EP1594942A1 - Novel use of phosphor-nitrogen-metal complex - Google Patents
Novel use of phosphor-nitrogen-metal complexInfo
- Publication number
- EP1594942A1 EP1594942A1 EP04701638A EP04701638A EP1594942A1 EP 1594942 A1 EP1594942 A1 EP 1594942A1 EP 04701638 A EP04701638 A EP 04701638A EP 04701638 A EP04701638 A EP 04701638A EP 1594942 A1 EP1594942 A1 EP 1594942A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- combustion zones
- application according
- combustion
- nitrogen
- phosphorus
- 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.)
- Withdrawn
Links
- 239000000446 fuel Substances 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 230000000536 complexating effect Effects 0.000 claims abstract description 4
- 238000002485 combustion reaction Methods 0.000 claims description 43
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003502 gasoline Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000010779 crude oil Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000003247 decreasing effect Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 21
- 239000007789 gas Substances 0.000 description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910000398 iron phosphate Inorganic materials 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 235000019391 nitrogen oxide Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000002737 fuel gas Substances 0.000 description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 230000009916 joint effect Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229940077478 manganese phosphate Drugs 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229940077935 zinc phosphate Drugs 0.000 description 1
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
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
Definitions
- the present invention relates to new applications of the alkali metal-phosphorus-nitrogen complex for reducing emission and decreasing fuel consumption.
- the present invention relates to the formation of alkali metal- phosphorus-nitrogen complex surfaces with complexing chemicals introduced into the fuels, for reducing emission and decreasing fuel consumption.
- the reduced emission, accompanied by fuel saving, is partly due to the newly formed surface, and to the result of catalytic processes.
- Iron-phosphate surfaces were used in Great-Britain even in
- 5,540,788 describes a procedure, in which an inorganic polimer complexing substance is added to the lubricating oil, this way creating an alkali-iron-phosphate surface on the inner surfaces of the combustion zone of the engines, and this results in the improvement of the efficiency of the engine, and the reduction of friction. But the procedure didn't provide solution for other highly used equipments, without direct lubricating in the combustion zone, like for example for the gas turbines, in which the surface of the combustion zone is exposed to extreme thermal and corrosive effects.
- the burner is suitable for the use of vanadium containing additives, because the vanadium-pentoxide, reacting with the magnesium ions in the introduced aqueous solution, inhibits their corrosive deposition.
- vanadium containing additives because the vanadium-pentoxide, reacting with the magnesium ions in the introduced aqueous solution, inhibits their corrosive deposition.
- iron-phosphate surfaces are the most widely used surfaces in the industry. Due to their numerous advantages they are excellently suitable for example for the application in the vehicle industry, for example for the priming of the car-body. Moreover these surfaces provide excellent corrosion protection for the different, iron containing structural components.
- the friction-coefficient of the iron- phosphate surface is significantly lower than that of the steel, and provides dry lubrication on the moving-gliding steel surfaces. Moreover the surface has many characteristics, which improve the efficiency of the oil lubrication.
- organic phosphate compounds are widely used, for example in the lubricating oil. It is known, that certain organic phosphates slowly burn into the gears and into another moving components, and provide excellent protection for the metals. But at the same time the burning shows random distribution, which reduces the application possibilities in the different machines.
- the present invention provides method for the formation of alkali metal-phosphorus-nitrogen complex surfaces in the combustion zone of gas turbines and similar equipments, in such a way that the surface builder substance is introduced into the combustion zone by mixing into the fuel and/ or into the air necessary for combustion.
- the surface builder substance can also be mixed with gasoline or diesel oil, and must be injected into natural gas.
- the surface builder substance and the gas can never be in the same state of condition - the natural gas is characteristically in gas state, while the surface builder substance is liquid. According to this, typically the surface builder substances must be injected into the natural gas used as fuel, because they form surface, and reduce the formation of deleterious element, and the total oxidation of the C-containing compound, and at the same time inhibit the formation of thermic nitrogen oxides. This results in the reduced emission and the higher performance per unit fuel.
- Solution 2 is added in portions to solution 1 while mixing, until the pH of the solution is 7,0.
- the resulting water soluble solution contains the alkali metal-phosphorus-nitrogen-metal complex.
- This water soluble, neutralized complex is added to a "poly-oil".
- the "poly-oil” is any one of a member of poly-glycol or poly-glycol-amine oils, which has a water solubility of at least ten percent, and has a solubility at least ten percent in the liquid hydrocarbon used for the introduction into the combustion zone. All the precipitated materials are filtered off the solution containing the alkali-phosphorus-nitrogen-metal complex, and is mixed into the chosen "poly-oil".
- one part of the complex is mixed into 9-25 part "poly- 5 oil".
- the mixture is continuously stirred, and heated just under the boiling point of 100 °C.
- the mixture is kept at this temperature, and stirred to drive out the water. Once the water is "cooked off, the remaining mixture will turn to a clear amber color very quickly. Then the heat is removed, and the o solution is allowed to cool.
- the color of the solution is normally determined by the used "poly-oil".
- concentration is computed for the amount required.
- concentration in diesel fuel is about 20 parts of phosphorus- 5 nitrogen-metal complex per billion parts of fuel.
- concentration of the surface builder substance must be 500 per one million.
- Characterization of the formed surface is as follows: 0l . Improved heat transfer properties for turbine blades, that make the turbine system perform closer to adiabatic conditions; 2. Improved wear properties for all combustion zone of the engine. 5 There are other benefits that can be associated with the
- the present invention relates to the use of the complex foming additive in the industrial turbines and jet engines.
- One characteristic of the surface builder substance is its ease of use in a variety of common hydrocarbon fuels.
- the surface builder can be formulated to be directly mixed with either gasoline, diesel fuel or aviation diesel (JP-4 and others) and in natural gas.
- the fuel gas pressure ranges from 4 to 10 atmospheres, and the surface builder is injected into the gas stream ranging in pressure from 20 to 500 atmospheres. By injecting the surface builder in this manner, the surface builder enters the gas stream in colloid state.
- FIG. 1 shows an uncoated metal surface
- Figure 2 and Figure 3 show a surface "under construction”.
- the clusters of the alkali-phosphorus-nitrogen-metal complexes can be noticed.
- Figure 2 and Figure 3 the clusters of the alkali-phosphorus- nitrogen complexes have reacted with the surface of the combustion zone, to form the new alkali-phosphorus-nitrogen- metal complex surface.
- the thickness of the new surface is measured in microne, but as it can be seen on Figure 2 and Figure 3, this alkali- phosphorus-nitogen-metal complex is sufficient to present a different surface composition with the fuel air mixture in the combustion zone.
- the alkali-phosphorus-nitrogen-metal surface catalyzes the fuel-air reaction, reducing the unburned hydrocarbon (UHC) and the CO, reduces the secondary reactions, producing nitrogen oxides. After formation of the new surface the nitrogen and the oxigen can not react directly with the metal surface, and the main source of the nitrogen- oxides ceases to exist. (Because the Ni and Cr containing metals catalyze the formation of NO x ).
- the emission reducing and fuel saving effects of the surface builder realizes to a greater extent.
- the complex forming additive can also be used in explosion engines. Certain complexes can be added to the fuel- system of the explosion engines or continuous combustion engines, which form a thin, new layer on the wall of the combustion zone and on the surfaces exposed to the combustion gas.
- This thin layer has beneficial effects for the operation characteristics of the engine, as a result of which the emission of carbon-monoxide (CO), the unburned hydrocarbon (UHC), the nitrogen oxides (NO x ), and the fuel consumption of the vehicle decreases. These beneficial characteristics can be attributed to the better and more complete combustion of the fuels, what is caused by the interaction between the fuel and the thin layer (The carbon deposit disappeared from the exhaust pipe of the experimental vehicles).
- the surface builder may be used with both diesel and gasoline engines, by simply adding the surface builder to the fuel system. The composition of the surface builder has been changed from the original water soluble form to oil soluble form, and as a result of this change the surface builder became soluble in gasoline and in diesel oil, and in any other hydrocarbon based fuel.
- the first step is a "clean-up" phase, when the carbon buildup, particularly carbon deposits in diesel engines are cleaned from the internal working surface, due to the increased reactivity of the surface builder and diesel fuel.
- This "cleanup phase” takes place at any time duration within hours up to two weeks.
- the second step is where the vehicle driver experiences a "sudden" increase in performance. This can be experienced as in sudden engine surge or an increased performance, quieter engine and decreased fuel consumption. This is the joint effect of the complex surface formed and the catalyzed combustion.
- the third and final step when the emission and the fuel consumption is reduced.
- the surface builder described above is only one of the thousand complexes, capable of changing the surface of the combustion zones.
- the surface builder can be any molecule group, which is characterized by joining a metal ion and an alkali-phosphorus-nitrogen bond.
- the present invention not only makes easier the use of the earlier described surface builders, but also by making possible their use in combustion equipments results in the decrease of emission to such an extent, which can initiate changes in the environmental protection up to now unthinkable.
- combustion equipments can be for example the gas firing heat treating furnaces, coal heating boilers and refuse burners.
- the surface builder is introduced into the combustion zone by mixing/ vaporizing into the fuel and/ or into the air necessary for combustion.
- the surface builder has corrosion reduction effects in each metal containing combustion zones. By catalyzing combustion, it reduces fuel consumption, and as a consequence of the more complete combustion, the emission also decreases.
- the additive according to the present invention is injected into the gas firing tube of a natural gas powered 10 MW General Electric gas turbine, before introducing it into the combustion zone.
- Digitally controlled injector is used for compounding, which keeps the fuel gas/ surface builder ratio constant during the 6 hour ' s measurement, i.e. 30-60 ml additive is vaporized into 100 Nm 3 natural gas.
- the emission of the gas turbine is constantly registered.
- the level of the unburned hydrocarbon drops under 0, 1 ppm from the starting 25-35 ppm value.
- the amount of carbon-monoxide drops under the measuring range of the instrument from the starting 0,01% value.
- the amount of nitrogen oxides (NO x ) drops under 2 ppm from the starting 80-90 ppm value.
- Example 1 With the gas turbine used in Example 1. the experiment is repeated for 72 hours, in such a way that the complex is dissolved in diesel fuel, which is more difficult to vaporize. This way additive of bigger particle size enters the combustion zone, which reduces its efficiency, because of the higher viscosity and the weaker vapour-liquid ratio. Despite this the turbine met the more rigorous emission requirements during the measuring.
- a carbon steel piece is heated with gas flame, under standard conditions, at 1100-1300 °C, for 6 hours, with and without additive.
- the addition of the complex compound in the gas in 1/ 1280 ratio results differences visible with the unaided eye both in scale formation and in corrosion.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention relates to new applications of the alkali metal-phosphorus-nitrogen complex for reducing emission and decreasing fuel consumption. In particular, the present invention relates to the formation of alkali metal-phosphorus-nitrogen complex surfaces with complexing chemicals introduced into the fuels, for reducing emission and decreasing fuel consumption. The reduced emission, accompanied by fuel saving, is partly due to the newly formed surface, partly is the result of catalytic processes.
Description
Novel use of phosphor-nitrogen-metal complex
The present invention relates to new applications of the alkali metal-phosphorus-nitrogen complex for reducing emission and decreasing fuel consumption. In particular, the present invention relates to the formation of alkali metal- phosphorus-nitrogen complex surfaces with complexing chemicals introduced into the fuels, for reducing emission and decreasing fuel consumption. The reduced emission, accompanied by fuel saving, is partly due to the newly formed surface, and to the result of catalytic processes.
Iron-phosphate surfaces were used in Great-Britain even in
1869; this solution was patent protected. This was followed by many developments, improving the original procedure. Due to these improvements not only surfaces of better quality were available, but these made possible the effectuation of better surface-cleaning procedures, or the addition of different metal ions, i.e. zinc, manganese, nickel, which resulted in the formation of an iron-phosphate coating, combined with a divalent metal ion, that is zinc-phosphate or manganese- phosphate coating formed. US Patent No. 5,540,788 describes a procedure, in which an inorganic polimer complexing substance is added to the lubricating oil, this way creating an alkali-iron-phosphate surface on the inner surfaces of the combustion zone of the
engines, and this results in the improvement of the efficiency of the engine, and the reduction of friction. But the procedure didn't provide solution for other highly used equipments, without direct lubricating in the combustion zone, like for example for the gas turbines, in which the surface of the combustion zone is exposed to extreme thermal and corrosive effects.
According to the description of the US Patent No. 6,458,473 the components exposed to high thermal and mechanical loads in the turbine are coated with a heat insulating ceramic layer, which is fixed with a metal bond on the surface of the equipment This way the hot components are protected with a 25-150 μm layer from the thermal load, from the erosion of the contamination in the intake air and in the combusted gas. But the application of the invention is very expensive, because the coating of the surface must be regularly renewed, and the inaction needed for this causes serious problems for those turbines, which are operated periodically and/ or are overloaded. The WO 89/08803 international publication describes a burner, which can be used in gas turbines, and the fuel gas gets into the combustion zone with an additive agent. The burner is suitable for the use of vanadium containing additives, because the vanadium-pentoxide, reacting with the magnesium ions in the introduced aqueous solution, inhibits their corrosive deposition. Although in case of proper mixing the formation of the compound (3 MgO.V^Os) can even be complete, but this solution does not give protection on the
surface of the hot components of the gas turbine, or it doesn't have advantageous effects in another gas-firing equipments, for example in a heat-treating furnace.
It can be known from the US Patent No. 6,328,911, that an additive containing W, Ta and Nb is injected into the fuel gas, which forms compounds with sodium and potassium, and this way inhibits that the sulphates of these alkalis form deposit on the metal surface. The disadvantage of the procedure, that although it significantly reduces the presence of the corrosive, it doesn't protect against oxidation, and it is an expensive method.
By now the iron-phosphate surfaces are the most widely used surfaces in the industry. Due to their numerous advantages they are excellently suitable for example for the application in the vehicle industry, for example for the priming of the car-body. Moreover these surfaces provide excellent corrosion protection for the different, iron containing structural components. The friction-coefficient of the iron- phosphate surface is significantly lower than that of the steel, and provides dry lubrication on the moving-gliding steel surfaces. Moreover the surface has many characteristics, which improve the efficiency of the oil lubrication.
Beyond the metal-phosphate compounds the organic phosphate compounds are widely used, for example in the lubricating oil. It is known, that certain organic phosphates slowly burn into the gears and into another moving components, and provide excellent protection for the metals. But at the same time the burning shows random distribution,
which reduces the application possibilities in the different machines.
The present invention provides method for the formation of alkali metal-phosphorus-nitrogen complex surfaces in the combustion zone of gas turbines and similar equipments, in such a way that the surface builder substance is introduced into the combustion zone by mixing into the fuel and/ or into the air necessary for combustion.
The surface builder substance can also be mixed with gasoline or diesel oil, and must be injected into natural gas.
Due to the differences in the molecular weights the surface builder substance and the gas can never be in the same state of condition - the natural gas is characteristically in gas state, while the surface builder substance is liquid. According to this, typically the surface builder substances must be injected into the natural gas used as fuel, because they form surface, and reduce the formation of deleterious element, and the total oxidation of the C-containing compound, and at the same time inhibit the formation of thermic nitrogen oxides. This results in the reduced emission and the higher performance per unit fuel. The essence of the injection technique is that the surface builder substance is introduced into the gas stream with high pressure - this is essentially a "flash injection" - as a result of which even the surface builder substance gets into colloid fume/fog state, due to the equilibrium characteristics of the liquid vapour.
The preparation of the surface builder substance is described in the US Patent No. 5,540,788, which is the antedecent of the present invention.
Hereunder the method of preparation of the concentrates serving the introduction of the complex builder substance, participating in the formation of the surface is described in details:
Table 1 Reagent solutions for the formation of the phosphorus- nitrogen-metal ion complex
Solution 2 is added in portions to solution 1 while mixing, until the pH of the solution is 7,0. The resulting water soluble solution contains the alkali metal-phosphorus-nitrogen-metal complex. This water soluble, neutralized complex is added to a "poly-oil". The "poly-oil" is any one of a member of poly-glycol or poly-glycol-amine oils, which has a water solubility of at least ten percent, and has a solubility at least ten percent in the liquid hydrocarbon used for the introduction into the combustion zone. All the precipitated materials are filtered off
the solution containing the alkali-phosphorus-nitrogen-metal complex, and is mixed into the chosen "poly-oil". Depending on the composition of the alkali-phosphorus-nitrogen-metal complex, one part of the complex is mixed into 9-25 part "poly- 5 oil". The mixture is continuously stirred, and heated just under the boiling point of 100 °C. The mixture is kept at this temperature, and stirred to drive out the water. Once the water is "cooked off, the remaining mixture will turn to a clear amber color very quickly. Then the heat is removed, and the o solution is allowed to cool. The color of the solution is normally determined by the used "poly-oil".
This solution is called "concentrate". A dilution factor is computed for the amount required. As an example the final concentration in diesel fuel is about 20 parts of phosphorus- 5 nitrogen-metal complex per billion parts of fuel. Using a dilution ratio of 1280 to 1, the concentration of the surface builder substance must be 500 per one million.
Characterization of the formed surface is as follows: 0l . Improved heat transfer properties for turbine blades, that make the turbine system perform closer to adiabatic conditions; 2. Improved wear properties for all combustion zone of the engine. 5 There are other benefits that can be associated with the
"thin layer". Other such benefits include a lower coefficient of friction (reduction in positive power losses), reduction of
surface corrosion, increased thermodynamic efficiency in turbine blades.
Gas turbine applications The present invention relates to the use of the complex foming additive in the industrial turbines and jet engines. One characteristic of the surface builder substance is its ease of use in a variety of common hydrocarbon fuels. The surface builder can be formulated to be directly mixed with either gasoline, diesel fuel or aviation diesel (JP-4 and others) and in natural gas. The fuel gas pressure ranges from 4 to 10 atmospheres, and the surface builder is injected into the gas stream ranging in pressure from 20 to 500 atmospheres. By injecting the surface builder in this manner, the surface builder enters the gas stream in colloid state.
As a result of the initial reaction of the surface builder in the combustion zone forms a phosphorus-nitrogen complex that has an excess of electrons. This complex is highly reactive with metal ions. An example of the surface construction may be seen in Figure 1, Figure 2 and Figure 3.. Figure 1 shows an uncoated metal surface, Figure 2 and Figure 3 show a surface "under construction". In the latter figures the clusters of the alkali-phosphorus-nitrogen-metal complexes can be noticed. In Figure 2 and Figure 3 the clusters of the alkali-phosphorus- nitrogen complexes have reacted with the surface of the combustion zone, to form the new alkali-phosphorus-nitrogen- metal complex surface.
The thickness of the new surface is measured in microne, but as it can be seen on Figure 2 and Figure 3, this alkali- phosphorus-nitogen-metal complex is sufficient to present a different surface composition with the fuel air mixture in the combustion zone. The alkali-phosphorus-nitrogen-metal surface catalyzes the fuel-air reaction, reducing the unburned hydrocarbon (UHC) and the CO, reduces the secondary reactions, producing nitrogen oxides. After formation of the new surface the nitrogen and the oxigen can not react directly with the metal surface, and the main source of the nitrogen- oxides ceases to exist. (Because the Ni and Cr containing metals catalyze the formation of NOx).
Using the surface builder in jet engines or gas turbines, the emission reducing and fuel saving effects of the surface builder realizes to a greater extent.
The complex forming additive can also be used in explosion engines. Certain complexes can be added to the fuel- system of the explosion engines or continuous combustion engines, which form a thin, new layer on the wall of the combustion zone and on the surfaces exposed to the combustion gas.
This thin layer has beneficial effects for the operation characteristics of the engine, as a result of which the emission of carbon-monoxide (CO), the unburned hydrocarbon (UHC), the nitrogen oxides (NOx), and the fuel consumption of the vehicle decreases. These beneficial characteristics can be attributed to the better and more complete combustion of the fuels, what is caused by the interaction between the fuel and the thin layer (The carbon deposit disappeared from the
exhaust pipe of the experimental vehicles). The surface builder may be used with both diesel and gasoline engines, by simply adding the surface builder to the fuel system. The composition of the surface builder has been changed from the original water soluble form to oil soluble form, and as a result of this change the surface builder became soluble in gasoline and in diesel oil, and in any other hydrocarbon based fuel.
Both diesel and gasoline engines build complex surface by using compounded fuel. Both engine types develop the surface in different steps. The first step is a "clean-up" phase, when the carbon buildup, particularly carbon deposits in diesel engines are cleaned from the internal working surface, due to the increased reactivity of the surface builder and diesel fuel. This "cleanup phase" takes place at any time duration within hours up to two weeks.
The second step is where the vehicle driver experiences a "sudden" increase in performance. This can be experienced as in sudden engine surge or an increased performance, quieter engine and decreased fuel consumption. This is the joint effect of the complex surface formed and the catalyzed combustion.
The third and final step, when the emission and the fuel consumption is reduced.
By stopping the compounding the advantageous surface slowly deteriorates, and the original disadvantageous condition is restored.
The surface builder described above is only one of the thousand complexes, capable of changing the surface of the combustion zones. The surface builder can be any molecule
group, which is characterized by joining a metal ion and an alkali-phosphorus-nitrogen bond.
The present invention not only makes easier the use of the earlier described surface builders, but also by making possible their use in combustion equipments results in the decrease of emission to such an extent, which can initiate changes in the environmental protection up to now unthinkable. Such combustion equipments can be for example the gas firing heat treating furnaces, coal heating boilers and refuse burners. In each case the surface builder is introduced into the combustion zone by mixing/ vaporizing into the fuel and/ or into the air necessary for combustion. The surface builder has corrosion reduction effects in each metal containing combustion zones. By catalyzing combustion, it reduces fuel consumption, and as a consequence of the more complete combustion, the emission also decreases. Using heat treating furnaces further advantage of the additive that significantly decreases the formation of scale, which means, that other environment polluting technologies can be replaced, and decrease of the quality (e.g. the hardening due to the removal of scale with graphite) of the heat treated metal can be avoided during removal of scale.
There have been numerous tests performed to demonstrate the features and performance of the surface builder. The tests were run by independent parties, and were controlled by independent experts. The stocks were provided by the inventors.
Companies running the tests:
1. Hungarian Environmental Institute, Budapest, Hungary
2. MOL Tests, Beregdarόc, Hungary
3. Bosch Service, Nyϊregyhaza, Hungary 4. Lithuanian Railway Systems, Vilnius, Lithuania
Example 1
The additive according to the present invention is injected into the gas firing tube of a natural gas powered 10 MW General Electric gas turbine, before introducing it into the combustion zone. Digitally controlled injector is used for compounding, which keeps the fuel gas/ surface builder ratio constant during the 6 hour's measurement, i.e. 30-60 ml additive is vaporized into 100 Nm3 natural gas. The emission of the gas turbine is constantly registered. The level of the unburned hydrocarbon drops under 0, 1 ppm from the starting 25-35 ppm value. The amount of carbon-monoxide drops under the measuring range of the instrument from the starting 0,01% value. The amount of nitrogen oxides (NOx) drops under 2 ppm from the starting 80-90 ppm value.
Example 2
With the gas turbine used in Example 1. the experiment is repeated for 72 hours, in such a way that the complex is dissolved in diesel fuel, which is more difficult to vaporize. This way additive of bigger particle size enters the combustion zone, which reduces its efficiency, because of the higher viscosity and the weaker vapour-liquid ratio. Despite this the turbine
met the more rigorous emission requirements during the measuring.
Example 3
A carbon steel piece is heated with gas flame, under standard conditions, at 1100-1300 °C, for 6 hours, with and without additive. The addition of the complex compound in the gas in 1/ 1280 ratio results differences visible with the unaided eye both in scale formation and in corrosion.
Example 4
The effects of the surface builder is investigated, mixed into the fuel of a DAF camion. The fuel consumption of the camion is monitored with a digital instrument (which can continuously record the distance covered and consumption). It is clear from the appendix, that the consumption decreased from the starting 43-44 1/ 100 km to 36-38 1/ 100 km (BOSCH diagram appendix, Figure 4).
Claims
1. Application of alkali-phosphorus-nitrogen-metal complexes for the formation of the surfaces of combustion zones, comprising that the complex forming substances are introduced into the combustion zone by mixing into the fuel and/ or into the air necessary for the combustion.
2. The application according to Claim 1, comprising that the combustion zones are combustion zones of diesel engines.
3. The application according to Claim 1, comprising that the combustion zones are combustion zones of gasoline engines.
4. The application according to Claim 1, comprising that the combustion zones are combustion zones of industrial turbines.
5. The application according to Claim 1, comprising that the combustion zones are combustion zones of jet engines.
6. The application according to Claim 1, comprising that the combustion zones are combustion zones of heat treating furnaces.
7. The application according to Claim 1, comprising that the combustion zones are combustion zones of coal heating boilers.
8. The application according to Claim 1, comprising that the combustion zones are combustion zones of refuse burners.
9. The application according to Claim 1, comprising that the complex forming additive is dissolved in crude oil destination products.
10. The application according to Claim 1, comprising that the complex forming additive is dissolved in water.
11. The application according to Claim 1 , comprising that the alkali metal-phosphorus-nitrogen complex is formed from the Al, Ni, Cr atoms of the surface to be protected, instead of the iron complexing.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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HU0300105 | 2003-01-13 | ||
HU0300105A HUP0300105A3 (en) | 2003-01-13 | 2003-01-13 | A new application of phosphorus-nitrogen-metal complex layer |
PCT/HU2004/000001 WO2004069965A1 (en) | 2003-01-13 | 2004-01-13 | Novel use of phosphor-nitrogen-metal complex |
Publications (1)
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EP1594942A1 true EP1594942A1 (en) | 2005-11-16 |
Family
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EP04701638A Withdrawn EP1594942A1 (en) | 2003-01-13 | 2004-01-13 | Novel use of phosphor-nitrogen-metal complex |
Country Status (5)
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EP (1) | EP1594942A1 (en) |
JP (1) | JP2006516301A (en) |
HU (1) | HUP0300105A3 (en) |
PL (1) | PL377902A1 (en) |
WO (1) | WO2004069965A1 (en) |
Families Citing this family (4)
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EA008844B1 (en) | 2003-06-23 | 2007-08-31 | Инвайрофьюэлз Л.П. | Additive for hydrocarbon fuel, fuel based thereon and related process |
UY29142A1 (en) * | 2004-09-28 | 2006-11-30 | Envirofuels Lp | LIQUID OR LIQUID HYDROCARBON FUEL ADDITIVE FOR DIRECT FIRE BURNERS, OPEN CALLS AND RELATED PROCESSES |
PE20060804A1 (en) * | 2004-11-15 | 2006-09-23 | Envirofuels Lp | PROCESS FOR THE PREPARATION OF A FUEL ADDITIVE CONTAINING SOLID HYDROCARBONS IN DIRECT FIRE BURNERS, OVENS OR OPEN FLAME |
WO2010026598A1 (en) * | 2008-09-08 | 2010-03-11 | Raju Alluri Sreenivasa | Fuel saving process using hollow micro spheres in internal combustion engine |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB776502A (en) * | 1954-07-12 | 1957-06-05 | Bataafsche Petroleum | Method of lubricating solid surfaces |
US3483178A (en) * | 1968-04-18 | 1969-12-09 | Monsanto Co | Esters,salts,and acids of organo-phosphono-amine oxides |
US3734963A (en) * | 1969-03-18 | 1973-05-22 | Exxon Co | Inorganic lithium-amine complexes |
JP3495043B2 (en) * | 1992-09-11 | 2004-02-09 | シェブロン リサーチ アンド テクノロジー カンパニー | Fuel composition for two-stroke engine |
US5540788A (en) * | 1995-02-24 | 1996-07-30 | Mdechem, Inc. | Method of preparing iron-phosphate conversion surfaces |
-
2003
- 2003-01-13 HU HU0300105A patent/HUP0300105A3/en unknown
-
2004
- 2004-01-13 EP EP04701638A patent/EP1594942A1/en not_active Withdrawn
- 2004-01-13 JP JP2006502342A patent/JP2006516301A/en active Pending
- 2004-01-13 WO PCT/HU2004/000001 patent/WO2004069965A1/en active Application Filing
- 2004-01-13 PL PL377902A patent/PL377902A1/en unknown
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See references of WO2004069965A1 * |
Also Published As
Publication number | Publication date |
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HUP0300105A2 (en) | 2004-05-28 |
PL377902A1 (en) | 2006-02-20 |
JP2006516301A (en) | 2006-06-29 |
HU0300105D0 (en) | 2003-03-28 |
HUP0300105A3 (en) | 2005-05-30 |
WO2004069965A8 (en) | 2005-08-25 |
WO2004069965A1 (en) | 2004-08-19 |
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