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WO1992019701A1 - Procede permettant de reduire les emissions d'oxydes azotes et d'augmenter le rendement de la combustion d'une turbine - Google Patents

Procede permettant de reduire les emissions d'oxydes azotes et d'augmenter le rendement de la combustion d'une turbine Download PDF

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Publication number
WO1992019701A1
WO1992019701A1 PCT/US1992/003328 US9203328W WO9219701A1 WO 1992019701 A1 WO1992019701 A1 WO 1992019701A1 US 9203328 W US9203328 W US 9203328W WO 9219701 A1 WO9219701 A1 WO 9219701A1
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WO
WIPO (PCT)
Prior art keywords
emulsion
water
emulsifier
fuel
dea
Prior art date
Application number
PCT/US1992/003328
Other languages
English (en)
Inventor
Alexander S. Dainoff
Barry N. Sprague
Donald T. Brown
Original Assignee
Nalco Fuel Tech
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
Application filed by Nalco Fuel Tech filed Critical Nalco Fuel Tech
Publication of WO1992019701A1 publication Critical patent/WO1992019701A1/fr

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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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328—Oil emulsions containing water or any other hydrophilic phase

Definitions

  • the present invention relates to a process which will improve the combustion efficiency of a gas turbine in order to reduce the emissions of nitrogen oxides (NO ⁇ ) and visible emissions (particulates, which lead to plume opacity) to the atmosphere.
  • NO ⁇ nitrogen oxides
  • visible emissions particles, which lead to plume opacity
  • nitrogen oxides are a significant contributor to acid rain and have been implicated in the undesirable warming of the atmosphere through what is known as the "greenhouse effect" and in the depletion of the ozone layer.
  • gas turbines often emit a visible plume, which is highly undesirable since it causes concern among the population in areas surrounding the facility.
  • oils primarily produced from relatively simple mechanical techniques
  • the oils emulsified are usually heavy oils (i.e., #6 oil).
  • #6 oil the oils emulsified are usually heavy oils (i.e., #6 oil).
  • gas turbines are peaking units, the fuel is required to remain emulsified for at least 30 days in a holding tank, and at least 2 hours during in-line mixing. This has been difficult to accomplish, especially when using mechanical emulsion methodology.
  • gas turbines are very sensitive to corrosion, which often leads the practitioner to avoid introducing emulsified water into the combustion zone.
  • FIGURE 1 is a schematic illustration of a gas turbine fuel supply system having an emulsification system according to the present invention installed therein;
  • FIGURE 2 is a schematic illustration of an emulsification system according to the present invention as installed in a gas turbine fuel supply system;
  • FIGURE 3 is a graphic representation of the results of Examples Ila and lib. Disclosure of Invention
  • the present invention relates to a method for reducing nitrogen oxides emissions and improving the combustion efficiency of a gas turbine (which term will be considered to be interchangeable with combustion turbine) .
  • this invention relates to a process involving the formation of a stable water-and- fuel oil emulsion, where the oil is a light fuel oil such as diesel fuel, distillate fuel or #2 oil.
  • the subject emulsion can be either a water-in-fuel oil or a fuel oil-in-water emulsion (although water-in-fuel oil emulsions are preferred for most applications) , and the introduction of the emulsion into at least one of the combustion cans of a gas turbine through its fuel system.
  • the oil phase in the inventive emulsions comprise what is conventionally known as diesel fuel, distillate fuel, or #2 oil, as defined by the American Society of Testing and Measurement (ASTM) Standard Specification for Fuel Oils (Designation: D 396-86) .
  • distillate fuels Included among these are kerosene and jet fuels, both commercial and military, commonly referred to as JP4 and JP5, respectivel .
  • demineralized water is not required for the successful control of nitrogen oxides and opacity
  • the use of demineralized water in the emulsion formed according to the process of this invention is preferred in order to avoid the deposit of minerals from the water on the blades and other internal surfaces of the gas turbine. In this way, turbine life is extended and maintenance and outage time significantly reduced.
  • the emulsions used in the fuel system of the gas turbine advantageously comprise water-in-fuel oil emulsions having up to about 50% water by weight.
  • the emulsions of this type which have the most practical significance in combustion applications are those having at least about 5% water and are preferably about 10% to about 35% water-in-fuel oil by weight.
  • this invention also relates to the formation of fuel oil-in-water emulsions having about 50% to about 80% water, which have practical applicability in certain situations.
  • the emulsions are prepared such that the discontinuous phase (i.e., the water in a water-in- fuel-oil emulsion and the oil in an a fuel oil-in-water emulsion) has a particle size wherein at least about 70% of the droplets are below about 5 microns Sauter mean diameter. More preferably, at least about 85%, and most preferably at least about 90%, are below about 5 microns Sauter mean diameter.
  • Emulsion stability is largely related to droplet size.
  • the primary driving force for emulsion separation is the large energy associated with placing oil molecules in close proximity to water molecules in the form of small droplets.
  • Emulsion breakdown is controlled by how quickly droplets coalesce.
  • Emulsion stability can be enhanced by the use of surfactants and the like, which act as emulsifiers or emulsion stabilizers. These generally work by forming repulsive layers between droplets prohibiting coalescence.
  • the gravitational driving force for phase separation is much more prominent for large droplets, so emulsions containing large droplets separate most rapidly. Smaller droplets also settle, but can be less prone to coalescence, which is the cause of creaming.
  • the force of gravity acting on the droplet is small compared to thermal fluctuations or subtle mechanical agitation forces.
  • the emulsion can become stable almost indefinitely, although given a long enough period of time or a combination of thermal fluctuations these emulsions will eventually separate.
  • the emulsifier utilized comprises a composition selected from one or more alkanolamides , by which is generally meant an amide formed by condensation of an alkyl or hydroxyalkyl amine or mixtures thereof, and an organic acid.
  • alkanolamides are fatty acids, such as lauric acid, linoleic acid, oleic acid, stearic acid, and coconut oil fatty acids.
  • alkanolamides having a molar ratio of alkanolamine group to acid group of from about 1:1 to about 2:1.
  • compositions can stabilize an emulsion of up to about 50% water-in-fuel oil, or up to about 80% fuel oil-in-water in alkanolamide amounts as low as about 0.05% by weight, and even as low as about 0.01% by weight.
  • emulsifier which can be used, there is usually no need for greater than about 1%, or, in fact, greater than about 0.5% by weight emulsifier in the subject emulsion.
  • the noted alkanolamides should be included in an amount of from about 0.1% to about 0.3% by weight.
  • Suitable alkanolamides which can function to stabilize the emulsion of the process of the present invention include any one or more of the following: cocamide diethanolamine (DEA) , lauramide DEA, polyoxyethylene (POE) cocamide, cocamide monoethanolamide (MEA) , POE lauramide DEA, oleamide DEA, linolea ide DEA, and stearamide MEA, as well as mixtures thereof.
  • Such alkanolamides are commercially available under trade names such as Clindrol 100-0, from Clintwood Chemical Company of Chicago, Illinois; Schercomid ODA, from Scher Chemicals, Inc. of Clifton, New Jersey; Schercomid SO-A, also from Scher Chemicals, Inc.; and M zamide ® , and the Mazamide series from PPG-Mazer Products Corp. of Gurnee, Illinois.
  • emulsifiers which may be useful include ethoxylated alkylphenols, such as nonyl phenol, octyl phenol, etc. and salts of alkylated sulfates or sulfonates, such as sodium lauryl sulfate.
  • emulsifiers or blends of emulsifiers may be also effective at maintaining the stability of the inventive emulsion.
  • the use of the noted emulsifiers provides chemical emulsification, which is dependent on hydrophylic- lipophylic balance (HLB) , as well as on the chemical nature of the emulsifier.
  • HLB hydrophylic- lipophylic balance
  • the HLB of an emulsifier is an expression of the balance of the size and strength of the hydrophylic and the lipophylic groups of the composition.
  • the HLB which was developed as a guide to emulsifiers by ICI Americas, Inc. of Wilmington, Delaware can be determined in a number of ways, most conveniently for the purposes of this invention by the solubility or dispersibility characteristics of the emulsifier in water, from no dispersibility (HLB range of 1-4) to clear solution (HLB range of 13 or greater) .
  • the emulsifiers useful in the present invention should most preferably have an HLB of 8 or less, meaning that after vigorous agitation they form a milky dispersion in water (HLB range of 6-8) , poor dispersion in water (HLB range of 4-6) , or show no dispersability in water (HLB range of less than 4) .
  • a physical emulsion stabilizer in combination with the chemical emulsifiers noted above to maximize the stability of the emulsion achieved in the process of the present invention.
  • Use of physical stabilizers also provides economic benefits due to their relatively low cost.
  • physical stabilizers increase emulsion stability either by increasing the solubility of immiscible phases or by forming an insoluble barrier attracted to the oil/water interface.
  • suitable physical stabilizers are waxes, cellulose products and gums such as whalen gum and xanthan gum.
  • the physical stabilizer is present in an amount of about 0.05% to about 5% by weight of the combination of chemical emulsifier and the physical stabilizer.
  • the resulting combination emulsifier/stabilizer can then be used at the same levels noted above for the use of emulsifier alone.
  • the emulsification provided must be sufficient to maintain the emulsion to a greater extent than if the emulsifier was not present and to as great an extent as possible.
  • the actual level of emulsification will vary depending upon the percentage of oil and water in the emulsion and the particular fuel oil utilized. For example, when the continuous phase is #2 oil, it is highly desired that no more than about 0.1% free water be present in the emulsion, and that the emulsion is maintained that way at ambient conditions for at least about two hours.
  • Ambient conditions that is, the conditions to which the emulsion is expected to be exposed, include the temperature in the gas turbine fuel feed lines. Such temperatures can be up to about 65"C, more typically up to about 90°C and even as high as about 100°C.
  • the emulsion used in the process of the present invention can be formed using a suitable mechanical emulsifying apparatus which would be familiar to the skilled artisan.
  • the apparatus is an in-line emulsifying device for most efficiency.
  • the emulsion is formed by feeding both the water and the fuel oil in the desired proportions to the emulsifying apparatus, and emulsifier or stabilizer when used can either be admixed or dispersed into one or both of the components before emulsification or can be added to the emulsion after it is formed.
  • the emulsifier and/or stabilizer is present at the time of emulsifying the water and fuel oil.
  • any emulsifier or stabilizer used is provided in the water phase, depending on its HLB. It has been found that the emulsions noted above with the chemical emulsifiers can be stabilized at up to about 50% water-in-fuel oil for up to 30 days and longer. In fact, with mild agitation, such as recirculation, it is believed that the emulsion can stay in suspension indefinitely.
  • the emulsion can then be introduced into a combustion can of the gas turbine through the fuel feed lines and burner nozzles conventionally used with such combustion apparatus. There is no need for modification of the gas turbine fuel feed lines or combustion can to accommodate the emulsion used in the process of this invention.
  • FIGS 1 and 2 illustrate a gas turbine fuel supply system having installed therein an emulsification system for the practice of the process of the present invention and a schematic illustration of the emulsification system itself.
  • an emulsification system 10 can be installed in a gas turbine fuel supply system 100 between the heater 122 and the final filter 124.
  • emulsification system 10 is illustrated as being installed in this position in fuel supply system 100, it will be recognized by the skilled artisan that other positions may be more advantageous in terms of emulsion stability in other fuel supply system embodiments, and emulsification system 10 can be installed at virtually any point along fuel supply system 100 for operability. Indeed, it will also be recognized that heater 122 and final filter 124 are preferred components of fuel supply system 100 and conventionally utilized, but not critically needed.
  • Fuel supply system 100 is typical of many gas turbine fuel supply systems and generally comprises a fuel supply line 110 which is fed by a fuel tank or other holding or storage apparatus (not shown) . Fuel flowing through fuel supply line 110 proceeds through a set of initial filters 112a and 112b, and is then fed to individual fuel supply systems 120, 220, and 320 which feed engines controlled by fuel supply system 100. For ease of understanding, fuel supply system 120 which feeds engine manifold 130 is specifically illustrated. Supply systems 220 and 320 are equivalent in operation.
  • Fuel supplied through fuel supply line 110 is fed along engine manifold 130 supply line 120 into heater 122. From there, the fuel flow continues past valve 114 into final filter 124. From final filter 124, the fuel flow continues along line 120 through engine pump 136 and from there into fuel distribution manifold 121 which then supplies the fuel through primary nozzle 132 and secondary nozzle 134 to engine manifold 130, which is the combustion zone of the subject gas turbine.
  • fuel supply system 110 further comprises recirculation lines 123a and 123b and recirculation pump 128 for recirculation of the fuel through line 120.
  • emulsification system 10 comprises an emulsifier supply line 30 which supplies emulsifier from a tank or other storage means (not shown) to a metering pump, and is then fed through line 50.
  • emulsification system 10 comprises water inlet line 40 which feeds water from a tank or other supply means (not shown) through a water pump 28a to supply line 50 where it is admixed with emulsifier supplied from emulsifier supply line 30.
  • the water/emulsifier fed through line 50 then meets fuel being fed through line 58 when valve 20 is open and valve 114 is closed. These are then fed through either one or both of 1 1/2 inch emulsifier 52 or 2 inch emulsifier 54, depending on whether one or both of valves 24 or 26 is open through feed lines 56a and 56b, respectively.
  • the emulsified water-in-fuel oil is then fed via line 58 back through fuel supply line 120 when valve 22 is open and from there into engine pump 136 and into engine manifold 130.
  • the heat of vaporization from the burning fuel causes the emulsified water droplets to become steam, which creates a secondary atomization.
  • This secondary atomization improves combustion and increases the gas volume.
  • the heal required to change the water to steam is believed to reduce the flame temperature of the combustion which helps to reduce formation of nitrogen oxides.
  • water/fuel oil emulsion results in substantial elimination of the need for an expensive, independent smoke suppressant additive.
  • additives are heavy metal based products which can form deposits on the turbine blades, reducing efficiency and increasing maintenance costs.
  • emulsions in the process of this invention a 90% or greater reduction in smoke suppressant additive use is often achieved, which increases the blade life due to reduced deposits, and creates less wear on the turbine blade coatings.
  • the use of the process of this invention leads to improved engine fuel system integrity; the engine burns cooler, which, as noted, leads to less thermal stress; it is believed that the gas turbine can assume a higher load capacity; and compliance with environmental regulations is more easily obtainable.
  • An emulsification system is prepared comprising two rotary emulsifiers and related storage, pumping and piping apparatus for preparation and supply of a water- in-fuel oil emulsion to a Pratt and Whitney Jet engine burning 30 gallons of fuel per minute at full load (21MW) .
  • Baseline emissions tests are run on the engine with non-emulsified distillate fuel oil, and then with emulsified fuel at water levels of 10%, 15%, 20%, 25%, 35%, and 50%.
  • the emulsifier used is oleamide DEA added at 2.5 gallons per 1,000 gallons of fuel (corresponding to .25% of emulsifier by weight) .
  • the emulsion remained stable (i.e., no visible water separation) for over two hours without agitation.
  • Blades and guide vanes are found to be cleaner with the emulsion prepared according to the present invention.
  • An emulsification system in accordance with Figures 1 and 2 is prepared for supply to a single TP&M A4 engine operating as part of a twinpack rated at approximately 35 MW. Flue gas samples are obtained through a three point probe installed on the outlet duct with the sample points located between the guide vanes. The samples are combined and the NO and N0 2 levels therein measured, and compared with baseline levels.
  • Figure 3 illustrates the fact that use of the process of the present invention permits equivalent reduction of nitrogen oxides with approximately 50% of the amount of water injected.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Catalysts (AREA)

Abstract

Procédé de formation d'une émulsion dans les émulsifiants (52) et (54) avec de l'eau provenant d'une admission d'eau (40) ainsi qu'un combustible provenant d'une alimentation en combustible (120) et facultativement un émulsifiant provenant d'une alimentation en émulsifiant (30), et injection de ladite émulsion dans une zone de combustion d'une turbine au moyen d'une pompe de moteur (136) afin de réduire les oxydes azotés ainsi que l'opacité des fumées, et d'améliorer le rendement de combustion d'une turbine.
PCT/US1992/003328 1991-04-25 1992-04-22 Procede permettant de reduire les emissions d'oxydes azotes et d'augmenter le rendement de la combustion d'une turbine WO1992019701A1 (fr)

Applications Claiming Priority (2)

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US69155691A 1991-04-25 1991-04-25
US691,556 1991-04-25

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EP (1) EP0581870A1 (fr)
AU (1) AU1900092A (fr)
CA (1) CA2109096A1 (fr)
WO (1) WO1992019701A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0763080A4 (fr) * 1994-05-31 1998-03-11 Fuel Tech Nv Reduction d'emissions d'oxyde d'azote a partir de moteurs diesel de vehicules
EP0924412A1 (fr) * 1997-12-17 1999-06-23 Asea Brown Boveri AG Procédé d'utilisation d'un groupe à turbine à gaz
US7018433B2 (en) 2000-01-12 2006-03-28 Cam Tecnologie S.P.A.. Fuel comprising an emulsion between water and a liquid hydrocarbon
US7041145B2 (en) 2001-07-09 2006-05-09 Cam Technologie S.P.A. Fuel comprising an emulsion between water and a liquid hydrocarbon
WO2013098630A1 (fr) 2011-12-29 2013-07-04 E.Fuel S.A. Émulsion de gasoil et d'eau
US8511259B2 (en) 2002-03-28 2013-08-20 Cam Technologie S.P.A. Method for reducing emission of pollutants from an internal combusion engine, and fuel emulsion comprising water and a liquid hydrocarbon
WO2014158262A1 (fr) * 2013-03-14 2014-10-02 Rolls-Royce Corporation Émulsion carburant/eau issue d'algues

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0763080A4 (fr) * 1994-05-31 1998-03-11 Fuel Tech Nv Reduction d'emissions d'oxyde d'azote a partir de moteurs diesel de vehicules
EP0924412A1 (fr) * 1997-12-17 1999-06-23 Asea Brown Boveri AG Procédé d'utilisation d'un groupe à turbine à gaz
US6178738B1 (en) 1997-12-17 2001-01-30 Asea Brown Boveri Ag Method of operating a gas-turbine group by directing a fuel/water mixture to the combustion chamber
US7018433B2 (en) 2000-01-12 2006-03-28 Cam Tecnologie S.P.A.. Fuel comprising an emulsion between water and a liquid hydrocarbon
US7994260B2 (en) 2000-01-12 2011-08-09 Cam Tecnologie S.P.A. Fuel comprising an emulsion between water and a liquid hydrocarbon
US7041145B2 (en) 2001-07-09 2006-05-09 Cam Technologie S.P.A. Fuel comprising an emulsion between water and a liquid hydrocarbon
US8511259B2 (en) 2002-03-28 2013-08-20 Cam Technologie S.P.A. Method for reducing emission of pollutants from an internal combusion engine, and fuel emulsion comprising water and a liquid hydrocarbon
WO2013098630A1 (fr) 2011-12-29 2013-07-04 E.Fuel S.A. Émulsion de gasoil et d'eau
WO2014158262A1 (fr) * 2013-03-14 2014-10-02 Rolls-Royce Corporation Émulsion carburant/eau issue d'algues
US9458768B2 (en) 2013-03-14 2016-10-04 Rolls-Royce Corporation Algae-derived fuel/water emulsion

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EP0581870A4 (fr) 1994-04-27
EP0581870A1 (fr) 1994-02-09
CA2109096A1 (fr) 1992-10-26
AU1900092A (en) 1992-12-21

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