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.

 

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