Solid composition for storage and transportation of natural gas
(57) Abstract:Usage: the use and transportation of natural gas without pressure vessels. The inventive clathrate compound include natural gases fluorinated graphite of the total composition CxFClyzCnH2n+2where x= 1.8 to 2.5; y=0,08-0,09; z=0,12-0,22, CnH2n+2methane, ethane, propane, butane. The product does not contain impurities in the graphite stable up to 80oC, does not change composition when treated with water at 20-30oC, the density of 2.2 g/cm3the dissociation pressure at the 22oC does not exceed 10-4ATM. The invention relates to solid compositions for storage and transportation of hydrocarbon gases, namely clathrate compounds include natural gas on the basis of the fluorinated graphite of the total composition CxFClyzCnH2n+2where x=1.8 to 2.5, y=0,08-0,09, z=0,12-0,22, CnH2n+2methane, ethane, propane and butane. These clathrates in a long time (up to 1 year) can be used both for storage and for transportation of natural gas without the use of special pressure vessels.It is known the use of solid clathrate hydrates of natural gases for storage and transportationi in regions of large consumption proposed to carry through pipelines in containers filled clathrate hydrates of these gases.For storage of natural hydrocarbon gases is proposed to use solid hydrates of these gases total composition H2OxCnH2n+2where CnH2n+2natural hydrocarbon gases.The disadvantages of the known solid hydrates of these gases due to their physico-chemical properties. First, relatively high pressure dissociation of these hydrates is already at 0oC and low values of the dissociation temperatures at 1 ATM. So, for example, hydrates of methane dissociation pressure is already at 0oC reaches 26 ATM, and the temperature of dissociation at 1 ATM is 83oC. as a Result, the storage of natural gas in the form of their solid hydrates is effective at low temperatures, for example in storage, made in permafrost soil. For this reason, transportation hydrates of natural gases is only possible in a sealed pressure vessels. Secondly, the relatively low density hydrates of natural gases (0.9 to 0.96 g/cm3and as a consequence of the relatively low mass of the gas content per unit volume of hydrate. For example, the methane content per unit volume of Eisenia efficiency particulate formulations based on clathrate compounds used for storage and transportation of natural hydrocarbon gases by reducing pressure dissociation, increasing the temperature of dissociation, increasing the mass of the gas content per unit volume of clathrates, by increasing their density and eliminate the need for use to store and transport natural gas pressure vessels.The problem is solved in that the composition for storage and transportation of natural hydrocarbon gas contains solid clathrate compounds include those gases fluorinated graphite of the total composition CxFClyzCnH2n+2where x= 1.8 to 2.5, y=0,08-0,09, z=0.12 to 0.21 and CnH2n+2methane, ethane, propane, butane.In clathrate compounds include natural gases in fluorinated graphite molecules of gases are between the carbon layers of graphite, which covalent bonds attached fluorine atoms. These fluorine atoms are perpendicular to the carbon layers and complicate the selection included gas clathrate. Therefore, the dissociation pressure of these clathrates even with the 22oC does not exceed 10-4ATM, and the temperature of dissociation at 1 ATM reaches 80-100oC, i.e., thermal stabil greatly exceeds the stability of hydrates. Another important property in determining the effectiveness of these compounds is a higher density of clathrates graphite, which reaches 2.2 g/cm3that provides a much greater mass concentration of gases in a unit volume of the clathrate. So, for example, clathrate methane composition Cthe 2.5FCl0,090,21 CH4containing 6% methane, mass methane content per unit volume of the clathrate is 132 kg/m3and for clathrate composition Ca 1.8FCl0,080,22 CH4containing 7.3% of methane, this number reaches approximately 160 kg/m3.Is the invention as follows. First obtained by known methods fluorinated graphite, which is then treated liquefied gases. The result is the corresponding clathrate compounds of these gases fluorinated graphite, which is then used for storage or transport of these gases without the use of pressure vessels.Example 1. 5 g of graphite is placed in a boat made of Nickel and is treated with a mixture of HF and ClF3(1:1 by volume) in a tubular Nickel reactor at 200oC for 3 hours Obtained fluorinated graphite incubated at 22oC in a stream of nitrogen until constant weight. SatimoC for 0.5 h, and filtered. The solid product 3 times washed on the filter with ethyl alcohol portions of 50 ml. then the product on the filter is washed 3 times with cooled to -20oC Bhutan portions of 50 ml of the resulting product stand in the air at the 22oC to constant weight. The result is 11 g of solid clathrate of Bhutan with fluorinated graphite, containing, by weight. C 42,8, F 37,7, Cl 5,6 and C4H1013,8, which is part of Ca 1.8FCl0,080.12 C4H10. 11 g of the obtained clathrate compound of this composition containing approximately 1.42 g of butane.Example 2. Repeat the synthesis as described in example 1, but the product on the filter after washing Bhutan washed 3 times with cooled to -60oC propane portions of 50 ml. After drying in air at 22oC to constant weight gain of 10.5 g of the solid clathrate of propane with fluorinated graphite, containing, by weight. C 43,2, F 38,0, Cl 5.7 and C3H813,2, which is part of Ca 1.8FCl0,080,15 C3H8. of 10.5 g of the obtained clathrate of this composition containing approximately 1,38 g of propane.Example 3. The product obtained as in example 2, after washing propane washed on the filter 3 times cooled to -100oC Ethan porciani with fluorinated graphite, containing, by weight. C 44,8, F 39,4, Cl 5.9 and C2H49,9, which is part of Ca 1.8FCl0,080,16 C2H4. 10.4 g of the obtained clathrate of this composition containing approximately equal to 1.03 g of ethane.Example 4. The product obtained as in example 3, after washing with ethane washed 3 times on the filter is cooled to -170oC methane portions of 50 ml. After drying in air at 22oC to constant weight obtain 10.2 g of the solid clathrate of methane with fluorinated graphite, containing, by weight. C 45,6, F 40,1, Cl 6.5 and CH47,8, which is part of Ca 1.8FCl0,080,22 CH4. 10.2 g of the obtained clathrate of this composition containing approximately 0.75 g of methane.Example 5. 5 g of graphite is placed in a Nickel boat and treated with a mixture of HF and ClF3(1 1 by volume) in a tubular Nickel reactor at 100oC for 3 hours Obtained fluorinated graphite is kept in a stream of nitrogen at 22oC to constant mass and sequentially treated with acetone, ethyl alcohol, butane, propane, ethane and methane, as described in example 1. The result of 8.7 g of solid clathrate of methane with fluorinated graphite, containing, by weight. C 53,8, F 34,0, Cl 5.7 and CH46,0, which is part of Cthe 2.5FCl0,090,21 CH4. 8.7 g floor is all products obtained in examples 1 to 5, do not contain impurities of the graphite and are clathrate compounds include the corresponding natural gases in fluorinated graphite of the total composition CxFClyzCnH2n+2where x is 1.8 to 2.5, y 0,08 0,09, z 0,12 0,22 and CnH2n+2methane, ethane, propane and butane. On thermographic data, these clathrates are stable until 80oC. For chromatographic data only gaseous products that stand out from these clathrates in the field 22 80oC are the corresponding natural hydrocarbon gases. These clathrates do not change their structure when they are processed water within 20 30oC. the Density of these clathrates is 2.2 g/cm3. The pressure of their dissociation in the 22oC does not exceed 10-4ATM, and the temperature of dissociation at 1 ATM is 80oC. These physico-chemical properties of clathrates natural gases fluorinated graphite practically does not depend on the nature of the introduced gas.Thus, the invention allows to:
to simplify the storage and transportation of natural gas in the form of clathrate compounds by eliminating the need to use pressure vessels;
to increase the efficiency of Tver mass of gas per unit volume of the proposed clathrates by increasing their density.Physico-chemical properties of clathrates according to the invention allows to store and transport natural gas in the form of clathrates in common, leaking containers using such vehicles as automobiles, cars, trucks, aircraft, boats and sea vessels. The most promising are the following areas of the proposed solid compositions for storage and transportation of natural gas. This is, firstly, delivery and storage of natural gas in remote and hard-to-reach residential and industrial areas. Secondly, the proposed solid compositions can be used as generators of combustible gases for internal combustion engines (cars, Autonomous power, and so on). It should be emphasized that the proposed solid compositions makes it possible to transport and store light hydrocarbon gases (methane, ethane), which at present are usually incinerated at the place of production, which significantly degrades the environment in the wide areas. Solid composition for storage and transportation of natural gas on the basis of clathrate compounds, characterized in that it contains a clathrate compounds include natural gas Forero,12 0,22, CnH2n+2methane, ethane, propane, butane.
FIELD: chemical industry branches, special technical equipment, possibly manufacture of different articles and heat exchanging systems.
SUBSTANCE: process comprises manufacture of preliminarily prepared coke-filler of green or baked petroleum coke by performing steps of disintegrating till fraction 90 micrometers at content of fraction 20 -50 micrometers no less than 60 -65 %, mixing it with coal cake in relation 5.0 - 2.0 respectively; heating up to 1100 -1300°C; cooling, disintegrating till fraction no more than 90 micrometers; using prepared coke-filler for making molding mass of articles; pressing articles, firing them and graphitizating. Steps of mixing disintegrated coke with cake at relation 5.0 - 2.0, heating mixture, cooling it and again disintegrating may be repeated twice. Density of articles 1.78 - 1.80 g/cm3, compression strength 67.0 - 72.0 MPa.
EFFECT: enhanced quality of articles having no surface flaws.
2 cl, 2 ex
FIELD: nonferrous metallurgy and precision engineering.
SUBSTANCE: invention is intended for use in manufacturing production accessories and tools for electronic treatment. Calcined coke is ground to average particle size between 2 and 20 μm and mixed with medium-temperature coal pitch taken in excess from 3 to 10% of the weight of composition relative to content of pitch providing maximum density and strength of graphite blanks without thermal-vacuum treatment. Resulting mix is subjected to thermal-vacuum treatment under pressure 80-320 hPa and temperature 250-320°C during 1 to 10 h. Thereafter, coke-pitch composition is ground to produce molding powder, from which blanks are pressed. Resulting blanks are fired at 1000-1300°C and graphitized at 2600-3000°C. Fine-grain graphite shows compaction strength 80-120 MPa, density 1.75-1.85 g/cm3, and density variations not exceeding ±0.1 g/cm3.
EFFECT: improved performance characteristics of product.
3 cl, 3 tbl, 22 ex
FIELD: manufacture of updated gasket materials from graphite tape, foil, strips or sheets.
SUBSTANCE: thermally expanded graphite powder is rolled into cloth, 0.1-10 mm thick. In the course of rolling, cloth is subjected to nondestructive testing by means of one or several pairs of measuring sensors placed along its width; each pair of sensors includes transmitting and receiving sensors which are placed on either side of cloth; They are subjected to electromagnetic radiation at frequency of 103-106 Hz and phase shift angle relative to phase of oscillations of wave falling on specimen is measured. Frequency of oscillations is fixed. For obtaining enhanced accuracy of measurements, correcting pair of sensors may be mounted in parallel with measuring sensors. Present density of material is determined by calibration graph of material density versus phase shift angle which is plotted before measurements. At plotting the graph, density of material is determined by direct weight method. Thus, rolling parameters are corrected according to results of determination of present density.
EFFECT: improved quality of flexible material; immediate elimination technological malfunction.
6 cl, 3 dwg, 1 ex
FIELD: chemical industry and special-purpose technique; manufacture of large-sized blanks of shaped articles for chemical and heat-exchange apparatus.
SUBSTANCE: starting coke-filler is mixed with coal-tar pitch and is impregnated with it; then mixture is calcined at temperature of 1100°C and ground to size not exceeding 1.25 mm at content of particles of no more than 0.07 mm in the amount not exceeding 50%. For obtaining fine-grained materials, grinding is continued till particles of 0.5 mm have been obtained. Powder thus obtained is mixed with pitch and blanks are molded from hot coke-pitch mass by extrusion through tip or in mold, after which blanks are subjected to roasting and graphitization. After roasting and graphitization, blanks may be again impregnated with coal-tar pitch and subjected to repeated roasting. Density of material thus made ranges from 1.65 to 1.78 g/cm3, compressive strength ranges from 30.0 to 51.3 Mpa and bending strength ranges from 16 to 26.4 Mpa.
EFFECT: avoidance of rejects.
3 cl, 3 ex
FIELD: atomic industry; chemical industry; metallurgy; heat-and-power engineering; a method and a device for production of the oxygenated graphite.
SUBSTANCE: the invention presents a method of production of the oxygenated graphite and a device for its realization and may be used in atomic, a chemical industry, in metallurgy and heat power engineering at production of a flexible graphite foil, heat-insulating and fire-proof materials, sorbents. Graphite suspension is prepared in 30-98 % sulfuric acid or nitric acid. The ratio of the electroconductivities of the suspension and each acid exceeds 1. The suspension may additionally contain H3POorCH3COOH. The produced suspension is continuously or discretely is discharged through a branch pipe 3 in the reaction chambers 11 of the merry-go-round type reactor 1 with a cylindrical body 2, an annular anode 6 made in the form of a chute and cathodes 10 made the form of vanes. The anode 6 is mounted in the body 2 coaxially with it and is supplied with a jacket of chilling 7. Cathodes 10 are supplied with the separation casings and fixed to a bracket 9 fixed on the shaft 8 of the rotary drives. Anodic oxidizing of graphite conduct without compacting of the anode 6 in absence of the free electrolyte at a constant value of the electric current or at a constant potential of the anode with a message confirming that the current value in both cases is no less than 30 A·h/kg graphite. Cathodes 10 transfer the suspension by a chute of the anode 6. The formed compound of implantation is unloaded through a branch pipe 4, hydrolyzed, flushed, filtered and dried. The invention allows to increase productivity and to produce a foamed graphite after dilatation at 900°C with a high degree of homogeneity and bulk density of 1.1-3.4 g/dm3.
EFFECT: the invention ensures increased productivity and production of the foamed graphite with a high degree homogeneity and good bulk density.
17 cl, 2 dwg, 3 tbl, 5 ex
FIELD: manufacture of articles from carbon materials, electrodes for example.
SUBSTANCE: articles made from carbon materials are heated in electrical furnace and are held to preset degree of graphitization. During heating and holding at heat, present magnitudes of temperature of characteristic point of articles located in end face of blank in center section of upper row is recorded. Moment of discontinuation of holding at heat and switching-off electric power is found from the following formula: : where γ is degree of graphitization; τ1-τ2 is time interval where graphitization takes place, h; F is function characterizing the time dependence of isothermal holding, h required for obtaining preset degree of graphitization versus graphitization temperature; T (τ) is present temperature of characteristic point of articles, °C; is present time, h.
EFFECT: reduced power requirements down to 5% at scheduled graphitization and down to 13% at forced graphitization.
FIELD: atomic industry; chemical industry; metallurgy; heat-and-power engineering; production of the oxidized black lead.
SUBSTANCE: the invention may be used is pertaining to the methods of production of the oxidized black lead and may be used in atomic industry, chemical industry, metallurgy, heat-and-power engineering at production of heat-insulating and refractory materials, a flexible graphite foil, sorbents. Prepare a non-laminated, having electronic conductivity suspension of black lead in 70-98 % H2SO4. The suspension may be further added with H3PO4 orCH3COOH. The gained suspension is fed into to the reactor 1 of the hopper 12 through a branch-pipe 3 by means of a piston 13. In the reaction chamber 9 it is moved by gravity flow along the hollow perforated cathode 7 and gets in contact with the anode 5. The anodic oxidation of the black lead conduct without its prepressing to the anode in absence of a free electrolyte with production of the electrical power in amount of no less than 30 A·h/kg of black lead at a constant value of the electric current or at a constant anode potential. Excess of an acid passes through a separator made out of a filtering fabric 8 and enters in the internal cavity of the cathode 7, one end 11 of which is open and then - into a collector 17. The ionic bond between the cathode 7 and the anode 8 is conducted through the separator 8, preventing an occurrence of a possible short circuit. The ring-type design of the reaction chamber 9 ensures uniformity of treatment of the anode and the least hydraulic resistance. The oxidized black lead is discharged through a branch-pipe 4, hydrolyzed, flushed, filtered and dried. The invention allows to boost productivity and to produce a foam-graphite after its frothing at the temperature of 900°C with a high degree uniformity and a bulk density of 1.5-3.2 g/l.
EFFECT: the invention ensures an increased productivity and production of a foam-graphite with a high degree uniformity and a good bulk density.
22 cl, 4 dwg, 2 tbl, 2 ex
FIELD: production of sorbent on base of thermally expanded graphite used for extraction of water-insoluble compounds from water, soil and hard surfaces; gathering concentrated acids.
SUBSTANCE: proposed plant includes loading bin, proportioner, branch pipe for delivery of carrier gas, branch pipe for delivery of starting raw material (oxidized graphite), expansion chamber, separator with vertical partition and receiving bin. Proposed plant is also provided with ejector and tangential flow swirler combined with it; branch pipe for delivery of starting raw material is provided with external envelope for passing the coolant; ejector is mounted at expansion chamber inlet under outlet hole of starting material delivery branch pipe.
EFFECT: reduced power requirements with no reduction in productivity; improved quality of sorbent.
4 cl, 3 dwg, 1 tbl
FIELD: metallurgy; semiconductor and aeronautical engineering; manufacture of electrodes, seals for aircraft engines and super clean articles.
SUBSTANCE: coke at yield of volatile agents of 4.0-12.0 mass-% in which fraction of size lesser than 0.09 mm is no less than 97 mass-% and fraction of size lesser than 0.045 mm is no less than 91 mass-% is mixed with 30-40 mass-% of coal-tar pitch, 0.015-2.0 mass-% of sterically hindered phenols and/or phenyl phosphites and 0.015-2.0 mass-% of stearic acid. Mass ratio of stearic acid to sterically hindered phenols and/or phenyl phosphites ranges from 1:1 to 2:1. Mixing with coal-tar pitch is performed at temperature of 110-160°C. Mass thus obtained is cooled to room temperature, crushed, ground and blanks at density of 1.01-1.25 g/cm3 are molded and roasted at 1000°C. Roasted blanks are graphitized at temperature rise by the following scheme: to 800°C, 30-60°C/h; to 1500, 5-25°C/h; to 2200°C, 15045°C/h. Holding time at each stage is equal to 3/7 h. Material thus obtained has apparent density of 1650-1870 kg/m3 at compressive strength of 103-160 Mpa and bending strength of 81-88 Mpa.
EFFECT: enhanced efficiency.
2 tbl, 1 ex
FIELD: atomic industry; chemical industry; metallurgy; heat power engineering; methods and reactors for graphite treatment.
SUBSTANCE: the invention is pertaining to the field of the atomic industry, chemical industry, metallurgy and heat power engineering and may be used for production the flexible graphite foil, sorbents, catalytic agents, chemical sources of electric current. Suspension of the graphite in the electrolyte, for example, in the nitric acid having the electronic conduction from the hopper (15) through the branch pipe (8) load into the reaction chamber formed by the cathode (3) and the consumed anode (7) from the anode-soluble in the electrolyte metal or its alloy. The anode (7) is arranged in the lower part of the body of the reactor(1) and is made in the form of the movable band, which ends are consolidated on the unwinding drum (10) and the winding drum (11). On the exterior side of the cathode (3) the diaphragm (5) is disposed. Conduct an anodic oxidation of the graphite with production of the compounds of the anodic oxidation containing the compounds of embedding in the graphite (CEG) and the cations of the metal of the anode (7) at the suspension movement through the reaction chamber. The products of the anodic oxidation are cleared off from the surface of the cathode (3) by the fluoroplastic knife (16) and through the branch pipe (9) unload it into the hopper-collector (17). Then they are subjected to the hydrolysis or they are added with the alkali or the soda ash, flushed and dried with production of the oxidized graphite with the hydroxides of metal or without them. After that they conduct the thermal expansion. The invention allows to make the technological process cheaper and to dilate the production capabilities due to production both of the conventional foam graphite and the composite material based on the foam graphite with addition of the metals or their oxides.
EFFECT: the invention allows to make the technological process cheaper, to dilate the production of the conventional foam graphite and the composite material based on the foam graphite with addition of the metals or their oxides.
11 cl, 1 dwg, 4 ex
FIELD: electric power and chemical industries; methods of production of the electric power and liquid synthetic fuel.
SUBSTANCE: the invention presents a combined method of production of the electric power and liquid synthetic fuel with use of the gas turbine and steam-gaseous installations and is dealt with the field of electric power and chemical industries. The method provides for the partial oxidation of hydrocarbon fuel in a stream of the compressed air taken from the high-pressure compressor of the gas turbine installation with its consequent additional compression, production of a synthesis gas, its cooling and ecological purification, feeding of the produced synthesis gas in a single-pass reactor of a synthesis of a liquid synthetic fuel with the partial transformation of the synthesis gas into a liquid fuel. The power gas left in the reactor of synthesis of liquid synthetic fuel is removed into the combustion chamber of the gas-turbine installation. At that the degree of conversion of the synthesis gas is chosen from the condition of maintenance of the working medium temperature at the inlet of the gas turbine depending on the type of the gas-turbine installation used for production of the electric power, and the consequent additional compression of the air taken from the high-pressure compressor of the gas-turbine installation is realized with the help of the gas-expansion machine powered by a power gas heated at the expense of the synthesis gas cooling before the reactor of synthesis. The invention allows simultaneously produce electric power and synthetic liquid fuels.
EFFECT: the invention ensures simultaneous production of electric power and synthetic liquid fuels.
2 cl, 2 dwg