EP0042367B1 - Method for reduction of sulfur content in exit gases - Google Patents

Method for reduction of sulfur content in exit gases Download PDF

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Publication number
EP0042367B1
EP0042367B1 EP81850107A EP81850107A EP0042367B1 EP 0042367 B1 EP0042367 B1 EP 0042367B1 EP 81850107 A EP81850107 A EP 81850107A EP 81850107 A EP81850107 A EP 81850107A EP 0042367 B1 EP0042367 B1 EP 0042367B1
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EP
European Patent Office
Prior art keywords
sulfur
fuel
fuels
calcium nitrate
combustion
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
Application number
EP81850107A
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German (de)
English (en)
French (fr)
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EP0042367A3 (en
EP0042367A2 (en
Inventor
Peter M. Scocca
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Individual
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Individual
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Application filed by Individual filed Critical Individual
Priority to AT81850107T priority Critical patent/ATE15688T1/de
Publication of EP0042367A2 publication Critical patent/EP0042367A2/en
Publication of EP0042367A3 publication Critical patent/EP0042367A3/en
Application granted granted Critical
Publication of EP0042367B1 publication Critical patent/EP0042367B1/en
Expired legal-status Critical Current

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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
    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1266—Inorganic compounds nitrogen containing compounds, (e.g. NH3)
    • 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 generally to the field of pollution control and more specifically to the reduction of sulfur dioxide and sulfur trioxide emissions in exit gases from combustion systems.
  • High sulfur content fuels are significantly less expensive than low sulfur content fuels; high sulfur content fuels are more readily and easily available, and high sulfur content fuels have significantly higher heating values than do low sulfur content fuels.
  • the regulatory agencies have established programs requiring the use of scrubbing systems designed to remove the objectionable sulfur dioxide and sulfur trioxide components in the exit gases. These scrubbers are required in installations burning fuels at 63 million kilocalories per hour or higher, and where the exit gases contain more than 0,36 kg of sulfur dioxide per million kilocalories in the fuel.
  • the scrubbers have high maintenance costs and require special handling of the extracted products.
  • the scrubber units are estimated to cost between 70-100 million dollars each depending upon the systems to which they are attached.
  • the present invention is concerned with a process for reducing the sulfur content of the combustion gases formed by continuous combustion of sulfur-containing fuels in the burning chamber of an industrial boiler of a power generating plant having an open flue, wherein the fuel is moved into the burning chamber and is ignited in the latter in an open flame by contacting the fuel with combustion air.
  • the invention is characterized by mixing the sulfur-containing fuel with an aqueous solution of calcium nitrate prior to the entering of the fuel into the burning chamber, thus permitting the fuel and the aqueous solution of calcium nitrate to move together into the burning chamber and to achieve reduction of the amount of sulfur available for conversion to sulfur oxide gases by reaction between the calcium nitrate in aqueous solution and the sulfur in said open flame.
  • the aqueous solution of calcium nitrate is metered into the fuel system at a point in time prior to actual ignition of the fuel and at a predetermined rate which may be varied to satisfy the reduction levels desired by the user.
  • the fuel and calcium nitrate are ignited simultaneously and, during the igniting process, the calcium nitrate reacts with the sulfur and oxygen present to form calcium sulfides, sulfites, sulfates and other sulfur bearing compounds thus preventing large quantities of sulfur from forming sulfur dioxide and sulfur trioxide.
  • Another object of the present invention is to provide a method for the burning of high sulfur content fuels while maintaining required low levels of sulfur dioxide and sulfur trioxide contents in exit gases.
  • Yet another object of the present invention is to provide a method for a sulfur bearing fuel combustion system which produces exit gases including emission levels of less than or equal to 0.36 kg of sulfur dioxide per million kilocalories of fuel and thus eliminating the need for purchasing and maintaining expensive scrubber units.
  • Still another object of the present invention is to provide a method for a sulfur bearing fuel combustion system which makes effective use of existing fuel resources (such as high sulfur bearing fuels), reduces the need for fuel supplies to produce expensive low sulfur content fuels, reduces fuel costs to utilities and industry, provides savings which can be passed on to consumers and reduces sulfur pollutants in the air.
  • French patent No. 980 969 is concerned with fuel compositions adapted to be used in diesel engines. Particularly, the patent is concerned with the use of fuels having a high content of sulfur and sulfur compounds, such ingredients being responsible for the formation of sulfur dioxide as a result of the combustion process. Sulfur dioxide when contacted with water, forms highly corrosive products. In order to avoid the action of corrosive products, the patent specification suggests to use specific salts which are capable of neutralizing the acidic compounds formed in the combustion process. Generally, metallic nitrates or carbonates shall be used as additives to the fuels. Preferably, alkali and. alkaline earth metal salts should be used. The inorganic salts can be incorporated into the fuels having a high content of sulfur in any manner.
  • Certain of the salts such as calcium nitrate are sufficiently soluble in hydrocarbons to be able to be inserted into the diesel engine as a solution or suspension.
  • Another advantageous method of applying the salts is to inject a solution, suspension or dispersion into the stream of air, which is led to the engine.
  • the figure is a representative schematic of a power generating plant utilizing the method of the present invention.
  • the figure depicts a preferred embodiment of the process of the present invention.
  • Sulfur bearing fuel oil or other sulfur bearing products are fed through feed lines 14 from their storage reservoir 16 to the combustion chamber 18 of a power generating unit 12. As the fuel approaches the combustion point 19 a quantity of the calcium nitrate is injected into the feed line 14 and thus into the fuel stream. The injection of the specific compound to the fuel is done preferably immediately prior to the combustion point 19. The calcium nitrate and the sulfur bearing fuel are ignited simultaneously at the combustion point. The calcium nitrate in the presence of the heat of the burning fuel reacts with sulfur of the fuel oil and oxygen forming calcium sulfides, sulfites, sulfates, and other sulfur bearing compounds which generally fall out of the combustion site into waste bins 20. As more sulfur is used up in the formation of various sulfur compounds, less sulfur remains to escape through the exhaust pipes or stacks 21 in the form of oxides, i.e. sulfur dioxide and sulfur trioxide.
  • oxides i.e. sulfur dioxide and sulfur trioxide.
  • Calcium nitrate (Ca(N0 3 ) 2 reacts with the sulfur in the fuel as seen in the following chemical formulations:
  • the calcium nitrate in the form of an aqeuous solution is stored in a metering tank 22 from which the solution is metered into the fuel line 14. Where large quantities must be used, the solution is held in a holding tank 23 from which it is pumped to the metering tank 22.
  • the solution of calcium nitrate is metered into the fuel line 14 at the point of combustion 19 or just prior to the point of combustion at a variable rate based on a unit quantity of sulfur bearing fuel or other sulfur bearing products and on the amount of reduction desired in the sulfur dioxide and sulfur trioxide in the exit gases.
  • the preferred embodiment calls for metering the calcium nitrate into the system at the point of combustion or immediately prior thereto, it is within the scope of this invention to "pretreat" the fuel or other sulfur bearing product. That is, the calcium nitrate, in its appropriate form, is injected into the liquid fuel (or dispersed onto a solid fuel) at any time prior to ignition, even for example, while the fuel is in the storage reservoir 16.
  • Applicant offers the following examples as samples of the invented process, depicting a preferred embodiment.
  • Preamble #6 fuel oil with 1.8% sulfur content was ignited and burned at a rate of 5443 liters per hour in a typical manner known in the art, in a power unit of a generating station.
  • the power unit was operated at full power, and exit gases were exhausted into and through the station's exhaust stack.
  • repeated samplings and analyses of the exhaust gases were made at a point half way up the stack.
  • the analysis of the exit gases resulting from the fuel burned in accordance with the prior art methods showed consistantly similar measurements of the total sulfur (S0 2 +S0 3 ) content of the exit gases, which averaged to approximately 2.69 mg sulfur (SO z +S0 3 ) per 15 liters of exit gas.
  • a solution of calcium nitrate was added to and ignited with the fuel oil at a rate of 15 liters of calcium nitrate solution per hour.
  • the solution was injected into the fuel stream by known metering methods and devices, at a point immediately prior to the point of ignition. Metering of the solution into the fuel stream immediately prior to ignition aided in assuring that the solution was ignited at the same rate at which it was metered into the fuel stream.
  • the power unit continued to operate at full power and exit gases were exhausted through the stack in the typical manner.
  • the solution of this example was 50% aqueous solution of technical grade calcium nitrate.
  • the calcium nitrate, tech. is that supplied by Hummel Chemical Company, Inc., having the chemical formula
  • H 2 S0 4 is formed when S0 2 /S0 3 is in the presence of water vapor. Since both water vapor and SO 2 /SO 3 are present upon combustion of sulfur bearing fuels, H I S0 4 mist is formed as temperatures drop. When aqueous alkali metal compounds are atomized into or onto the sulfur bearing fuel at the hottest part of the flame, at combustion point, the above reactions take place almost instantaneously converting the SO 2 /SO 3 into neutral alkali sulfates as a dense precipitating particulate.
  • Example 2 above was repeated this time igniting and burning two (2) gallons per hour of the calcium nitrate solution together with the #6 fuel oil with 1.8% sulfur at 5353 liters per hour.
  • the analysed sulfur content of the exit gases was approximately 0.33 mg sulfur (S0 2 +S0 3 ) per 15 liters of exit gas.
  • the sulfur content of the exit gases in the above examples will be converted to kg of sulfur dioxide per million kilocalories in the fuel. This is the measurement used by the U.S. Environmental Protection Agency which has set a maximum content for new facilities at 0,36 kg SOJ106 kilocalories.
  • the following figures are computed and compared:
  • the sulfur dioxide content was calculated on the basis of factors derived from a calculated quantity of sulfur in the fuel, namely 1.6 kg sulfur per million kilocalories of fuel which is equivalent to 3.3 kg of sulfur dioxide per million kilocalories of fuel.
  • the fuel oil feed rate was 5500 liters or 5265 kg per hour.
  • the sulfur content of the untreated fuel oil was 1.78%. This is equal to 93.5 kg or 2.90 kg moles per hour of sulfur available for reaction with the elements in the fuel oil, the additive, the boiler surfaces, and with oxygen to form sulfur dioxide, sulfur trioxide, other oxides of sulfur, and other products some of which may contain sulfur.
  • the reactions will occur at temperatures of 1260 to 1538°C and, in some instances, at higher temperatures.
  • the total amount of sulfur measured as sulfur dioxide and sulfur trioxide in the exit gases during treatment of the fuel oil with this quantity of calcium nitrate solution was 0.134 kg moles per hour.
EP81850107A 1980-06-16 1981-06-11 Method for reduction of sulfur content in exit gases Expired EP0042367B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81850107T ATE15688T1 (de) 1980-06-16 1981-06-11 Methode fuer die reduktion des schwefelgehalts in abgasen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15945780A 1980-06-16 1980-06-16
US159457 1980-06-16

Publications (3)

Publication Number Publication Date
EP0042367A2 EP0042367A2 (en) 1981-12-23
EP0042367A3 EP0042367A3 (en) 1982-02-03
EP0042367B1 true EP0042367B1 (en) 1985-09-18

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Family Applications (1)

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EP81850107A Expired EP0042367B1 (en) 1980-06-16 1981-06-11 Method for reduction of sulfur content in exit gases

Country Status (6)

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EP (1) EP0042367B1 (sv)
AT (1) ATE15688T1 (sv)
DE (1) DE3172318D1 (sv)
ES (1) ES503058A0 (sv)
IL (1) IL63081A (sv)
SE (1) SE8006781L (sv)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4031379A1 (de) * 1990-04-27 1991-10-31 Sueddeutsche Kalkstickstoff Verfahren zur reduzierung von schadstoffemissionen bei verbrennungsprozessen

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4503785A (en) * 1980-06-16 1985-03-12 Scocca Peter M Method for reduction of sulfur content in exit gases
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
US5513584A (en) * 1986-06-17 1996-05-07 Intevep, S.A. Process for the in-situ production of a sorbent-oxide aerosol used for removing effluents from a gaseous combustion stream
US4834775A (en) * 1986-06-17 1989-05-30 Intevep, S.A. Process for controlling sulfur-oxide formation and emissions when burning a combustible fuel formed as a hydrocarbon in water emulsion
GB2395722A (en) * 2002-11-27 2004-06-02 Polarchem Internat Ltd The prevention or removal of deposits from heating and ancillary surfaces

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE499650A (sv) *
FR863485A (fr) * 1940-02-20 1941-04-02 Perfectionnements apportés aux procédés pour l'amélioration du rendement des moteurs à combustion interne et substances d'adjonction utilisées à cet effet
GB669056A (en) * 1948-02-26 1952-03-26 Bataafsche Petroleum Improvements in and relating to fuels for internal combustion engines and to the operation of such engines
US2949008A (en) * 1958-01-29 1960-08-16 Gulf Research Development Co Residual fuels
DE2228467A1 (de) * 1972-06-10 1973-12-13 Deutsche Bundesbahn Chemischer russvernichter
DD112660A1 (sv) * 1973-06-26 1975-04-20
DK143163C (da) * 1977-09-06 1981-11-09 H C M Andersen Fremgangsmaade til hel eller delvis neutralisation af de ved forbraending af svovlholdigt braendsel dannede sure forbraendingsprodukter,samt middel til anvendelse ved udoevelsen af fremgangsmaaden
DE2961969D1 (en) * 1978-07-25 1982-03-11 Drivex Sa Liquid agent for the chemical destruction of soot and method of application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4031379A1 (de) * 1990-04-27 1991-10-31 Sueddeutsche Kalkstickstoff Verfahren zur reduzierung von schadstoffemissionen bei verbrennungsprozessen

Also Published As

Publication number Publication date
IL63081A0 (en) 1981-09-13
DE3172318D1 (en) 1985-10-24
ES8203632A1 (es) 1982-04-01
ES503058A0 (es) 1982-04-01
EP0042367A3 (en) 1982-02-03
SE8006781L (sv) 1981-12-17
EP0042367A2 (en) 1981-12-23
IL63081A (en) 1985-03-31
ATE15688T1 (de) 1985-10-15

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