Method for hydrocarbon mixture separation

FIELD: oil production industry, particularly for oil product separation.

SUBSTANCE: method involves mixing gaseous hydrocarbon with aqueous acid solution with pH value of not more than 4 so that hydrate-generation gas is converted into hydrate phase under hydrate phase forming control.

EFFECT: increased efficiency due to increased separation degree, increased simplicity, possibility to utilize separation products and enhanced safety.

15 cl, 2 dwg

 

The invention relates to the oil and gas industry and, in particular, the separation of hydrocarbon (oil and gas) mixture in the well during production, or after extraction of the hydrocarbon mixture from the well.

The separation produced from hydrocarbon wells (oil and gas) mixture is performed, as a rule, from the conditions of its infield, regional or industrial applications and in preparation for transport. Associated oil or low-pressure gas produced, for example, the first and/or second stage of oil separation, not subjected to any further separation (purification or processing) and released through the outlets of the separators in the atmosphere or, as a rule, are burned at flares without their disposal.

Separation of hydrocarbon (oil and gas) mixture in the well conducted, for example, in order, for example, a stable operation of centrifugal pumps used for pumping oil or isolation gotoododa intervals.

Widely known methods of separation of the oil and gas mixture in the well, including the placement of the separator (anchor) under the receiving borehole centrifugal pump.

The disadvantage of these methods is their low efficiency due to the fact that this method does not allow for recycling separated from the oil and natural gas.

Known method of separation of gas mixtures and, produced from wells, including the selection of the gas mixture passing and/or low-pressure gas and discharge it to the processing unit, where the gas is compressed and accumulates to supply to the consumer (see, for example, U.S. Pat. Of the Russian Federation No. 2172762, 27.08.2001).

The disadvantage of this method is that the known method provides for complex energy-intensive Park blocks separation with compressors and pressure vessels, dangerous operation, with low profitability and occupying large areas. In addition, the known method does not provide for the separation and concentration of themselves hydrocarbon gases.

The technical result of the invention is to improve the efficiency of separation of gas mixtures by increasing the depth of separation, easier way to recycle products separation and energy emitted during separation, and security of production.

Required technical result is achieved by the method of separation of hydrocarbon (oil and gas) mixture includes a gas from a gas mixture, mixing the selected gas with the aqueous acid solution when the pH is not more than 4) with switching gidratoobrazovaniya gas in the hydrate phase, and the rate of formation of hydrated phases govern.

In addition,

separation of gas from oil and gas mixture is syshestvyut at down hole conditions, when the gas, which does not form hydrates additionally used as natural gas for lifting fluids from the production well, and hydrate phase is used for insulation hasaudio interval in a production well;

separation of gas from oil and gas mixture is performed after the extraction of oil and gas mixture from the well;

from the oil and gas mixture produced from the well, there are the associated and/or low-pressure gas to the first and/or second stage of separation at low and/or high temperatures and assign the selected gas in the processing unit for education in it hydrated phases;

the selected gas is bubbled through a column of an aqueous solution of an acid;

the selected gas is passed through a porous or fibrous material soaked in an aqueous acid solution;

as a porous or fibrous material take silica gel and/or activated carbon, and/or cotton and/or tissue;

as acids are acetic or hydrochloric acid;

the node processing is performed in a container, at least one, with the ability to regulate its temperature and pressure;

the node processing is performed in a container with drainage for liquid phase hydrocarbons;

the capacity to perform consumable hot release from hydrate phase;

the node processing is performed with the opportunity features the who and heat;

gases do not form hydrates, divert their throttling;

due to gases, does not form a hydrate, increase letterwise and fluid properties of oil;

warm gases form hydrates, regulate temperature separation of gas mixtures.

The method in accordance with the invention provides for the transfer of gas extracted from the oil-gas mixture and forming hydrates, in a stable hydrate phase and the disposal of other gases do not form hydrates, and thermal energy accompanying the formation of hydrates. One part of the gas, gidratoobrazovaniya use as a means of isolating the well, for example, cazoodle interval. Another part of the gas, forming hydrates, are used as a means for regulating the rate of formation of hydrated phases. Among the different methods of speed control of formation of hydrated phases employ the technique of heat in the reaction of hydrate formation. This is carried out through the use of cooling devices or due to the gases do not form hydrates. Allocated warmly disposed, for example, in the well, raised by him letterwise gas properties and fluid properties of the oil, and on the earth's surface, for example, regulate the temperature separation of gas mixtures.

The density of the gas in the hydrated state, as this is learn from the molar ratio of the gas-water, exceptionally high. Density of gas in the hydrate lattice is greater than its density in the gaseous state. Storage of gas, for example, on the earth's surface in the hydrated state is most effective at relatively low pressures, when the same pressure per unit volume in the hydrated state contains much more gas than free. Hence, the hydrated form of storage and transportation of natural gas does not require compressor stations, pressure vessels, and absolutely safe. For any kind of separation of hydrocarbon mixtures containing petroleum or low-pressure gas even in very small amounts, it can be used for the savings Fund that does not require much time and cost. The combusted gas or released into the atmosphere in any, even small amounts of irreparable environmental harm. Besides small for one well or object gas loss, as summarized for a field or region is not only tangible, but very significant.

The proposed invention allows to increase the depth separation of the oil and gas mixture, when sephirot mixture not only on liquid and gaseous phase, but when sephirot gaseous mixture. By increasing the depth of the separation can be divided, for example, propane is tanouye mixture, and allocate helium from natural gas, etc. In a hydrated phase moving light aliphatic components of the gas. The components of the oily gas from Bhutan and above this will become liquid. Essentially, the proposed invention is a method of translating low-pressure gas in the hydrate phase (gas hydrate).

It is known that hydrated phase (hydrates of natural gases) is an unstable physical-chemical combination of water with gas, which with increasing temperature or decreasing pressure decompose into gas and water. In appearance it is a white crystalline mass, like snow.

However, an essential condition for the formation of hydrated phases is the presence of water in the liquid state, i.e. the temperature of the system "gas - water must be below the dew point for a given composition of the gas and aqueous phase. Therefore, the formation of hydrate phase begins at temperatures below the dew point (the appearance of the liquid phase).

As you know, water in the liquid state dissociates to ions hydrogens and hydroxyl ions. The degree of electrolytic dissociation (the number of molecules dissolved ions in relation to the total number of molecules) of water is small and amounts to about 10-7of the total (62 g-molecules in a liter of water).

Positively charged hydrogen ion (prot is n) due to the small size of the ionic radius less than 0,002 Å (Artemenko A.I., etc.. reference guide for chemistry, Moscow, Higher school, 2003, s) does not feel repulsion from the electron shells of the molecules.

In the presence of the dipole (the uneven distribution of electron density within the molecule) hydrogen ion can penetrate in this molecule and due to the hydrogen bonds formed a new chemical compound, which has a positive charge. For example, ammonia after introducing hydrogen ions forms the ammonium ion, which is able to hydrogenate itself, and begins a series of compounds on the basis of ammonium ion type NH4OH, NH4Cl or (NH4)2SO4.

For a molecule of methane proved the existence of ion SN+ - Methoni (Weltalls, Aka. Dokl. An SSSR, 1952, t, s). Metoni able to hydrogenate itself by analogy with ammonia, which forms with water an unstable under normal conditions of connection (Nekrasov B.A. Course in inorganic chemistry // M, Mir,1968).

Hydrates of natural gases have the structure CH4·6N2On;2H6·8H20; C3H8·17H2About; out4H10·17H2O. methane Hydrates are stable at 0°if the pressure exceeds 2.8 MPa. For other hydrocarbons aliphatic series (C2H6;3H8; out4H10pressure of the existence of hydrates is 0.53; 0,173; ,122 MPa at temperatures of minus 15,8; 8,5; 0,0 °respectively (Uofmichigan. Hydrates of natural gases. The subsoil, M., 1974, 206 S.).

In practice, the conditions of hydrate formation is determined using the equilibrium graphs depicted in figure 1, which shows the number of equilibrium curves depending on the temperature and pressure for gases with different relative densities. Numbers on the curves indicate the density of the gas relative to air (Degtyarev BV and others Struggle with hydrates during the operation of gas wells in the Northern regions, Moscow, Nedra, 1976, s).

Relative gas density (the ratio of the mixture density to air density) is the amount that indirectly indicates the content of heavy aliphatic with respect to methane. As shown in figure 1 the data suggests that even with a significant amount of heavy hydrocarbons in a mixture of natural gas, hydrate phase can exist only under significant pressures and low temperatures.

Therefore, utilization of low-pressure gas in the form of hydrates on freshwater technically difficult and economically impractical.

To increase the concentration of ions matonia possible by increasing the concentration of hydrogen ions in the aqueous phase, which will greatly enhance the stability of gas hydrates.

It is known that the presence of methane acidic gases significantly alters the equilibrium parameters coord is gas hydrates. For example, the content of hydrogen sulfide in the amount of 10% reduces the equilibrium pressure of the formation of gas hydrates at least 4-5 MPa at a constant temperature, or the equilibrium temperature for 12-15°at constant pressure in the system.

Figure 2 (Bekirov T.M., Field and factory processing of natural oil and gas, Moscow, Nedra, 1980, C) shows the zones of the formation of gas hydrates (above the specified limits) depending on the number of acidic gases (the content of H2S): 1% (line 1), 2% (2), 4% (3), 6% (4), 10% (5), 20% (6), 40% (7), 60% (8).

To justify the way in laboratory conditions at atmospheric pressure were determined temperatures of formation of hydrated phases (hydrate of natural gases) when bubbling propane-butane mixture through aqueous solutions of acids.

In acetic acid solution with a pH of 4 crystalline mass of white (gas hydrate) was stable at a temperature of +17°C.

In General, the pH should not be more than 4.

The acid solution may be in the tank in the form of wetting phase in a porous or fibrous material (for example, wool and/or silica gel and/or activated carbon, and/or tissue).

In bubble tanks must also be a selection of the resulting liquid phase hydrocarbons.

The method provides speed control of education the Oia hydrate phase. The experiments conducted at several temperatures and pressures, showed that lowering the process temperature and pressure increase leads to an increase in the rate of formation of hydrated phases. The time required to complete a hydrated phase of the gas contained in the bubble (bubbling)is called the contact time of the gas-solution. Largely it depends on the design of the processing unit, and more specifically its height, providing the necessary contact time of the gas with the acid solution, and sizes of gas bubbles. With decreasing diameter of the bubbles, for example, by supplying a gas in the form of dispersed flow contact time may be reduced or the rate of formation of the hydrate phase can be increased. Direct contact of the gas with a solution provides the best conditions of the exothermic heat of reaction of hydrate formation. In addition, the heat dissipation can be ensured through the wall of the processing unit or using a heat exchanger. It also helps to regulate the rate of formation of hydrated phases. Gases do not form hydrates, before their removal to accumulate to create the necessary pressure in the processing unit and control the rate of formation of hydrated phases. In addition, with the removal of these gases from throttling you can create a bore is ationary mode processing unit for better mixing of gas bubbles with acid solution and further improving the regulation of the rate of formation of hydrated phases.

In conditions well hydrated phase using, for example, to isolate gotoododa intervals in the borehole when the processing operations of critical areas. This reduces the contamination of productive gotoododa intervals in the borehole when the processing operations of critical areas.

The method is as follows.

Depending on the operating conditions of the well, the adopted technology exploitation (for example, natural or wellhead, sucker rod pumps or centrifugal pumps) are a variant of the separation of hydrocarbon (oil and gas) mixture. This separation can be carried out in one case in terms of the well to provide, for example, optimum operating conditions of centrifugal pumps. In another case, the separation of gas / oil mixture can be carried out on the earth's surface. In any case, from the oil and gas mixture produces gases. In the well or on the earth's surface is carried out using the respective separators: downhole separator (anchors) or surface of the separator with greater separation. The selected gas is mixed with the aqueous acid solution. When the downhole separation can be adopted, for example, the scheme of pre-injection of an aqueous solution of the acid in the desired interval of the well. Then in the borehole can be deflated pump with separator (the anchor. The acid solution thus take the stock in the subsequent reaction of the formation of hydrated phases. In the process of operation, for example, when the cycles of production stops periodically to pump up the water solution of the acid through the tube pump tubes. For ground separator mixing the selected gas with the aqueous acid solution is not difficult. An aqueous solution of acid take with a pH not greater than 4. The mixing produced with switching gidratoobrazovaniya gas in the hydrate phase. Thus the rate of formation of hydrated phases regulate, for example, by regulating pressure and temperature. The regulate temperature due to heat dissipation, for example, with the use of cooling devices. You can, for example, to create such conditions that the gas does not form hydrates, did not dissolve (not mixed with oil, and stood out from her in bubble mode and to the maximum extent reduced the density of oil and ensured the maximum letterwise properties. The oil from the additional heat does not form hydrates of gases increases its fluid properties by reducing viscosity. This is the waste heat gases form hydrates and removes heat exothermic reaction gases form hydrates. On the surface this process is more adjustable, for example, which is the group of refrigeration devices. But the heat of hydrate formation used for the separation with the use of heat. In this case, provide a more economical mode temperature separation.

In terrestrial separator selected gas it is possible to barbthroat through the thick aqueous acid solution with a uniform distribution of gas over the cross section of the strata acid solution. In this case, the separator shall allocate, for example, low-pressure gas to the first and second stage low-temperature separation of oil. The selected gas is directed to a treatment unit in the form of bubbling tanks of a certain height, providing the necessary contact time of the gas with the acid solution. In this form a stable gas hydrates. The rate of formation of hydrated phases regulate temperature, pressure and degree of dispersion of gas bubbles. Additionally regulate the process by throttling the exhaust gases, does not form a hydrate, by increasing the degree of mixing of gas bubbles and acid solution and increasing the degree of homogeneity of the environment. After lling hydrated phase, it is freed and the process is repeated. To carry out the separation of gas from liquid phase, and the separation gas species without loss, without causing harm to the environment and safety of its production.

1. How is apararii hydrocarbon mixture, including the allocation of gas from hydrocarbon - oil mixture by mixing the gas with the aqueous acid solution when the pH is not more than 4, with the possibility of transition gidratoobrazovaniya gas in the hydrate phase, and the rate of formation of hydrated phases govern.

2. The method according to claim 1, characterized in that the gas from the oil and gas mixture is performed under conditions well, and the gas, forming hydrates additionally used as natural gas for lifting fluids from the production well, and hydrate phase is used for insulation hasaudio interval at the production wells.

3. The method according to claim 1, characterized in that the gas from the oil and gas mixture is performed after the extraction of oil and gas mixture from the well.

4. The method according to claim 3, characterized in that the oil-gas mixture produced from the well, there are the associated and/or low-pressure gas to the first and/or second stage of separation at low and/or high temperatures and assign the selected gas in the processing unit for education in it hydrated phase.

5. The method according to claim 3 or 4, wherein the selected gas is bubbled through a column of aqueous acid solution.

6. The method according to claim 3 or 4, wherein the selected gas is passed through a porous or fibrous material soaked in an aqueous acid solution.

7. the procedure according to claim 6, characterized in that the porous or fibrous material take silica gel and/or activated carbon, and/or cotton and/or tissue.

8. The method according to claim 1, characterized in that, as the acids are acetic or hydrochloric acid.

9. The method according to claim 4, characterized in that the processing unit is performed in a container, at least one, with the ability to regulate its temperature and pressure.

10. The method according to claim 4 or 6, characterized in that the processing unit is performed in a container with drainage for liquid phase hydrocarbons.

11. The method according to claim 9, characterized in that capacity to perform consumable hot release from hydrate phase.

12. The method according to claim 4 or 9, characterized in that the processing unit executes with the possibility of disqualification from the heat.

13. The method according to claim 1, characterized in that the gases do not form hydrates, divert their throttling.

14. The method according to claim 1 or 2, characterized in that the gases do not form hydrates, increase letterwise and fluid properties of oil.

15. The method according to claim 1 or 4, characterized in that the heat of the gases do not form hydrates, regulate temperature separation of gas mixtures.



 

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