367A3 (en) * 1980-06-16 1982-02-03 Peter M. Scocca Method for reduction of sulfur content in exit gases
FR2585360A1 (fr) * 1985-07-29 1987-01-30 Rosenbluth Germain Procede de reduction des imbrules de combustion et agent pour sa mise en oeuvre
EP0270719A1 (de) * 1986-12-12 1988-06-15 TECHNIQUE FRANCAISE DE DETARTRAGE dite T.F.D., Société Anonyme Verfahren zur Reduzierung von nichtverbrannten Anteilen bei der Verbrennung und Agens zu dessen Durchführung

Also Published As

Publication number Publication date
IT7968534A0 (it) 1979-07-24
EP0007862B1 (de) 1982-01-27
LU81539A1 (fr) 1980-02-14
IT1121017B (it) 1986-03-26
DE2961969D1 (en) 1982-03-11

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