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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/188—Carboxylic acids; metal salts thereof
  • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
• • 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
  • C10L1/14—Organic compounds
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
  • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters

Definitions

• This invention relates to residual fuel oil compositions and the preparation and combustion thereof, which fuel oil compositions contain certain zirconium salts to reduce the amount of particulate matter formed during combustion.
• Residual fuel oils including Grades Nos. 4, 5 and 6 (ASTM D-396), are widely used in a variety of industrial heating and steam boiler applications.
• a particularly desired fuel oil is No. 6, which is extensively used by utility and power companies.
• emission standards tend to be different and compliance by a residual fuel oil in one location may not necessarily be achieved in another. Further, since standards are continuously subject to change, a residual fuel oil currently in compliance with emission standards may not be in compliance in the near future in the same location and under the same end-use conditions.
• Residual fuel oils which tend to produce excessive amounts of particulate emission generally have one or more characteristics associated with them: a sulfur content above about 1 percent; a Conradson Carbon Residue (ASTM D-189, also termed "Con Carbon” in the art) above about 7 percent; or a high asphaltene content. Residual fuel oils yielding pariculate emissions that surpass the existing standards can't be directly used, but in some cases can be blended in admixture with fuels that do meet existing standards, which are generally low in sulfur and/or low in "Con Carbon” and asphaltene content. This situation has resulted in an overall increased demand for fuel oils which meet emission standards despite their diminishing supply and attendant increase in cost.
• What is desired is a process for increasing the utility of these high emission yielding residual fuel oils for industrial heating purposes in a manner that results in acceptable particulate emissions, despite a high sulfur content, a high Con Carbon residue and/or high asphaltene content.
• the novelty of the present invention resides in the discovery that zirconium salts of certain alcohols/ phenols or sulfonic acids exert a beneficial effect on residual fuel oil, particularly No. 6 fuel oil, in reducing the amount of particulate matter formed during combustion.
• residual fuel oil particularly No. 6 fuel oil
• residual fuel oil is well-known and as described hereinabove, and includes Grades No. 4, No. 5 and No. 6 residual fuel oils, meeting the specifications of ASTM D-396. Particularly preferred is No. 6 fuel oil.
• the subject zirconium salts or compounds also termed “additives” herein, operative in the instant invention, comprise oil soluble zirconium salts of an alcohol/phenol or sulfonate.
• the zirconium salt of selected alcohols or phenols will be a zirconium salt of an alcohol or phenol having the formula: where R is a hydrocarbyl group of 2 to 24 carbon atoms. More particularly R is a branched or unbranched, hydrocarbyl group preferably having 2 to 13 carbon atoms.
• Preferred compounds are those where R is a saturated or unsaturated aliphatic group having 2 to 8 and more preferably 3 to 4 carbons.
• R is a saturated aliphatic group, and particularly those having 3 to 4 carbons.
• Compounds of this type include R groups which may be alkyl, aryl, alkaryl, aralkyl and alkenyl.
• Illustrative alcohol or phenol compounds of this type include ethanol, propanol, butanol, hexanol, decanol, octadecanol, eicosanol, phenol, benzyl alcohol, xylenol, naphthol, ethyl phenol, crotyl alcohol etc. Further information and description of the useful alcohols of this type may be found in Kirk-Othmer, "Encyclopedia of Chemical Technology" Second Edition, 1963, Vol 1, pp 531-638.
• the zirconium salt of sulfonic acids useful in this invention are the zirconium salts of sulfonic acids having the formula: where R is a hydrocarbyl group having 2 to 200 and preferably 10 to 60 carbon atoms. More particularly, the R group in said sulfonic acids will be an alkyl, cycloalkyl, aryl, alkaryl or aralkyl and said salt will have a molecular weight of about 100 to about 2500, preferably about 200 to about 700.
• the sulfonic acids are characterized by the presence of the sulfo group -S0 3 H (or -S0 2 0H) and can be considered derivatives of sulfuric acid with one of the hydroxyl groups replaced by an organic radical.
• Compounds of this type are generally-obtained by the treatment of petroleum fractions (petroleum sulfonates). Because of the varying natures of crude oils and the particular oil fraction used, sulfonates generally constitute a complex mixture and it is best to define them in a general manner giving the molecular weight as defined above.
• Particularly preferred sulfonates are those having an alkaryl group, i.g. alkylated benzene or alkylated naphtalene.
• Illustrative examples of sulfonic acids useful in this invention are: dioctyl benzene sulfonic acid, dodecyl benzene sulfonic acid, didodecyl benzene sulfonic acid, dinonyl naphthalene sulfonic acid, dilauryl benzene sulfonic acid, lauryl cetyl benzene sulfonic acid, polyolefin alkylated benzene sulfonic acid such as polybutylene and polypropylene, etc. Further details regarding sulfonic acids may be found in Kirk-Othmer, "Encylo- pedia of Chemical Technology", Second Edition, 1969, Vol. 19, pp 311 to 319 and in "Petroleum Sulphonates" by R. Leslie in Manufacturing Chemist, October 1950 (XX1, 10) pp 417 to 422.
• the zirconium additive is incorporated into the residual fuel oil by dissolving therein. This is accomplished by conventional methods as by heating, stirring and the like.
• the amount of zirconium additive to be used is an "effective trace amount" that will reduce the amount of particulate matter formed during combustion of the residual fuel oil as compared to the combustion of said fuel oil in the absence of said additive.
• "effec- tive trace amount” is quantitatively generally meant an amount of about 1 to 1000 ppm by weight and preferably 10-500 ppm by weight, zirconium additive, taken as metallic zirconium, in said fuel oil, and particularly preferred about 50 to 150 ppm by weight zirconium additive, taken as metallic zirconium, in said fuel oil.
• lower and higher amounts than the 1-1000 ppm range can also be present provided an effective trace amount, as defined herein, is present in the residual fuel oil.
• reduce the amount of particulate matter formed during combustion is normally meant that at least about a five percent reduction in formed particulate matter, and preferably from about 10 to 25 percent and greater, reduction in formed particulate matter is achieved as compared to the combustion of the residual fuel oil in the absence of the subject zirconium additive.
• the fuel oil containing said additive is generally mixed with oxygen, usually in the form of air, to form a fuel/air mixture prior to combustion.
• oxygen usually in the form of air
• the amount of air utilized is an excess over the stoichiometric amount to completely combust the fuel oil to carbon dioxide and water. The reason for utilizing this excess is that complete mixing does not always occur between the fuel oil and the air, and that also a slight excess of air is desirable since it serves to reduce the tendency of soot and smoke formation during combustion.
• the excess of air used is about 2 to 35 percent (0.4 to 7 percent based on oxygen) over the stoichiometric amount depending upon the actual end-use conditions which may vary considerably from one type of industrial boiler to the next.
• the above-described step of mixing fuel oil and air is conventional and is usually accomplished for example, by steam or air atomization to produce a fine spray which is then combusted to maintain and support a flame.
• the combustion is controlled and conducted at a particular "firing rate" which is usually expressed as lbs/minute of fuel oil combusted.
• the combustion of residual fuel oil is usually carried out in conventional industrial boilers, utility boilers, refinery furnaces and the like.
• the amount of particulate matter formed during combustion of residual fuel oil will vary over a broad range and is dependent upon a number of factors such as type of boiler, boiler size, number and type of burners, source of the residual fuel oil used, amount of excess air or oxygen, firing rate and the like. Generally, the amount of particulate matter formed will be in the range of about 0.01 to 1.0 weight percent of the fuel oil used and higher. One weight percent corresponds to one gram particulate matter formed from the combustion of 100 grams of fuel oil.
• total particulate matter The amount of particulate matter formed, herein termed “total particulate matter,” is actually the sum of two separate measurements; “tube-deposits,” the amount of particulate matter deposited inside of the boiler, and two, “filtered stack particulate,” which is the amount of particulate matter formed which escapes the boiler and is actually emitted out of the stack into the air.
• EPA measurements are generally only concerned with filtered stack particulate which is directly released into the air environment and contributes to a decrease in air quality.
• “tube deposits” lead to corrosion of the equipment, frequent “clean-outs” and add to the total operating costs.
• tube deposits collect on the inside of the apparatus, a critical crust thickness is reached and further tube deposits are then entrained in stack particulate, which significantly increases the amount of particulate emission.
• the amount of tube deposits should also be considered, as well as total stack particulate for compliance with emission standards.
• the amount of allowed stack particulate will vary from state to state and is also subject to a minimum amount allowed under Federal EPA standards. For example, in Florida, the currently allowable limit for existing power plants is 0.10 lbs. particulate emission per million BTU, which is equivalent to about 0.185 weight percent of particulate stack emission per weight of combusted fuel oil. Since the allowable emission standards will vary from jurisdiction to jurisdiction, differing amounts of the subject zirconium additive will be necessary to produce a residual fuel oil composition in compliance with those standards.
• the particulate stack emissions are generally comprised of particulate carbon, sulfur-containing hydrocarbons, inorganic sulfates and the like.
• the first pass is a 49 cm (18.375 in.) diameter x 178 cm (5 ft. 10 in.) long fire tube; the second pass consists of 52 tubes each 6 cm (2.375 in.) diameter x 188 cm (6 ft. 2 in.) long.
• Atomization of the fuel was accomplished using a low pressure air-atomizing nozzle. Viscosity of the fuel oil at the nozzle was maintained at 30 centistokes by heating the oil to a predetermined temperature (about 105°C). Prior to contacting the burner gun, the atomized fuel oil was mixed with a measured amount of excess "secondary" air which was forced through a diffuser plate to insure efficient combustion. The secondary air was provided by a centrifugal blower mounted in the boiler head. The amount of secondary air was controlled by means of a damper which was regulated to keep the oxygen level in the atomized fuel at about 1.5% in excess (over that needed stoichiometrically to completely combust the fuel).
• a run was started by firing the boiler and heating it to operating temperature for 55 minutes using No. 2 oil.
• the feed was then switched to test fuel and after allowing sufficient time for conditions to stabilize (about 25 minutes) samples of about 10 minutes duration were collected isokinetically from the stack on tared, Gelman, Type A (20.3 x 25.4 cm) fiber glass filters.
• the test fuel was a No. 6 fuel oil.
• Total particulate matter formed was determined by adding the amount of Stack particulate measured isokinetically (EPA Method 5 Stack Sampling System) to the amount deposited in the tubes of the boiler i.e. "tube deposits".
• the EPA Method 5 Stack Sampling System was conducted with a commercially available system for this purpose. This unit consisted of an 18-inch glass lined probe, a cyclone, a 125 mm glass fiber filter and four impingers. The first two impingers contained water, the third was empty and the last one contained silica gel. With the exception of the impingers, the entire sampling train was maintained at about 175°C to insure that the stack gases entering the sampling system were above the H 2 SO 4 dew point.
• the deposits laid down in each of the 52 tubes is collected on a separate, tared 20.3 x 25.4 cm fiberglass filter.
• Deposits are collected by positioning a specially-designed filter holder against the end of each tube in turn, pulling air through the tube and the filter using a high-volume vacuum pump and manually brushing the tube from end-to-end ten times with a 2.50 inch diameter wire shank brush.
• the brush is mounted on a 8 ft. long, 0.25 in. diam. SS rod driven by an electric drill. This method gives almost 100% recovery of the deposits laid down in the tubes.
• the zirconium additive used in the run was zirconium propoxide an alcohol salt and was present in a concentration of 100 ppm taken as metallic zirconium.
• the stack particulate was 0.34 wt% on fuel, while the tube deposits was 0.20 wt% on fuel for a total test particulate wt% of 0.54.
• the sample of fuel containing the zirconium propoxide measured a stack particulate of 0.24 wt% on fuel and tube deposits of 0.16 wt% on fuel for a total particulate wt% of 0.40.
• the improvement in using the zirconium additives was a reduction in total particulates of 25.9%.
• Example 1 Following the same general procedure and using the ABCO boiler described in Example 1, a sample run using 100 ppm of a zirconium sulfonate additive, i.e. zirconium salt of dodecyl benzene sulfonic acid, was made with the same No. 6 fuel oil as in said Example 1.
• a zirconium sulfonate additive i.e. zirconium salt of dodecyl benzene sulfonic acid
• the results for the sample containing zirconium sulfonate were a stack particulate of 0.29 wt% on fuel and tube deposits of 0.18 wt% on fuel for a total particulate of 0.47 wt% on fuel.
• the improvement in using the zirconium additive was a reduction in total particulate of 13.0 %.

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Citations (3)

• 1982
  • 1982-07-19 CA CA000407533A patent/CA1187285A/fr not_active Expired
  • 1982-08-11 NO NO822742A patent/NO157788C/no unknown
  • 1982-08-20 EP EP82304401A patent/EP0073615B1/fr not_active Expired
  • 1982-08-20 DE DE8282304401T patent/DE3271555D1/de not_active Expired
  • 1982-08-24 ES ES515204A patent/ES8400479A1/es not_active Expired
  • 1982-08-25 DK DK380782A patent/DK380782A/da not_active Application Discontinuation
  • 1982-08-25 JP JP57146325A patent/JPS5842692A/ja active Pending
  • 1982-08-25 AU AU87574/82A patent/AU546503B2/en not_active Ceased

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