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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 effective for reducing the emissions of nitrogen oxides (NO ⁇ , where x is an integer, generally 1 or 2) and visible emissions (particulates or gases which lead to plume opacity) from a gas turbine to the atmosphere.
• NO ⁇ nitrogen oxides
• visible emissions partates or gases which lead to plume opacity
• Gas or combustion turbines have been utilized by many utilities as base load or peaking units to rapidly bring additional electrical generation on line as required and, hence, are preferred for many applications.
• the temperatures at which gas turbines operate tend to cause the production of thermal N0 ⁇ , the temperatures being so high that free radicals of oxygen and nitrogen are formed and chemically combine as nitrogen oxides.
• Nitrogen oxides are troublesome pollutants and comprise a major irritant in smog. It is further believed that nitrogen oxides can cause or enhance the process known as photochemical smog formation through a series of reactions in the presence of sunlight and hydrocarbons.
• nitrogen oxides are a significant contributor to acid rain, and have been implicated in adverse environmental and health effects.
• Gas turbines have historically been a source of NO ⁇ emissions due to their high combustion temperatures, excess oxygen levels, and pressures , which have been found to accelerate thermal NO ⁇ production. Recently, gas turbines have been designed with the capability of separate water injection into the combustion process, which has been found to be effective in controlling nitrogen oxides formation by reducing peak flame temperatures. Although capable of reducing NO ⁇ emissions to 25 parts per million (ppm) on turbines fired with natural gas, water injection rates equal to or in excess of 1.5 x the fuel injection rates are often required.
• DenHerder in U.S. Patent 4,696,638, discusses such emulsions and indicates that the positive effects therefrom include "cleaner exhaust.” Although the disclosure of DenHerder refers to emulsions containing up to about 40% water, DenHerder is primarily directed to emulsions having only up to about 10% water in the form of droplets having a diameter of about 1 to about 10 microns.
• Dainoff and Sprague in U.S. Patent Application entitled “Process for Reducing Nitrogen Oxides Emissions and Improving the Combustion Efficiency of a Turbine", Serial No. 07/691,556, filed April 25, 1991, the disclosure of which is incorporated herein by reference, have discovered that water-in-fuel oil emulsions up to about 50% water by weight are useful for reducing nitrogen oxides and particulate emissions from combustion turbines.
• the Dainoff/Sprague disclosure is directed to those instances when the water-in-fuel oil emulsions are used as the primary fuel for the combustion turbine. They do not address those situations involving turbines being fired primarily with natural gas.
• FIGURE 1 is a schematic illustration of a representative gas turbine liquid fuel supply system having an emulsification system according to the present invention installed therein;
• FIGURE 2 is a schematic illustration of a representative emulsification system according to the present invention as installed in a gas turbine liquid fuel supply system.
• the present invention relates to a method for reducing nitrogen oxides emissions from a gas turbine (which term will be considered to be interchangeable with combustion turbine) fired with natural gas.
• 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, and simultaneously combusting the emulsion with natural gas.
• 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 is into at least one of the combustion cans of the gas turbine through the fuel system.
• Natural gas is, in many cases, the fuel of choice for firing gas turbines because of its lower cost as compared with, alternative fuels.
• Many combustion turbines have the capability to fire either natural gas or a liquid fuel such as a light fuel oil, depending on availability and other combustion characteristics.
• a gas turbine can be modified to permit the simultaneous firing of both natural gas and liquid fuel.
• a turbine designed to fire natural gas alone can be retrofitted to add a liquid fuel system and dual fuel nozzle to thereby permit dual fuel firing.
• the emulsion used in the present invention has as its oil phase what is conventionally known as light fuel oils.
• Light fuel oils contain very little to almost no aromatic compounds and consist of relatively low molecular weight aliphatic and naphthenic hydrocarbons.
• Such fuels generally comprise diesel fuel, distillate fuel, #2 oil, or #4 oil as defined by the American Society of Testing and Measurement (ASTM) standard specification for fuel oils (designation: D 396-86) .
• ASTM American Society of Testing and Measurement
• distillate fuels Included among these are kerosene and jet fuels, both commercial, commonly referred to as Jet A, and military, commonly referred to as JP-4 and JP-5, respectively.
• demineralized water is not required for the successful control of nitrogen oxides and opacity, the use of demineralized water in the emulsion 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 present invention advantageously comprise water in fuel oil emulsions having up to about 92% water by weight.
• the emulsions of this type which have the most practical significance in combustion applications are those having at least about 40% water and are preferably about 45% to about 87% water in fuel oil by weight.
• emulsions having up to about 92% water in fuel oil may easily invert into fuel oil in water emulsions which are equally utilizable for the present invention.
• the emulsions are prepared such that the discontinuous phase (i.e., the water in a water in fuel oil emulsion and the oil in 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..
• the discontinuous phase i.e., the water in a water in fuel oil emulsion and the oil in a fuel oil in water emulsion
• 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.
• the water/fuel oil emulsion exhibit a high degree of stability.
• gas turbines are "peaking" units, as noted, which do not operate regularly. Accordingly, an emulsified fuel may sit stagnant for extended periods or with little recirculation in the fuel line.
• an emulsifier or emulsion stabilizer is also desirable in the water/fuel oil emulsion.
• 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 92% 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, poly- oxyethylene (POE) cocamide, cocamide monoethanolamide (MEA) , POE lauramide DEA, oleamide DEA, linoleamide 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 Mazamide ® , and the Mazamide series from PPG-Mazer Products Corp. of Gurnee, Illinois.
• emulsions 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 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 system 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 dispersability characteristics of the emulsifier in water, from no dispersability (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 or opaque 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/stabil- izer 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.
• the continuous phase is #2 oil
• 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 92% water-in-fuel oil for several 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 the combustion process of a gas turbine through the liquid fuel feed lines and burner nozzles conventionally used with such combustion apparatus while simultaneously introducing and combusting natural gas.
• the gas turbine liquid fuel feed lines or combustion can accommodate the emulsion.
• FIGS 1 and 2 illustrate a representative 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 123 b and recirculation pump 128 for recirculation of the fuel through line 120.
• valve 114 in fuel supply line 120 When valve 114 in fuel supply line 120 is closed and valves 20 and 2.2 in emulsification system 10 are open, fuel flowing along fuel supply line 120 is shunted through emulsification system 10 after heater 122, and is resupplied to fuel supply line 120 before final filter 124 for feeding to engine manifold 130 or recirculation.
• a representative 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 use of the emulsion along with natural gas comprises striking advantages over separate water injection systems because the water is provided internal to the flame (that is, the flame is formed in part by the water-bearing element) . By doing so, less water is required to achieve superior results which reduces the deleterious effects of directly introducing large amounts of water into the combustion process. Accordingly, the reduced use of demineralized water and less thermal stress is provided.
• a Turbo Power and Marine Company (TP and M) Model A-9 gas turbine operating as part of a twinpak rated at approximately 33 megawatts which is designed to operate on either 100% gas or 100% distillate fuel oil is modified to allow the unit to operate on both fuels simultaneously.
• An emulsification system comprising two rotary emulsifiers and related ' storage pumping and piping apparatus for preparation and supply of a water in fuel oil emulsion is installed on the distillate fuel oil line just ahead of the last chance filter through a by-pass valve arrangement.
• Baseline data is obtained by firing natural gas alone and then a 50/50 mixture of natural gas and distillate fuel oil for comparison. The unit is then run with water in fuel oil emulsions using various emulsion levels and fuel oil feed rates. The results are set out in Table 1 (the final nitrogen oxides values are each corrected to 15% oxygen) .
• Table 1 illustrates the fact that excellent reductions in nitrogen oxides are obtained when a gas turbine is fired using both natural gas and a water in fuel oil emulsion simultaneously.

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• General Chemical & Material Sciences (AREA)
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• 1991
  • 1991-08-28 US US07/751,170 patent/US5344306A/en not_active Expired - Fee Related
• 1992
  • 1992-01-31 TW TW081100767A patent/TW218395B/zh active
  • 1992-08-19 WO PCT/US1992/007005 patent/WO1993005127A1/en active Application Filing
  • 1992-08-19 AU AU25453/92A patent/AU2545392A/en not_active Abandoned

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