Chemical marker and method for production thereof
SUBSTANCE: invention relates to a method of producing a fraction of polymethyl-substituted C18-C36 alkanes of formula: , where n=4-10 by reacting molten atactic polypropylene with atmospheric oxygen at 150-250°C for 1-6 hours with air flow rate of 0.6-1.9 l/min∙kg using secondary low-molecular oxidation products as raw material. The method is characterised by that first, low-molecular products are fractionated collection of the basic fraction at 200-310°C followed by catalytic hydrofining from impurities of alkenes in gas phase or oxidation of alkenes at 100°C with aqueous solution of KMnO4 with weight ratio of the fraction to KMnO4 of 2.5-3.0:1.0, followed by freezing the organic layer at minus 20°C and separating the crystalline water-containing precipitate. The invention also relates to use of said fraction as a chemical marker for hydrocarbon fuels.
EFFECT: disclosed marker has a low cost and high concealment.
2 cl, 5 ex, 1 tbl, 4 dwg
The invention relates to petrochemistry, specifically to the production of special chemicals (SHV)used for covert marking of petroleum fuels, and can be applied when carrying out different types of expertise in the commercial and industrial enterprises for the purpose of detection of oil theft and counterfeit fuels, identifying channels for their implementation and identification of petroleum products in the residues of combustible materials in the investigation of arson [Nekhoroshev SV and other Identification of gasoline hydrocarbon markers. The journal analytical chemistry. 2009, v.64, No. 10, s-1039].
It is known the use of special compounds used for covert marking petroleum fuels [see article Nekhoroshev SV and other Identification and chemical labelling of substances, materials and products (review). The journal analytical chemistry. 2010, t, No. 10, s-1019]. For marking of hydrocarbon liquids is proposed to use one or more dyes of a particular class, to identify which used various spectroscopic methods of analysis (IR, Raman spectroscopy or fluorescence analysis). For marking petroleum fuels using carbonyl compounds, which can only be detected by the absorption in the Central region of the infrared spectrum. Proposed is a device for marking fuels and their subsequent Eden is ificati on specific markers, each of which is introduced into the fuel in a certain concentration. Identification determine the content of each marker using specific sensors optical type. Parameter identification using the ratio so determined concentrations. Chemical labeling of hydrocarbon fuels as markers of the additive used cyanobenzoyl and benzoylisothiocyanate at a concentration of 0.01 to 0.02 wt.%, which are then determined by the method of IR-spectroscopy [Asher W., R. Clarke, Farahat M.S. US Patent No. 09/219288(2005)].
The disadvantages of the known chemical marker are high toxicity and cost of nitrogen-containing benzene derivatives, low variability of the chemical composition, which allows for criminal purposes to copy the token. In addition, the combustion bulleted fuel forming the oxides of nitrogen, which affects the environmental performance of fuels. Spectroscopic methods of analysis of markers in the fuels perform on expensive imported equipment.
Known chemical marker based on n-alkanes C16-C26or their mixtures [Patent RU 2199574 from 27.02.2003,, MKI C10L 1/00]. Alkanes are injected directly into the composition of marked substances (fuel, paraffin, vaseline, anti-corrosion agents, cosmetics or drugs) or prepare compositions containing chemical is Archer, applied to the packaging of the product, introduced in adhesives and other components. Chemical marker corresponds to the requirements for its application:
- is strictly individual, truepowerii and unchanging during prolonged storage structure;
is defined in relatively low concentrations in the range of 1.0 to 5.0 wt.%. widespread GLC;
has no toxic properties;
- has a large number of variations of the marker, which excludes the possibility of its occurrence or coincidence;
- easily made in the laboratory and just pretending to be a serial substances, materials and products.
A feature of the proposed chemical marker is the possibility of its use for marking complex mixtures of organic compounds, such as petroleum products. Add gasoline 1·10-4% alkanes C26-C30allows to reliably distinguish the marked fuel from falsified (see Nekhoroshev SV and others in the Journal analytical chemistry. Identification of gasoline hydrocarbon markers. 2009, v.64, No. 10, s-1039).
For preparing chemical compositions token-based n-alkanes put a thin layer on the external surface of the powder particles of the silica gel from a solution of paraffin in hexane with PEFC is blowing drying the powder in a thin layer first on the air, and then in an oven at 35°C for 2 hours. Cooked medium with a chemical marker due to the high adsorption capacity of silica gel is easily masked by the color marked under preparation by physical mixing it with a tea extract. Waxes are non-polar compounds that cannot be chemically interact with polar molecules of dyes, i.e., not painted.
The disadvantages of the known chemical marker is the high cost of individual alkanes C18-C26obtained synthetically (up to 2.0 million R./kg), which prevents their widespread use in industrial production.
A method of obtaining oxidized atactic polypropylene (APP) with polar functional groups by reacting molten polypropylene with oxygen when it is bubbling in the reaction mass at a temperature of 150-250°C for 1-6 hours and air flow rate of 0.6-1.9 l/(min·kg) [Patent RU 2301812, C08F 8/06]. The method is implemented by continuous synthesis technology on a pilot installation with a capacity of 400 t/year LLC Tactica" , Tomsk. As a byproduct of low molecular weight oxidation products formed water and condensing in the cooler-separator liquid organic substances consisting of alkanes, alkenes, alcohols and ketones. Output low the molecular organic compounds depends on the reaction temperature, the time of oxidation and varies from 1.0 to 6.0% by weight of atactic polypropylene [see article Nekhoroshev V.P. et al. in the Journal of applied chemistry", 2006, t, issue 3, s-496].
Liquid low molecular weight oxidation products APT at 20°C have a light yellow color, with a density of 800 kg/m3the refractive index - 1,4485, kinematic viscosity - 13.9 mm2/s, are distilled at atmospheric pressure in the temperature range 80-310°C. the Objective of the invention is a high conspirationist application token and reduce its cost due to the use as a chemical marker polymethylsiloxane alkanes C18-C36General formula:
The problem is solved in that for obtaining chemical marker based polymethylsiloxane alkanes C18-C36the above General formula spend the first fractionation of low molecular weight oxidation products APP with a selection of the main fraction 200-305°C with subsequent catalytic Hydrotreating of impurities alkenes in the gas phase. Literature search polymethylsiloxane alkanes C18-C36used for chemical marking of fuels, showed a complete absence of the methods of obtaining these compounds in the patent and technical literature and scientific literature.
Substantially the feature differences of the proposed chemical marker from the prototype is the new structure of the token, the new method thereof of the side of low molecular weight oxidation products of APP that provides high conspirationist application token and its low cost (50,0 thousand rubles per ton). Proposed chemical marker based polymethylsiloxane alkanes C18-C36reliably identified in fuels for domestic appliances using gas-liquid chromatography (GLC) due to its unique molecular mass distribution. The proposed concentration of the marker in order to ensure reliable identification of fuels by GLC, are for diesel fuel 1.0% wt., as for gasoline and jet fuel of 0.02-0.2% by weight. The proposed token does not degrade performance fuels.
Obtaining chemical marker carried out as follows. First conduct fractionation side of low molecular weight oxidation products APT the boiling point of the compounds on the plant for distillation at atmospheric pressure. The output of the following fractions (wt.%): 80-120°C - 6,1; 120-160°C and 9.7; 160-200°C - 12,3; 200-310°C - 64,4; VAT residue is 7.5. Light fractions, peregonnaja up to 200°C, cannot be used as a chemical marker for fuels, as in the chromatograms low-intensity signals polymethylsiloxane alkanes C9-C15overlap intense signals of hydrocarbon fuels is. CBM distillation residue contains oligomers of polypropylene and it cannot be used for marking of fuels because of the risk of precipitation when stored fuel. For marking of fuels used target faction 200 to 310°C, which contains an 80.2 wt.% polymethylsiloxane alkanes C18-C36with impurities of alkenes by 16.7% and oxygen-containing compounds (alcohols, ketones, carboxylic acids and their esters) of 3.1 wt.%. For identification of compounds contained in the faction 200-310°C, held its separation on a column of silica gel. Elution was carried out successively with hexane, chloroform and a mixture of chloroform with ethanol (1:1). Solvents drove under vacuum. The composition of the obtained fractions was investigated by the methods of gas chromatography-mass spectrometry, IR, NMR1H and13C-spectroscopy. NMR spectra were recorded on the instrument VARIAN VXR-400.
IR spectra were obtained on the instrument PerkinElmer Spectrum 100 half pans NaCl layer thickness of 0.1 mm, the solvent used carbon tetrachloride.
Chromato-mass-spectrometric analysis was performed on the instrument PerkinElmer Clarus 500 MS using a capillary column with a stationary phase SE-54 (L=30 m, d=0.25 mm). Programming mode thermostat temperature chromatograph: isotherm at 80°C for 3 minutes, then heating at a rate of 10°C/min to 280°C. the Temperature of ispar the indicator 250°C, the flow of carrier gas (helium) - 0.5 cm3/min. Method ionization - electron impact energy of ionizing electrons 70 eV. Based on the results of the study polymethylsiloxane alkanes C18-C36these physico-chemical methods of analysis taking into account the most likely schemes fragmentation of the molecular ions of these compounds we have determined the structure of alkanes.
As samples we used diesel fuel 3-0,05-45 (GOST 305-82), fuel for jet engines brand TC -1 (GOST 10227-86) and gasoline Regular-92 (GOST R 51105-97), produced by LLC "Gazprom pererabotka Surgut plant condensate stabilization. Marking of spent fuels added to the fuel samples are small (0.02 to 1.0% wt.) additives marking substances polymethylsiloxane alkanes With18-C36(purified fraction 200-310°C).
Marking of fuels was carried out according to the following procedure. In a sample of fuel was made minimal additives detection agents: 1.0% wt. in the sample of diesel fuel and 0.02% wt. in samples of gasoline and jet fuel. The sample is thoroughly homogenized. For the detection of markers in samples of the original and bulleted was evaporated fuel: diesel 300, gasoline and jet fuel 100 times (by volume). Evaporation was carried out on an installation for the distillation under vacuum (pressure ≤of 6.7 PA). MA the maximum heating temperature in the case of diesel fuel was 280°C, in the case of gasoline and jet fuel 200°C. After evaporation was prepared ~1% solution of the obtained materials in hexane and analyzed the samples by gas chromatography (GC).
The presence polymethylsiloxane alkanes With18-C36in marked fuel was discovered on the results of the analysis on a gas chromatograph Crystal 2000M. In the analysis of diesel fuel used capillary column with a stationary phase SE-54 (L=15 m, d=0.32 mm). Programming mode thermostat temperature chromatograph: isotherm at 70°C for 5 minutes, then heating with a rate of 4°C/min to 280°C. the temperature of the evaporator 250°C, the speed of the carrier gas (helium) - 3.0 cm3/min
In the analysis of gasoline and jet fuel used capillary column with a stationary phase ULTRA-1 (L=25m, d=0.20 mm). Programming mode thermostat temperature chromatograph: isotherm at 35°C for 2 minutes, then heated at 3°C/min to 280°C. the temperature of the evaporator 250°C, the speed of the carrier gas (helium) - 1.0 cm3/min
Chromatogram of fraction 200-310°C low molecular weight oxidation products of APP is shown in figure 1. Signals polymethylsiloxane alkanes With18-C36the most intense. On the chromatogram observed periodically recurring groups of peaks belonging alkanal and alkenes. Molecular weight alkane is in differ to 42 Amu, which indicates a random break the chain of the polymer during oxidation. The observed gomologichnosti number polymethylsiloxane alkanes is unique in the scientific literature it is not described. In the fuel oil fractions polymethylsiloxane alkanes With18-C36are not, therefore, put markers easy to spot on the chromatogram fuel composition of heavy hydrocarbons by their characteristic molecular weight distribution. Adulterated fuel is usually diluted with straight-run fraction of oil. The number of introduced chemical markers in high-quality fuel possible to calculate the degree of dilution. Impurities alkenes contained in the faction 200-310°C, degrade performance fuels: reduce thermal-oxidative stability during storage due to intensive oxidation by atmospheric oxygen; increase the acidity and concentration of actual pitches.
Cleaning alkanes With18-C36from impurities unsaturated compounds in an industrial environment is carried out on the existing schema Hydrotreating fuel fractions in the gas phase using a hydrogenating catalyst systems. In laboratory conditions, when cleaning small amounts of alkanes With18-C36(up to three liters), using the reaction of oxidative cleavage of alkenes to carboxylic what the slot and ketones strong oxidizers when heated: KMnO 4, K2Cr2O7, Na2Cr2O7. Experimentally proved that the optimum cleaning method at 100°C boiling aqueous solution of KMnO4when the weight ratio of fractions 200-310°C to KMnO4= 2,5-3,0:1,0 subsequent freezing of the organic layer at minus 20°C and separating the crystalline slurry of sediment. When cleaning bichromate sodium and potassium significantly reduced the yield of n-alkanes up to 60% and hardly separated form stable emulsions of alkanes in water.
The invention is illustrated in the examples to obtain and use chemical marker.
Example 1. Raw materials for preparation of chemical marker are side low molecular weight oxidation products of APP, which is obtained at the experimental-industrial plant LLC "Tactica" (Tomsk) at a temperature of 150-250°C. Oxidation of the polymer was carried out at air flow rate of 1.5 l/(min·kg) for 6 hours. One liter (0.8 kg) of low molecular weight oxidation products APT fractionary on the installation for the distillation at atmospheric pressure. The output of the following fractions (% wt): 80-120°C - 6,1; 120-160°C and 9.7; 160-200°C - 12,3; 200-310°C - 64,4. VAT residue is 7.5. Got 515,2 g (644 ml) target faction 200-310°C, which contains 16.7% of wt. (86,0 g) impurities alkenes and 3.1 wt.%. (16.0 g) impurities of oxygen-containing compounds [see article gaevoy LN. and other Structural-group composition of niskama the molecular products thermo-oxidative degradation of the APC. In Journal of applied chemistry. 2011, t, issue 3, s-477]. Chromatogram of fractions is shown in figure 1. The relative content polymethylsiloxane of the following alkanes (% wt.): C18H38- 6,0; C21H44- 28,3; C24H50- 34,2; C27H56- 19,0; C30H62- 8,7; C33H68- 2,7; C36H74is 1.1. The fraction Hydrotreating 200-310°C were performed in a laboratory setup flow-type fixed bed catalyst RC - 442 (alumonickelsilicate catalytic system) at a temperature of 390°C, a pressure of 4.0 MPa. The catalyst with a particle size of 0.4-0.7 mm load in the amount of 30 cm3. The volumetric rate of dispensing of the liquid fraction of 75.0 ml/h, the ratio of hydrogen:fraction = 100:1. The yield of purified fractions 200-310°C was are 507, 5 g (98.5% wt.). According to the results of the analyses of the purified fractions the relative content polymethylsiloxane alkanes has not changed, impurities alkenes and oxygenated compounds are absent. In a round bottom flask with 1000 ml (780 g) jet fuel (GOST 10227-86, grade TS-1, first grade) production Surgut condensate stabilization plant dosing syringe 0.2 ml (0.156 g) hydrotreated fraction 200-310°C polymethylsiloxane alkanes With18-C36(0,02% wt.), the solution is thoroughly mixed with a mechanical stirrer for 3 minutes. The sample labeled fuel volume of 50 ml was placed in the flask of a rotary COI is rites brand IL-1-LT heated to 80-90°C and evaporated under vacuum to 100 times by volume to 0.5 ml
Microspace selected aliquot part one stripped off the sample in a volume of 20 μl, which is transferred into the vial containing 2.0 ml of hexane, the mixture is stirred and analyzed by gas chromatograph "Crystal 2000 M". Chromatogram source and bulleted jet fuels, one stripped off 100 times shown in figure 2. Put the tokens marked with numbers that correspond polymethylsiloxane alkanal in figure 1. The signals of the markers in the source neopreno bulleted fuel TS-1 on the chromatograms are missing, which provides a latent marking of fuel. Because jet fuel is composed of lighter hydrocarbons, the peaks markers are observed at the end of the chromatogram. Introduction to fuel TS-1 less than 0.02 wt.%. markers does not provide reliable detection by the GLC. A small number of introduced chemical marker has virtually no effect on basic physical and chemical indicators of fuels. The most sensitive characteristics of the fuels are: the actual concentration of resins, oxidation resistance, thermal-oxidative stability, iodine number and acidity. These parameters depend on the presence of the marker of organic acids and alkenes. The results of determination of physico-chemical and performance bulleted fuels are given in table 1. Pokazatel the original and branded fuel coincide within the errors of determination, that confirms the possibility of using polymethylsiloxane alkanes as a chemical marker. Fuel analysis was performed in the Central laboratory Surgut condensate stabilization plant. Consider the indicators marked fuels do not go beyond the limits established by regulatory documents for each fuel type (table 1).
Example 2. Perform analogously to example 1, but the clean fractions 200-310°C from impurities unsaturated compounds is conducted in an aqueous solution of KMnO4when the weight ratio of the fraction:KMnO4= 2.5 to 1. First prepare an aqueous solution with 47.4 g KMnO4in 120 ml of H2O that is transferred into a three-neck glass reactor fitted with mechanical stirrer, thermocouple, temperature controller and heater. In the reactor pour 150 ml (120 g) fractions 200-310°C, include the stirrer reactor and heated to 100°C.
The bottom layer of an aqueous solution of a constant humming that promotes good mixing of heterogeneous phases. The reaction is carried out for 2 hours. The reaction mixture is cooled to room temperature, defend 1 hour and separated in a separating funnel the organic layer from the water. At the bottom of the flask falls dark brown precipitate MnO2. Cloudy organic layer is placed in a sealed plastic container in the freezer overnight. At the bottom of the tank rolled small Cree is of Tallaght water mixed with the products of the oxidation of alkenes (ketones and acids). The organic part is carefully decanted from the crystalline precipitate and used for marking fuel TS-1. Output fraction 200-310°C after cleaning is 100 g (125 ml) or 83% wt. The test results bulleted fuel are similar to those of example 1 in table 1. Experimentally proved, that the ratio of the fraction of 200-310°C:KMnO4cannot be greater than 3:1, so as to 4% wt. alkenes contained in the purified fraction due to the lack of an oxidant at a ratio of 3.1:1.
Example 3. Perform analogously to example 1, but mark diesel fuel 3-0,05-45 (GOST 305-82) production Surgut condensate stabilization plant hydrotreated fraction 200-310°C polymethylsiloxane alkanes C18-C36(1.0 wt.%). Chromatogram one stripped off 300 times the original and marked diesel fuel is shown in figure 3. From the comparison of the chromatograms, it follows that the samples differ markedly in composition of heavy hydrocarbons. The chromatogram of diesel fuel with additive observed intense peaks substances 4, 5, 6 and 7, which in the original chromatogram of diesel fuel no. Therefore, these substances belong to the introduced marker. Peaks marking substances are easily found on the chromatogram, and the presence of these peaks can be identified fuel related to the marked party. Marking substances are the ultimate threat is vodorodny branched structure and on the chromatogram their peaks clearly visible in the background peaks of hydrocarbons of normal structure, prevailing in the original diesel fuel. Introduction to diesel fuel less than 1.0 wt.%. marker does not provide reliable detection by the GLC. Indicators source and marked' diesel fuel does not change, which proves that the proposed use of the chemical marker (table 1).
Example 4. Perform analogously to example 2, but the clean fractions 200-310°C is carried out at a ratio faction:KMnO4= 3:1. Output fractions after treatment is 85% wt. The test results are marked diesel fuel to 1.0% by number of the marker, cleared oxidation, similar to those in example 3 in table 1. Chromatogram fuel marker coincide completely with the chromatograms in figure 1.
Example 5. Perform analogously to example 1, but mark unleaded gasoline Regular-92 (GOST 51105-97) production Surgut condensate stabilization plant hydrotreated fraction 200-310°C polymethylsiloxane alkanes C18-C36in the amount of 0.02% by weight. Chromatogram one stripped off 100 times the original and marked gasoline produced in figure 4. Chromatogram neoprene source and bulleted gasoline are the same, which confirms the increased conspirationist marking of fuels proposed markers. Peaks polymethylsiloxane alkanes with 1 to 5 are observed at the end of the chromatogram of gasoline. Exploitationindicated gasoline are shown in table 1. Introduction marker does not degrade the performance of gasoline.
Similar results labeling of gasoline obtained using 0.02 wt.% marker prepared by oxidative degradation of olefins KMnO4.
Thus, the proposed polymethylsiloxane alkanes C18-C36used as a chemical marker for petroleum fuels, reduce the cost of the marker, and reliable identification of marked fuel with high conspirationally application. Properties marked fuels are not changed.
|Physico-chemical characteristics and performance of fuels|
|Sample fuel||Name of indicator||Test method||The standard for grade||The result of the analysis|
|The concentration of gums, mg / 100 cm3fuel, no more than||GOST 8489||5||no (less than 2)|
|1. Marked jet fuel (additives is 0,02% wt.) examples of 1.2.||Thermal-oxidative stability under static conditions at 150°C, the concentration of sediment, mg / 100 cm3fuel, no more than||GOST 11802||10||6,0|
|Acid, 1 mg KOH per 100 cm3fuel, no more than||GOST 5985||0,7||0,5|
|Iodine number, g I2100 g of fuel, no more than||GOST 2070||3,5||0,5|
|2. Marked diesel fuel (additive 1% wt.) examples 3,4.||The concentration of gums, mg / 100 cm3fuel, no more than||GOST 8489||30||no (less than 2)|
|Acidity, mg KOH per 100 cm3fuel, no more than||GOST 5985||5||42|
|Iodine number, g I2100 g of fuel, no more than||GOST 2070||6||0,7|
|3. Bulleted gasoline (the addition of 0.02 wt.%. for example, 5||The concentration of the resin is washed with a solvent in mg per 100 cm3gasoline, not more than||GOST 1567||5||no (less than 2)|
|Oxidation stability, min, not less than||GOST R EN ISO 7536||360||more than 360|
Explanation of figures 1-4.
Figure 1. Chromatogram of fraction 200-310°C low molecular weight oxidation products APT. Numbers indicate peaks polymethylsiloxane alkanes:
1 - C18C38(2,4,6,8,10-pentamethylchroman),
2 - C21H44(2,4,6,8,10,12-geksametilentetramin),
3 - C24H50(2,4,6,8,10,12,14-heptamolybdate),
4 - C27H56(2,4,6,8,10,12,14,16-octamethylene),
5 - C30H62(2,4,6,8,10,12,14,16,18-nonemergency),
6 - C33H68(2,4,6,8,10,12,14,16,18,20-geometrician),
7 - C36H74(2,4,6,8,10,12,14,16,18,20,22-undercapitalization).
Figure 2. Chromatogram one stripped off 100 times the original (a) and labeled (b) jet fuel.
Figure 3. Chromatogram one stripped off 300 times the original (a) and labeled (b) of diesel fuel. Figures 4, 5, 6, 7 marked peaks detection agents.
Figure 4. Chromatogram one stripped off 100 times the original (a) and labeled (b) of gasoline.
1. Coat the Oia polymethylsiloxane alkanes C
18-C36obtained by the method according to claim 2, as a chemical marker for hydrocarbon fuels General formula:
2. The method of obtaining the fraction polymethylsiloxane alkanes according to claim 1 by reacting a melt of atactic polypropylene with oxygen at 150-250°C for 1-6 h at air flow rate of 0.6-1.9 l/(min·kg) using as the raw material side of low molecular weight oxidation products, characterized in that the first fractionary low molecular weight products from the selection of the main fraction 200-310°C with subsequent catalytic Hydrotreating of impurities alkenes in the gas phase or by oxidation of alkenes at 100°C with a water solution of KMnO4when the weight ratio of the fraction:KMnO4= about 2.5-3.0:1.0 and subsequent freezing of the organic layer at minus 20°C and separating the crystalline slurry of sediment.
FIELD: weapons and ammunition.
SUBSTANCE: invention relates to application of a compound for detection of availability of a vegetated explosive substance on the surface of combustible cartridge cases, combustible cylinders, from which missiles are made for tank guns. To confirm availability of the defect of combustible cartridge cases and combustible cylinders it is proposed to analyse observed crystals for determination of their qualitative composition.
EFFECT: method improvement.
FIELD: blasting operations.
SUBSTANCE: weighed portion of the explosive of a predetermined mass is initiated, and the medium pressure level is recorded in the point remote from the test sample of the explosive at a predetermined distance.
EFFECT: improvement of certain characteristics, such as improvement of accuracy of evaluating the properties of explosives, reducing the required amount of explosives for testing, and simplification of the test procedure.
SUBSTANCE: method involves contact sampling from the surface of the object to be analysed for presence of explosives, treating the sample with a polar solvent with reaction thereof with a cationic dye, physical and chemical analysis of the obtained solution in a sorbent layer with visual inspection of the presence of the perchlorate ion from displacement of the coloured zone of the formed ion-associate.
EFFECT: simple and rapid detection of traces of perchlorate compounds with sufficient selectivity.
5 cl, 2 tbl
SUBSTANCE: chemical sensor used is a composite sorbent of the following composition, wt %: finely ground silica gel KSMG - 20, gypsum - 5, 20% liquid glass - 5, water - the balance, which is thoroughly mixed, deposited on aluminium foil, passed through a compression device, dried under an air current from a ventilator and then in a temperature-controlled cabinet until the surface of the sorbent becomes white, cut into sensor strips which are dipped into an engine fuel sample, held for not less than 5 seconds and the colour of said strips is compared with a given scale.
EFFECT: simpler and faster analysis.
2 cl, 1 tbl
FIELD: engines and pumps.
SUBSTANCE: method involves the stage of determination of type and content of biofuel contained in fuel, control stage of injection intensity of reagents and/or additives, control stage of at least one of injection parameters and control stage of at least one of combustion parameters depending on content and type of biofuel in the fuel supplied to internal combustion engine to minimise polluting emissions. Content and type of biofuel are determined by means of a spectroscopic sensor. Injection parameters are as follows: number of injections, injection advance, duration of injection, intensity of injections, control of supercharging mode - flow rate, pressure and temperature of inlet air, change of the section of the turbine guide vanes at operation with turbines with variable geometry. Combustion parameters are as follows: exhaust gas recirculation intensity, cooling of recirculated exhaust gases, compression degree in engines with variable compression degree, and opening and closing of valves. Engine system and equipment using the above method are described.
EFFECT: determination of content and type of biofuel in fuel considering the use of fuel - polluting emissions combination.
15 cl, 3 dwg
FIELD: power industry.
SUBSTANCE: method is based on introduction of microparticles of porous ceramic elements to heat carrier (HC) flow. Simulation is performed by means of experimental plant (2) by introducing a gas jet with the specified parameters to it through inlet connection pipe (1). Perforated funnel (3) is installed into connection pipe (1). Model liquid is arranged in doses, for example in drops throughout the surface of the plant. Besides, HC flow with the specified parameters catches microparticles from surface of funnel (3). Microparticles are heated in hot HC flow to a certain temperature. When coming in contact with model liquid, they are crushed and intensify the evaporation process of that liquid (by transferring their heat to it). When leaving the plant through cyclone filter (4), the flow is cleaned from microparticles, supplied again to perforated funnel (3) via outlet connection pipe (5), and the process is repeated. Input and output values of temperature and pressure are measured during the whole experiment at different points of the experimental plant.
EFFECT: reduction of toxicity; increase in gasification velocity of liquid fuel component; simpler simulation means and provision of their usability both for scientific investigations, and for training purposes.
3 cl, 2 dwg
FIELD: engines and pumps.
SUBSTANCE: proposed unit consists of carcass with sold-state thermostat accommodating sealed reaction pot with tested fuel. Reaction pot cover is provided with hollow cylinder rigidly secured therein to accommodate part of disconnector thread-jointed to cylindrical platform with radial grooves and annular groove distributed over platform circumference to accommodate rubber specimen. Moving platform and stationary bottom of hollow cylinder are arranged in tested fuel to make the elements of electric circuit to be broken by rubber specimen arranged there between. In moving said disconnector upward, rubber specimen is contracted to get metallic platform in contact with hollow cylinder bottom to make electric circuit. Note here that signal is fed to control unit to initiate disconnector direction change. With aforesaid disconnector moving downward, electric circuit between platform and bottom is broken. Rubber specimen contraction force is recorded at circuit breaking at preset axial strain ensured by horizontal platform groove depth. Disconnector is driven in both directions by assembly designed to convert rotation of motor shaft comprising drive gear, driven gear, tie rod, and stopper. Said motion converter is arranged in separate box that displaces over vertical post and may be locked at preset height.
EFFECT: higher accuracy and faster estimation.
2 tbl, 7 dwg
FIELD: engines and pumps.
SUBSTANCE: proposed method comprises identifying magnitudes for, at least, three fuel combustion characteristics selected from the set including ignition delay, maximum pressure difference, maximum temperature difference, intensity of heat release, combustion duration, and time where for maximum pressure develops. It includes comparing identified magnitudes with desirable combustion characteristics for ICE of given configuration for compliance. Said comparison is used to estimate aptitude of tested fuel for ICE of given configuration. Invention covers also method of estimation of said characteristics for updating ICE and method of identification of fuel combustion characteristics.
EFFECT: higher accuracy and reliability of tests.
16 cl, 17 dwg
SUBSTANCE: method involves the following steps: putting crystalline hexogene into a matrix; analysing a sample of the matrix loaded with crystalline hexogene by differential scanning calorimetry; wherein the matrix mainly consists of at least one liquid polymer which is suitable for obtaining binder for energy-yielding materials loaded with nitrated organic explosives and at least one adsorbent of volatile organic compounds which is resistant to analysis temperature and has low affinity for water. The invention also relates to a matrix loaded with crystalline hexogene which is suitable for realising this method.
EFFECT: invention enables to accurately identify the nature of regular hexogene from insensitive hexogene.
11 cl, 1 dwg, 1 tbl
FIELD: machine building.
SUBSTANCE: device includes hollow housing, turbulator housing, separator, positive electrode, turbulator, fastener, and terminal. In upper part of turbulator housing there installed perpendicular to longitudinal symmetry axis of device is inlet connection pipe of non-treated biofuel. In lower part of separator there located perpendicular to longitudinal symmetry axis of the device is outlet connection pipe of dirty biofuel. Outlet connection pipe of treated biofuel is installed along longitudinal symmetry axis of device in lower part of separator. Heater, temperature sensor and fuel turbidity sensor are installed on inlet connection pipe. Monitoring turbidity sensor is installed on outlet connection pipe of treated biofuel.
EFFECT: effective monitoring of quality and improvement of biofuel quality.
SUBSTANCE: gasoline composition primarily consists of gasoline and also includes 1-5 wt % base oil, with respect to the entire gasoline composition, the base oil having kinematic viscosity at 100°C of at least 1 cSt. The invention also relates to a method of operating a spark-ignited four-stroke internal combustion engine, involving feeding a gasoline composition into the combustion chamber of said engine, said composition primarily containing gasoline and 1-5 wt % base oil with respect to the entire gasoline composition. Also described is a gasoline composition for a four-stroke engine, primarily containing gasoline and 1-5 wt % base oil, with respect to the entire gasoline composition, the base oil being based on liquid hydrocarbons and having kinematic viscosity at 100°C of at least 1 cSt.
EFFECT: improved accelerating power of a spark-ignited four-stroke internal combustion engine.
11 cl, 6 tbl, 22 ex
FIELD: oil and gas industry.
SUBSTANCE: invention refers to fuel for detonation kick motor on the basis of synthetic high-density fuel T-10, which differs by the fact that in order to increase its detonation activity, prodetonator - butylhydroperoxide (wt %) is added additionally to the fuel: fuel T-10 99 - 99.3%; tert-butylhydroperoxide 0.7-1%.
EFFECT: creation of fuel for detonation kick motor with increased sensitivity to detonation pulse and improved conditions of its detonation combustion in the chamber of detonation kick motor at introduction to it of tert-butylhydroperoxide as a prodetonator.
SUBSTANCE: present invention relates to use of at least one oil-soluble olefin copolymer B), which acts as a nucleating agent for paraffin crystallisation for improving response of additives C) for improving cold flow of mineral oil, different from B), in middle distillates which contain at least one ash-free, nitrogen-containing detergent additive A), which is an oil-soluble amphiphilic compound which contains at least one alkyl or alkenyl radical bound to a polar group, said alkyl or alkenyl radical having 10-500 carbon atoms and the polar group having 2 or more nitrogen atoms. The additives C) used to improve cold flow contain oil-soluble polar nitrogenous compounds. The present invention also relates to an additive for middle distillates and a middle distillate having sulphur content lower than 100 ppm and 90% final boiling point lower than 360°C.
EFFECT: present invention provides use of oil-soluble olefin copolymers as nucleating agents for paraffin crystallisation in order to prevent deterioration of efficiency of traditional additives for improving cold flow under the action of nitrogen-containing detergent additives.
26 cl, 47 ex, 4 tbl
SUBSTANCE: present invention relates to use of at least one oil-soluble compound B) which acts as a nucleating agent for paraffin crystallisation and is selected from essentially linear hydrocarbons having at least 20 carbon atoms in order to improve response of additive C), which improves cold flow of mineral oil in middle distillates which contain at least one ash-free nitrogen-containing detergent additive A) which is an oil-soluble amphiphilic compound which contains at least one alkyl or alkenyl radical bound to a polar group, the alkyl or alkenyl radical containing 10-500 carbon atoms and the polar group containing 2 or more nitrogen atoms. The present invention also relates to an additive for middle distillates and a middle distillate having sulphur content lower than 100 ppm and 90% final boiling point lower than 360°C.
EFFECT: use of oil-soluble compounds as nucleating agents for paraffin crystallisation in order to prevent deterioration of efficiency of traditional additives for improving cold flow under the action of nitrogen-containing detergent additives.
24 cl, 45 ex, 4 tbl
SUBSTANCE: method of producing low-sulphur diesel fuel and high-octane naphtha is characterised by that the output stream of distillate from the hydrodesulphurisation reaction zone and the output stream from the hydrocracking reaction zone, supplied with dealkylated, high-aromatic material, are mixed and separated to obtain a gas stream of hydrogen, low-sulphur diesel fuel and high-octane naphtha.
EFFECT: feeding hydrogen as a source of hydrogen for the hydrodesulphurisation reaction zone minimises the load on the recirculation compressor, and use of a common separation and fractionation zone gives the advantage of lower capital and operational costs.
10 cl, 1 dwg, 2 tbl, 1 ex
SUBSTANCE: polymer additive which enhances viscosity index is a composition of a hydrogenated block copolymer having at least one polymer block B and, optionally, at least one polymer block A. Before hydrogenation, each block A is a monoalkenylarene homopolymer block, and each block B is a copolymer block with regulated distribution, containing at least one conjugated diene and at least one monoalkenylarene. After hydrogenation, approximately 0-10% arene double bonds are restored and at least approximately 90% conjugated diene double bonds are restored; each block A has number-average molecular weight ranging from approximately 3000 to approximately 60000, and each block B has number-average molecular weight ranging from approximately 20000 to approximately 300000. Each block B has terminal parts adjacent to blocks A, which are rich in conjugated diene links, and one or more parts which are not adjacent to blocks A, which are rich in monoalkenylarene links. The total amount of monoalkenylarene in the hydrogenated block copolymer ranges from approximately 20 wt % to approximately 80 wt %. Content of monoalkenylarene in each block B ranges from approximately 10 wt % to approximately 75 wt %, under the condition that when there is no block A, each block B has terminal parts rich in conjugated diene links, and one or more non-terminal links rich in monoalkenylarene links, and further under the condition that if there is more than one block A, each block A has molecular weight not less than 5000. The composition of the hydrogenated block copolymer is used in amount of 0.2-2.0 wt % in oil compositions for high-efficiency engines.
EFFECT: improved viscosity index of base oil, usually used for engine oil.
8 cl, 1 tbl, 1 ex
FIELD: power industry.
SUBSTANCE: invention can be used for reducing losses of volatile hydrocarbons and associated gases during oil production and refining, and for increasing fire safety of hydrocarbons. Fuel gel includes the following, vol. %: surface active substance products of processing of mixture of mono- and dialkylphenols with ethylene oxide 0.10, water 1.40, ethanol 0.50 and kerosene - the rest.
EFFECT: gel has high cold resistance during storage.
SUBSTANCE: additive represents solution of highly-molecular polyisobutylene, which has molecular weight from, approximately 3.7·106 to, approximately 4.9·106, in used hydrocarbon liquid. Hydrocarbon liquid for machines with hydraulic systems with thermo- and/or energy-strained operation conditions contains additive in amount, ensuring energy characteristics of said machines. Mainly, hydrocarbon liquid represents kerosene or aviation spirit or Diesel fuel or liquid jet fuel. Liquid hydrocarbon fuel for jet engines contains additive in amount ensuring concentration of highly-molecular polyisobutylene in liquid hydrocarbon fuel from 0.015 to 0.095 wt %.
EFFECT: improvement of operating energy characteristics of machines, efficiency of engines, pump force.
8 cl, 1 tbl, 11 dwg
FIELD: oil and gas industry.
SUBSTANCE: invention is used in oil processing and petrochemistry. There is described the method of producing depressant; this method includes thermo-oxidising of decomposition reaction of crushed synthetic ethylene-propylene rubber with molecular weight of 300000-1000000 at presence of a dissolvent - hydrocarbon C10-C18. Thermo-oxidising decomposition reaction is carried out at atmospheric pressure and reaction medium temperature of 170-210°C, at that oxidising is performed with molecular air oxygen. Air is bubbled through the reaction medium and is stabilised with amino compound stabiliser. There is also suggested a depressant, produced in accordance with the above described method and diesel fuel on base fuel, containing produced depressant at amount of 0.05-0.2 wt %. Also there is described a facility for producing of depressant for diesel fuel, including a reactor of thermo-oxidising decomposition of ethylene-propylene copolymer; the said reactor has a source products input region, a case for its heating, and a device for bubbling of air through the reaction medium; the facility includes a homogeniser, an input of which is connected to the reactor output; at that the homogeniser is equipped with a closed circuit for circulation of a homogenised medium, connected with its input and output with the homogeniser.
EFFECT: reduction of power costs.
14 cl, 2 tbl, 14 ex, 1 dwg
SUBSTANCE: fuel contains, wt %: isooctane - 1-35, motor oil for two-stroke engine - 0.05-0.5, high-octane oxygenate - 10-30, aromatic hydrocarbons - 10-45, isomerizate - up to 25, alkylate - up to 10, and catalytic reforming gasoline - to 100. As aromatic hydrocarbons the fuel preferably contains C7-C9 aromatic hydrocarbons fraction; as high-octane oxygenate, C5-C6 dialkyl ether or its mix with C1-C5 aliphatic alcohols. The fuel also contains motor oil for two-stroke engine having maximum viscosity 11 mm2/sec at 100°C. In some cases the fuel may contain up to 1.5 wt % N-methyl aniline.
EFFECT: antiknock quality increase without applying lead and other metal-based additives; increase in combustion speed and purity; decrease in deposit formation on cylinders, pistons, and spark-plugs.
5 cl, 2 tbl
SUBSTANCE: fuel composition contains an additive which is a product of a Mannich reaction, carried out with: (a) aldehyde, (b) polyamine and (c) phenol, having one or more optionally substituted alkyl substitutes. The polyamine component (b) includes a R1R2NCHR3CHR4NR5R6 group, wherein each of R1, R2 R3, R4, R5 and R6 is independently selected from a hydrogen atom and an optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl or arylalkyl substitute. The composition also includes an additive which contains a quaternary ammonium salt which includes a product of reaction of (a) a hydrocarbyl-substituted acylating agent and a compound which contains an oxygen or nitrogen atom, capable of condensing with said acylating agent, and containing a tertiary amino group, and (b) an agent under the action of which a quaternary salt forms, selected from a group consisting of dialkyl sulphates, benzyl halides, hydrocarbyl-substituted carbonates, hydrocarbyl epoxides combined with an acid or mixtures thereof.
EFFECT: using the additive in a diesel fuel composition improves performance of the diesel engine, particularly reduces engine power loss, reduces deposits on injectors and the fuel filter, and increases fuel saving.
13 cl, 1 dwg, 7 tbl, 9 ex