RU2159794C1 - Environmentally safe fuel additive - Google Patents

Abstract

FIELD: environmental protection. SUBSTANCE: additive containing tetraethoxysilane and 0.1-1.0% acetylacetonate transition metal salts. When added to fuel in 0.01% concentration, additive reduces concentrations (by %) of injurious substances in combustion products as follows: carbon monoxide 20-85, unburned hydrocarbons 15-80, nitrogen oxides 15-55, smokes 40-90, and benzpyrene 15-70. EFFECT: significantly improved quality of exhaust. 5 tbl

Description

 The invention relates to the field of ecology, specifically to reducing the content of harmful substances in fuel combustion products.

 Known composite mixture for cleaning the working surfaces of the combustion chamber and gas exhaust tract of internal combustion engines from soot containing 0.1-1.0% metal acetylacetonate and up to 100% additives based on tetraethoxysilane mixed with products of its hydrolysis - dimer, trimer and tetramer [Patent Russian Federation 2027742].

 We propose to use the composite mixture according to RF Patent 2027742 for a new purpose - as an environmental additive to fuel in order to reduce the content of harmful substances that adversely affect the environment and human health in fuel combustion products.

 The proposal to use the known substance for a new purpose confirms the compliance of the proposed technical solution with the criterion of "novelty."

 The composite mixture according to RF Patent 2027742 during combustion together with fuel modifies the structure of soot in the combustion chamber and gas exhaust tract, reduces their adhesion to metal surfaces and reduces the temperature of burnout.

 From the ability of the composite mixture according to RF Patent 2027742 to modify the structure of soot, it is not obvious that its ability to reduce the content of harmful substances in exhaust gases, i.e. from the known properties of the composite mixture according to RF Patent 2027742 it is impossible to draw an unambiguous conclusion about the effect of the composition on the mechanism and kinetics of fuel combustion, leading to a decrease in the content of harmful substances in the fuel combustion products. Therefore, the proposed technical solution meets the criterion of "inventive step".

 The study of the impact of the proposed environmental additives on the content of toxic components and soot in the exhaust gases of a diesel engine was carried out on an experimental setup (Fig. 1), consisting of a 8CH 9.5 / 11 diesel engine with standard systems 1, a measuring tank 3 and a fuel supply tank 8 connected between themselves and the fuel system of the engine with a three-way valve 2, manometers 4 mounted on the intake and exhaust manifolds of the diesel engine, weights 6 and weights 5 mounted on the scales, and a thermometer 7 for determining the spent temperature gases.

 A standard alternator was used as a load device, the load of which varied in the interval 0 - 100% with the help of rheostats.

 The soot content in the exhaust gas of a diesel engine was determined with an OMD-21 optical smoke meter, and the content of unburned hydrocarbons, carbon monoxide and nitrogen oxides with an OPTOGAZ-21 gas analyzer.

 During the tests, the diesel engine was powered by diesel fuel L-0.2-40 GOST 305-82 and MT-16p engine oil GOST 6360-83.

The installation was carried out as follows:
- set the specified engine operation mode:
- number of revolutions - 1700 revolutions per minute
- load - 30 kW;
- the engine warmed up for 45 minutes on the test fuel until the temperature of the coolants and exhaust gases stabilized;
- the temperature of the coolants - water and oil - was maintained in the range of 90 + 5 degrees Celsius;
- simultaneously measured the concentration of harmful substances in the exhaust gas and fuel consumption;
- fuel consumption was determined by the weight method;
- when working on each additive, ten parallel measurements of each parameter were performed and the value obtained by statistical processing of the measured values was taken as the result.

 For testing, various additives were prepared in accordance with US Pat. RF 2027742. All the additives prepared contained 1% metal acetylacetonate of qualification “h” or “hch” and 99% tetraethoxysilane mixed with products of its hydrolysis - dimer, trimer and tetramer according to MPTU 6-09-3074-66.

 Metal acetylacetonates were weighed on an analytical balance of the VLDP-100 brand GOST 19491 = 74 with an accuracy of 0.05 mg, and their solution in tetraethoxysilane was prepared in a volumetric flask with a 100 mL conical thin section type 1-a GOST 1770-74.

 Additives were introduced into diesel fuel L-0.2-40 GOST 305-82 at a concentration of 0.01% using a syringe dispenser DShP-5 TU 64-1-1146-74.

The tests were carried out in two stages:
- at the first stage, the engine was running on clean diesel fuel
- at the second stage - on diesel fuel with additives according to Pat. RF 2027742.

 The results of measurements of the content of harmful substances and soot in the exhaust gases of a diesel engine are presented in table. 1.

 The results of bench tests confirm the effectiveness of using the composite mixture according to US Pat. RF 2027742 as an environmental additive to reduce the content of harmful substances in fuel combustion products.

Considering that of all the tested metal acetylacetonates, the products of iron acetylacetonate combustion - iron oxides - are the least toxic, widespread in nature and their release into the atmosphere cannot cause environmental damage, all subsequent experiments were carried out with an environmental additive of the following composition:
- tetraethoxysilane with an admixture of products of its hydrolysis - dimer, trimer and tetramer of qualification “h” MRTU 6-09-3074-66 - 99%
- iron (III) acetylacetonate qualification "h" MRTU 6-09-2584-68 -1%.

 To determine the effect of our chosen environmental additive on reducing the content of harmful substances in the exhaust gases of a diesel engine, we conducted bench tests of the KamAZ-740 engine in accordance with GOST 14848-81 (ST SEV 765-77). As a loading device, an electric brake stand of VESTIN brand DS 1036-4N was used.

 The tests were carried out on diesel fuel 3-0.2-minus 45 GOST 305-82 and motor oil M10G2k GOST 8581-78.

Engine mode:
- power 500N
- rotation speed - 1500 revolutions per minute.

The tests were carried out in two stages:
- at the first stage, the engine was running on clean diesel fuel without additives;
- at the second stage, the engine was running on the same fuel with 0.01% of the environmental additive of the composition indicated above.

The effectiveness of the environmental additives was evaluated by the content of diesel fuel in the combustion products:
- benz (a) pyrene;
- the amount of aldehydes for acrolein;
- oil spray;
- total content of nitrogen oxides;
- iron oxides;
- silicon dioxide.

 To determine the concentration of benzo (a) pyrene, the "Methodology for measuring the mass concentration of benzo (a) pyrene in the air of the working area using the Fluorat-02 analyzer was used. The lower detection limit is -0.00001 mg / m3. [Physicochemical research methods environmental objects. "Shipbuilding". L., 1979] and the gas chromatographic method [MU N 4171-86. Issue 9].

 Determination of the concentration of the sum of aldehydes was carried out by the photometric method [MU N 2719-83. Issue 18]. The lower limit of detection of acrolein is 0.1 mg / m3. Determination selectively in the presence of ketones, formaldehyde, nitrogen oxides, benzaldehyde, acetaldehyde.

 Nitrogen oxides were determined by the photometric method using the Griss-Ilosvay reagent. The lower limit of measurement of nitric oxide (IV) is 1 mg / m3; nitric oxide (II) - 0.65 mg / m3 {Guidelines for the determination of harmful substances in a welding spray. M., 1990].

 Silicon dioxide concentrations were determined by the photometric method. The lower limit of measurement is 0.25 mg / m3.

 The iron content was determined by the polarographic method. The lower limit of measurement is 0.05 mg / m3 [MU for the determination of harmful substances in a welding aerosol. M., 1990].

The determination of oil aerosol was based on the formation of an emulsion when a solution of oil in isopropanol was diluted with distilled water. The detection limit of 2.0 mg / m3 [TU on methods for determining harmful substances in the air. Release. XI, 1976, M ,,
Reklaminformburo, MMF, MU N 1292-75].

 Presented in the table. 2 results confirm the effectiveness of the claimed environmental additives while reducing the content of harmful substances in the exhaust gases of a diesel engine.

 Evaluation of the effectiveness of the proposed environmental additives in gasoline A-76 and A-92 GOST 2084-77 was carried out on a roller stand of the company "Zolner" RPL 510/22 C M6.8-23 / GPM-100.

 The tests were carried out on a GAZ-24-10 car with an engine ZMZ-24-10 N 010806. Carburetor K-126G.

Diagnostics of the ignition system and adjustment of the engine idling (chemical engine), including the carbon monoxide content, was carried out in accordance with GOST 17.2.2.03-87 (n = 700 rpm; CO _{chemical engine} = 1, 5%; 0.35 - 0.4%).

 Comparative tests for the content of harmful substances in the exhaust gases of the car were carried out according to UNECE Regulation N 83-01 with starting the engine from a warm state.

 Comparative tests for fuel efficiency in the urban cycle were carried out according to GOST 20306-90.

 The acceleration time of a car on gasoline with an additive in direct transmission from a speed of 30 km / h to 100 km / h was determined.

 To analyze the composition of the exhaust gases of the company "Pirburg", AMA-224, the company "Bukman".

 Fuel consumption was measured by a Pirburg meter.

Comparative tests were carried out in two stages:
- at the first stage, the car was tested on clean gasoline A-76 and A-92 without additives
- at the second stage, the proposed environmental additive in a concentration of 0.01% was introduced into gasolines.

Conducted comparative tests of gasoline showed:
- the use of environmental additives for gasolines A-76 and A-92 on a GAZ-24-10 car does not lead to deterioration of engine performance when controlling CO _x.x. within the limits of GOST 17.2.2.03-87 ;.

- the use of an environmental additive for A-76 and A-92 gasolines when testing a GAZ-24-10 car for toxicity according to Rules N 83-10 with starting the engine from a warmed state compared with non-additive gasolines leads to a reduction in emissions:
- carbon monoxide by 4 - 17.8%
- unburned hydrocarbons by 13%
- nitrogen oxides by 2.8 - 10%.

- the use of environmental additives reduces the CO content in the exhaust gases at idle with a minimum speed of 43.0 -60.0%;
- fuel consumption in the urban cycle according to GOST 20306-90 with the use of environmental additives is reduced on average:
- with gasoline A-92 by 3.05%
- with A-76 gasoline by 5.1%;
- the acceleration time of the Gaz-24-10 automobile on a roller stand in direct transmission from a speed of 30 km / h to a speed of 100 km / h when applying an environmental additive practically does not change (within the accuracy of measurements).

 The above test results confirm the effectiveness of the proposed environmental additives. We draw attention to the fact that in addition to reducing the content of harmful substances in the fuel combustion products, the additive also leads to a decrease in fuel consumption, i.e. to reduce any emissions with the same operation of the engine on fuel with an additive compared to its work on fuel without an additive.

 To determine the effect of our chosen environmental additive on reducing the content of harmful substances in the exhaust gases of a gasoline engine, we conducted bench tests of the ZIL-5081 engine in accordance with GOST 14848-81 (ST SEV 765-77). As a loading device, an electric brake stand of VESTIN brand DS 1036-4N was used.

 The tests were carried out on gasoline A-76 GOST 2084-77 and motor oil M8B1 GOST 10541-78.

Engine mode:
- rated power 26.5 kW;
- rotation speed - 1800 revolutions per minute.

The tests were carried out in two stages:
- at the first stage, the engine was running on clean gasoline without additives;
- at the second stage, the engine was running on the same fuel with 0.01% of the environmental additive of the above composition selected by us.

The effectiveness of environmental additives was evaluated by the content of gasoline in the combustion products:
- benz (a) pyrene;
- the amount of aldehydes for acrolein;
- oil spray;
- total content of nitrogen oxides;
- iron oxides;
- silicon dioxide.

 To determine the concentration of benzo (a) pyrene, the "Methodology for measuring the mass concentration of benzo (a) pyrene in the air of the working area using the Fluorat-02 analyzer was used. The lower detection limit is -0.00001 mg / m3. [Physicochemical research methods environmental objects. "Shipbuilding". L. 1979] and the gas chromatographic method [MU N 4171-86. Issue. 9].

 Determination of the concentration of the sum of aldehydes was carried out by the photometric method [MU N 2719-83. Release. 18]. The lower limit of detection of acrolein is 0.1 mg / m3. Determination selectively in the presence of ketones, formaldehyde, nitrogen oxides, benzaldehyde, acetaldehyde.

 Nitrogen oxides were determined by the photometric method using the Griss-Ilosvay reagent. The lower limit of measurement of nitric oxide (1U) -1 mg / m3; nitric oxide (II) - 0.65 mg / m3. {Guidelines for the determination of harmful substances in a welding aerosol. M., 1990].

 Silicon dioxide concentrations were determined by the photometric method. The lower limit of measurement is 0.25 mg / m3.

 The iron content was determined by the polarographic method. The lower limit of measurement is 0.05 mg / m3 [MU for the determination of harmful substances in a welding aerosol. M., 1990].

 The determination of oil aerosol was based on the formation of an emulsion when a solution of oil in isopropanol was diluted with distilled water. The detection limit of 2.0 mg / m3 [TU on methods for determining harmful substances in the air. Release. XI, 1976, Moscow, Reklaminformburo, MMF, MU N 1292-75].

 The test results are presented in table. 3.

 Presented in the table. 3 results confirm the effectiveness of the claimed environmental additives while reducing the content of harmful substances in the exhaust gas of a gasoline engine.

 Operational tests of the proposed environmental additives were carried out on vehicles of the Petersburg Fuel Company on diesel and gasoline engines during their regular work.

 Measurements of the total content of nitrogen oxides, as the most environmentally hazardous component of the exhaust gases of an internal combustion engine, standardized by all international and domestic standards for the content of harmful substances in the exhaust gases of internal combustion engines, were determined at idle at a warmed up engine at higher speeds.

The tests were carried out in two stages:
- at the first stage, the cars ran on commercial fuel without additives;
- at the second stage, the cars ran on fuel of the same batch with the addition of 0.01% of the environmental additive we selected.

 Measurements of the total content of nitrogen oxides in the exhaust gases were carried out with the Testo-therm-300 instrument.

 The brands of tested cars with gasoline engines, fuel brands, methods of preparing the fuel mixture and test results are presented in table. 4.

 The above data show that the use of the proposed environmental additives can reduce the total content of nitrogen oxides in the exhaust gases of various types of gasoline engines running on various grades of gasoline by 15-80%.

 Tests of diesel engines were carried out on winter diesel fuel of the D3p-15 / -25 brand TU 38.101-889-81.

 The test results and brands of test vehicles are presented in table. 5.

 The above data show that the use of the proposed environmental additives allows to reduce the total content of nitrogen oxides in the exhaust gases of diesel cars by 26-28%.

 Tests of the proposed GOST 10585-75 fuel oil, ecological in heavy boiler fuel, were carried out on a steam boiler DKVR-2.5-13 in the boiler house "Shuvalovsky Park" of the Vyborg branch of the State Fuel and Energy Complex of St. Petersburg. The boiler was in good operating condition and operated in the modes and loads determined by the purpose of the boiler room.

The tests were carried out in two stages:
- at the first stage, the boiler worked on a standard boiler fuel without additives;
- at the second stage, 0.01% of the proposed environmental additive was introduced into the fuel oil fuel oil 100.

 The tests showed that the total emission of nitrogen oxides with combustion products is reduced by 25-30% in the entire range of regulation of the boiler, and the efficiency of the boiler is increased by 0.5-1% (large values for lower loads).

 The given results of operational tests confirm the compliance of the proposed technical solution with the criterion of "industrial applicability".

Claims (1)

 The use of a composite mixture for cleaning the working surfaces of the combustion chamber and gas exhaust tract of internal combustion engines from soot containing 0.1 - 1.0% metal acetylacetonate and up to 100% additives based on tetraethoxysilane mixed with products of its hydrolysis - dimer, trimer and tetramer as environmental fuel additives.

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