CN114058357B - Preparation method and application of thickened oil viscosity reducer - Google Patents
Preparation method and application of thickened oil viscosity reducer Download PDFInfo
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- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
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Abstract
The invention relates to a preparation method and application of a thick oil viscosity reducer, wherein the method comprises the following steps: (1) Soaking porous carbon powder with a solution containing catalyst metal ions, adding a reducing agent to reduce the metal ions into metal simple substances, enriching and adsorbing the metal simple substances on the porous carbon powder, and separating the porous carbon powder to obtain a catalyst precursor for later use. (2) And carrying out hydrophilic modification treatment on the catalyst precursor, and then carrying out oleophylic modification treatment to obtain the modified catalyst. (3) And mixing the modified catalyst with water, and then carrying out ultrasonic dispersion to obtain an ultrasonic dispersion liquid, namely the thickened oil viscosity reducer. The viscosity reduction oil displacement agent enriches catalytic components on a porous carbon powder carrier, and has both hydrophilicity and lipophilicity, so that a catalyst can be fully contacted with thick oil, and the viscosity reduction effect on the thick oil is effectively improved.
Description
Technical Field
The invention relates to the technical field of thick oil viscosity reducers, in particular to a preparation method and application of a thick oil viscosity reducer.
Background
The heavy oil is low in light component content and high in asphaltene and colloid content, so that most of heavy oil has the characteristics of high viscosity and high density, the heavy oil exploitation industry is gradually promoted along with less and less light oil reserves, but the heavy oil is high in viscosity and low in fluidity and is difficult to exploit, and the heavy oil is difficult to stratify from an oil layer by adopting a conventional exploitation method, so that the heavy oil needs to be subjected to viscosity reduction before exploitation, for example, a heating method, a thin oil mixing method, a chemical agent viscosity reduction method and the like, and the heavy oil is converted into an emulsified state with water as an external phase from a water-in-oil emulsified state through viscosity reduction, so that the viscosity of the heavy oil is reduced. Among them, the heating method has been implemented due to its advantages of low cost, relatively simple process, etc. The process mainly reduces the viscosity of the thick oil by utilizing heat brought by high-temperature steam, but the reduction of the viscosity is reversible, and when the high-temperature steam is injected, the thick oil is gradually cooled, and the viscosity rises again to influence subsequent exploitation. In order to overcome the above problems, a catalyst is also added to irreversibly lower the viscosity of the thick oil when injecting steam into the oil well. Although the method overcomes the problem of re-increasing the viscosity of the thick oil, the viscosity reduction effect is not ideal, and the viscosity reduction efficiency of the whole process is low and needs to be further improved.
Disclosure of Invention
The viscosity-reducing oil displacement agent can reversibly reduce the viscosity of the thick oil and can effectively improve the viscosity-reducing effect on the thick oil. In order to realize the purpose, the invention discloses the following technical scheme:
in a first aspect of the invention, a preparation method of a thick oil viscosity reducer is disclosed, which comprises the following steps:
(1) Soaking porous carbon powder in a solution containing catalyst metal ions, adding a reducing agent to reduce the metal ions into a metal simple substance, enriching and adsorbing the metal simple substance on porous carbon, and separating the porous carbon to obtain a catalyst precursor for later use.
(2) And (3) carrying out hydrophilic modification treatment on the catalyst precursor, and then carrying out oleophylic modification treatment to obtain the modified catalyst.
(3) And mixing the modified catalyst with water, and then carrying out ultrasonic dispersion to obtain an ultrasonic dispersion liquid, namely the viscous oil viscosity reducer.
Further, in the step (1), the catalyst metal ions include: at least one of iron ion, ferrous ion, copper ion, nickel ion, zinc ion, etc. The metal ions are reduced into nano metal simple substance particles by a reducing agent and are attached to the porous carbon.
Alternatively, the catalyst metal ion-containing solution includes a solution in which at least one of chloride, sulfate, nitrate, acetate, and the like of a metal ion is dissolved in water.
Preferably, in step (1), the solution containing the catalyst metal ions is a saturated solution at room temperature so as to provide sufficient catalyst metal ions.
Further, in the step (1), the reducing agent is any one of a sodium borohydride solution and a potassium borohydride solution. The amount of the reducing agent added may be such that the metal ions are sufficiently reduced.
Further, in the step (2), the catalyst precursor is mixed with liquid alcohol and then subjected to solvothermal reaction, so that a hydrophilic group is introduced into the catalyst precursor, and hydrophilic modification treatment of the catalyst precursor is realized.
Optionally, the temperature of the solvothermal reaction is 100 to 120 ℃, and the time is 20 to 40min.
Optionally, the liquid alcohol comprises at least one of methanol, ethanol, propanol, butanol, and the like.
Further, in the step (2), the catalyst precursor subjected to hydrophilic modification treatment is mixed with a silane coupling agent solution, and then the mixture is heated to a set temperature and then is subjected to heat preservation, so that the modified catalyst is obtained.
Further, the silane coupling agent includes any one of vinyltriethoxysilane, vinyltrimethoxysilane, and the like.
Further, the heat preservation temperature is 50 to 65 ℃, and the time is 3 to 5 hours, so that a lipophilic group is grafted on the surface of the catalyst precursor, and the catalyst precursor has the characteristics of lipophilicity and hydrophilicity.
Further, in the step (3), the ratio of the modified catalyst to water is 1g:80 to 110ml.
In a second aspect of the invention, the application of the thick oil viscosity reducer obtained by the preparation method of the thick oil viscosity reducer in petroleum engineering is disclosed.
Further, the thick oil viscosity reducer is used for reducing viscosity of thick oil, and the using method comprises the following steps: injecting hot steam into the thickened oil recovery well to preheat the thickened oil, adding the thickened oil viscosity reducer, and sealing the oil well to perform a hydrothermal catalytic cracking reaction on the thickened oil.
Further, the addition amount of the thickened oil viscosity reducer is 0.6-1.5% of the mass of thickened oil according to the mass calculation of the modified catalyst in the thickened oil viscosity reducer.
Furthermore, the temperature of the preheating treatment is 130-170 ℃, and macromolecular substances such as colloid, asphalt and the like in the thickened oil are cracked into micromolecular substances under the action of high temperature and a catalyst, so that the viscosity of the thickened oil can be obviously reduced.
Compared with the prior art, the invention has the following beneficial effects:
(1) The thick oil viscosity reducer takes the porous carbon powder as a carrier, has huge surface area and good adsorption performance, can adsorb metal ions in the carrier, and has better capability of enriching catalytic active components compared with other carriers, so that more catalytic active components can be carried in thick oil, and the catalytic efficiency and the viscosity reduction effect are improved. In order to load the catalytic active component on the porous carbon, the invention adopts a method of chemically reducing the metal ions adsorbed on the porous carbon, and has the advantages that the metal ions can be converted into the metal simple substance to become the catalytic active component, and the metal simple substance is reduced by the metal ions, so the obtained metal simple substance is nano-scale particles, can play a nanometer effect in the catalytic process, and plays a role in promoting the cracking of the catalytic thick oil.
(2) The invention also carries out hydrophilic and oleophylic double modification treatment on the prepared catalyst, and hydrophilic and oleophylic groups are introduced on the surface of the catalyst simultaneously, so that the hydrophilic group can enable the catalyst to be uniformly dispersed in a water phase to form a dispersion liquid so as to be conveniently injected into an oil well. After the lipophilic group is introduced on the catalyst, the catalyst can migrate to the oil phase and be fused with the oil phase, so that the catalyst is fully contacted with the oil phase, and the viscosity reduction rate and the viscosity reduction effect are effectively improved.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. The invention will now be further illustrated by specific examples.
Example 1
1. A preparation method of a thick oil viscosity reducer comprises the following steps:
(1) Taking 50g of porous carbon powder, adding the porous carbon powder into 200ml of saturated ferric chloride solution to infiltrate the porous carbon powder, stirring for 5min, adding an excessive sodium borohydride solution with the mass fraction of 20%, and filtering and separating out porous carbon in a reaction liquid to obtain a catalyst precursor for later use.
(2) Adding the catalyst precursor obtained in the step (1) and 300ml of absolute ethyl alcohol into a high-pressure reaction kettle, reacting for 25min at 115 ℃, and then filtering and separating out a solid product.
(3) And (3) adding the solid product obtained in the step (2) into an alcoholic solution of vinyl triethoxysilane, and then preserving heat at 60 ℃ for 5 hours to obtain the modified catalyst.
(4) Mixing the modified catalyst in the step (3) with water according to the proportion of 1g: and mixing the components in a proportion of 90ml, and performing ultrasonic dispersion to disperse the modified catalyst in water to obtain the thick oil viscosity reducer.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) A thick oil sample having a viscosity of 36600 mPas at 50 ℃ is taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 1.0% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 150 ℃ for 24 hours, opening the high-pressure reaction kettle, continuously heating to remove water in the reacted thickened oil sample, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
Example 2
1. A preparation method of a thick oil viscosity reducer comprises the following steps:
(1) Taking 50g of porous carbon powder, adding the porous carbon powder into 200ml of saturated ferrous sulfate solution to infiltrate the porous carbon powder, stirring for 5min, adding an excessive sodium borohydride solution with the mass fraction of 20%, and filtering and separating out porous carbon in a reaction liquid to obtain a catalyst precursor for later use.
(2) Adding the catalyst precursor obtained in the step (1) and 300ml of propanol into a high-pressure reaction kettle, reacting for 40min at 100 ℃, and then filtering to separate a solid product.
(3) And (3) adding the solid product obtained in the step (2) into an alcoholic solution of vinyl trimethoxy silane, and then preserving the temperature for 3 hours at 65 ℃ to obtain the modified catalyst.
(4) Mixing the modified catalyst obtained in the step (3) with water according to the proportion of 1g: and mixing the components in a proportion of 80ml, and performing ultrasonic dispersion to disperse the modified catalyst in water to obtain the thick oil viscosity reducer.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) A thick oil sample having a viscosity of 36600 mPas at 50 ℃ is taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 1.5% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 170 ℃ for 24 hours, opening the high-pressure reaction kettle, continuously heating to remove water in the reacted thickened oil sample, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
Example 3
1. A preparation method of the thick oil viscosity reducer comprises the following steps:
(1) Taking 50g of porous carbon powder, adding the porous carbon powder into 100ml of saturated nickel nitrate solution and 100ml of saturated copper nitrate solution to infiltrate the porous carbon powder, stirring for 5min, adding excessive potassium borohydride solution with the mass fraction of 20%, and filtering and separating out porous carbon in reaction liquid to obtain a catalyst precursor for later use.
(2) Adding the catalyst precursor obtained in the step (1) and 300ml of methanol into a high-pressure reaction kettle, reacting for 20min at 120 ℃, and then filtering to separate a solid product.
(3) And (3) adding the solid product obtained in the step (2) into an alcoholic solution of vinyl trimethoxy silane, and then preserving the temperature for 4 hours at 50 ℃ to obtain the modified catalyst.
(4) Mixing the modified catalyst in the step (3) with water according to the proportion of 1g: and mixing the components in a proportion of 110ml, and performing ultrasonic dispersion to disperse the modified catalyst in water to obtain the thick oil viscosity reducer.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) A thick oil sample having a viscosity of 36600 mPas at 50 ℃ is taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 0.6% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 130 ℃ for 24 hours, opening the high-pressure reaction kettle to continue heating to remove moisture in the reacted thickened oil sample, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
Example 4
1. A preparation method of the thick oil viscosity reducer comprises the following steps:
(1) Taking 50g of porous carbon powder, adding the porous carbon powder into 200ml of saturated ferric acetate solution to infiltrate the porous carbon powder, stirring for 5min, adding an excessive sodium borohydride solution with the mass fraction of 20%, and filtering and separating out porous carbon in a reaction liquid to obtain a catalyst precursor for later use.
(2) Adding the catalyst precursor obtained in the step (1) and 300ml of butanol into a high-pressure reaction kettle, reacting for 35min at 110 ℃, and then filtering and separating out a solid product.
(3) And (3) adding the solid product obtained in the step (2) into an alcoholic solution of vinyl trimethoxy silane, and then preserving the temperature for 3.5 hours at 55 ℃ to obtain the modified catalyst.
(4) Mixing the modified catalyst in the step (3) with water according to the proportion of 1g:105ml of the mixture is mixed and subjected to ultrasonic dispersion, so that the modified catalyst is dispersed in water, and the thick oil viscosity reducer is obtained.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) A thick oil sample having a viscosity of 36600 mPas at 50 ℃ is taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 1.2% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 160 ℃ for 24 hours, opening the high-pressure reaction kettle, continuously heating to remove water in the reacted thickened oil sample, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
Example 5
1. A preparation method of the thick oil viscosity reducer comprises the following steps:
(1) Taking 50g of porous carbon powder, adding the porous carbon powder into 200ml of saturated ferric chloride solution to infiltrate the porous carbon powder, stirring for 5min, adding excessive sodium borohydride solution with the mass fraction of 20%, and filtering and separating out porous carbon in a reaction solution to obtain a catalyst precursor for later use.
(2) And (2) adding the catalyst precursor obtained in the step (1) into an alcoholic solution of vinyl triethoxysilane, and then preserving heat at 60 ℃ for 5 hours to obtain the modified catalyst.
(3) Mixing the modified catalyst in the step (2) with water in an amount of 1g: and mixing the components in a proportion of 90ml, and performing ultrasonic dispersion to disperse the modified catalyst in water to obtain the thick oil viscosity reducer.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) A thick oil sample having a viscosity of 36600 mPas at 50 ℃ is taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 1.0% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 150 ℃ for 24 hours, opening the high-pressure reaction kettle, continuously heating to remove water in the reacted thickened oil sample, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
Example 6
1. A preparation method of a thick oil viscosity reducer comprises the following steps:
(1) Taking 50g of porous carbon powder, adding the porous carbon powder into 200ml of saturated ferric chloride solution to infiltrate the porous carbon powder, stirring for 5min, adding an excessive sodium borohydride solution with the mass fraction of 20%, and filtering and separating out porous carbon in a reaction liquid to obtain a catalyst precursor for later use.
(2) And (2) adding the catalyst precursor obtained in the step (1) and 300ml of absolute ethyl alcohol into a high-pressure reaction kettle, reacting for 25min at 115 ℃, and then filtering and separating out a solid product to obtain the modified catalyst.
(3) Mixing the modified catalyst in the step (2) with water in an amount of 1g: mixing the components in a proportion of 90ml, and performing ultrasonic dispersion to disperse the modified catalyst in water to obtain the thick oil viscosity reducer.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) A thick oil sample having a viscosity of 36600 mPas at 50 ℃ is taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 1.0% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 150 ℃ for 24 hours, opening the high-pressure reaction kettle, continuously heating to remove water in the reacted thickened oil sample, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
Example 7
1. A preparation method of the thick oil viscosity reducer comprises the following steps:
(1) Taking 50g of porous carbon powder, adding the porous carbon powder into 200ml of saturated ferric chloride solution to infiltrate the porous carbon powder, stirring for 5min, and filtering and separating out porous carbon in reaction liquid to obtain a catalyst precursor for later use.
(2) Adding the catalyst precursor obtained in the step (1) and 300ml of absolute ethyl alcohol into a high-pressure reaction kettle, reacting for 25min at 115 ℃, and then filtering and separating out a solid product.
(3) And (3) adding the solid product obtained in the step (2) into an alcoholic solution of vinyl triethoxysilane, and then preserving heat at 60 ℃ for 5 hours to obtain the modified catalyst.
(4) Mixing the modified catalyst in the step (3) with water according to the proportion of 1g: mixing the components in a proportion of 90ml, and performing ultrasonic dispersion to disperse the modified catalyst in water to obtain the thick oil viscosity reducer.
2. A method for reducing viscosity of thick oil comprises the following steps:
(i) A thick oil sample having a viscosity of 36600 mPas at 50 ℃ is taken and heated to 80 ℃ for use.
(ii) Adding 200g of the preheated thickened oil sample and the thickened oil viscosity reducer of the embodiment into a high-pressure reaction kettle together, wherein the addition amount of the thickened oil viscosity reducer is 1.0% of the mass of the thickened oil based on the mass of the modified catalyst, reacting at 150 ℃ for 24 hours, opening the high-pressure reaction kettle, continuously heating to remove water in the reacted thickened oil sample, measuring the viscosity of the obtained thickened oil sample at room temperature after the temperature of the reaction kettle is reduced, and calculating the viscosity reduction rate.
As shown in table 1, the viscosity and viscosity reduction rate calculation results of the thick oil samples in the above examples are shown. It can be seen that the viscosity reducing effects of the viscosity reducers prepared in examples 1 to 4 on thick oil are obviously better than those of examples 5 to 7, wherein in example 5, no hydrophilic group is introduced into the catalyst, so that the catalyst is agglomerated in water to influence the dispersion effect of the catalyst in thick oil, and the catalytic effect and the catalytic efficiency are reduced. In the embodiment 6, lipophilic groups are not introduced into the catalyst, and the layering phenomenon is caused due to water-oil incompatibility, so that the catalyst in water is difficult to effectively contact with the thickened oil, the catalyst cannot fully play a role, and the viscosity reduction effect is not high and the viscosity reduction speed is low. On the other hand, the reduction process of the metal ions on the porous carbon is not completed in example 7, and the metal ions are re-dissolved in water after the catalyst is added into water, so that the effective catalysis effect is difficult to achieve.
TABLE 1
| Example number | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Viscosity (Pa. S) | 2060 | 1142 | 2492 | 1859 | 12916 | 22823 | 33943 |
| Viscosity reduction Rate (%) | 94.37 | 96.88 | 93.19 | 94.92 | 64.71 | 37.64 | 7.26 |
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the thick oil viscosity reducer is characterized by comprising the following steps:
(1) Soaking porous carbon powder with a solution containing catalyst metal ions, adding a reducing agent to reduce the metal ions into metal simple substances, enriching and adsorbing the metal simple substances on the porous carbon powder, and separating the porous carbon powder to obtain a catalyst precursor for later use; the ratio of the porous carbon powder to the solution containing the catalyst metal ions is 50g:100 to 200ml;
(2) Carrying out hydrophilic modification treatment on the catalyst precursor, and then carrying out oleophylic modification treatment to obtain a modified catalyst;
(3) Mixing the modified catalyst with water, and then carrying out ultrasonic dispersion to obtain an ultrasonic dispersion liquid, namely the thickened oil viscosity reducer;
in the step (1), the catalyst metal ions include: at least one of iron ions, ferrous ions, copper ions, nickel ions and zinc ions;
the solution containing the catalyst metal ions is a saturated solution at room temperature;
in the step (1), the reducing agent is any one of a sodium borohydride solution and a potassium borohydride solution;
in the step (2), the catalyst precursor is mixed with liquid alcohol and then subjected to solvothermal reaction;
the temperature of the solvent thermal reaction is 100 to 120 ℃, and the time is 20 to 40min;
the liquid alcohol comprises at least one of methanol, ethanol, propanol and butanol;
in the step (2), mixing the catalyst precursor subjected to hydrophilic modification treatment with a silane coupling agent solution, heating to a set temperature, and then carrying out heat preservation to obtain a modified catalyst;
the silane coupling agent comprises any one of vinyl triethoxysilane and vinyl trimethoxysilane;
the heat preservation temperature is 50 to 65 ℃, and the time is 3 to 5 hours;
in the step (3), the ratio of the modified catalyst to water is 1g:80 to 110ml.
2. The method for preparing the thick oil viscosity reducer according to claim 1, wherein the solution containing the catalyst metal ions comprises a solution formed by dissolving at least one of chloride, sulfate, nitrate and acetate of the metal ions in water.
3. The use of the viscosity reducer for thick oil obtained by the method for preparing the viscosity reducer for thick oil according to claim 1 or 2 in petroleum engineering.
4. The use of claim 3, wherein the thick oil viscosity reducer is used for viscosity reduction of thick oil, and the use method comprises the following steps: injecting hot steam into the thickened oil recovery well to preheat the thickened oil, adding the thickened oil viscosity reducer, and sealing the oil well to perform a hydrothermal catalytic cracking reaction on the thickened oil.
5. The application of claim 4, wherein the addition amount of the heavy oil viscosity reducer is 0.6-1.5% of the mass of the heavy oil, calculated according to the mass of the modified catalyst in the heavy oil viscosity reducer.
6. The use according to claim 4, wherein the temperature of the pre-heat treatment is 130 to 170 ℃.
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| CN115011323B (en) * | 2022-07-19 | 2023-06-02 | 胜利油田方圆化工有限公司 | Viscosity reducer for aquathermolysis of thick oil and preparation method and application thereof |
| CN115142830A (en) * | 2022-08-11 | 2022-10-04 | 安东石油技术（集团）有限公司 | Yield and efficiency increasing method for fracturing and reforming heavy oil reservoir |
| CN115651627B (en) * | 2022-12-27 | 2023-03-10 | 胜利油田方圆化工有限公司 | Preparation process and application of modified polymer oil-displacing agent for oil exploitation |
| CN115948155B (en) * | 2023-03-13 | 2023-05-12 | 胜利油田方圆化工有限公司 | Preparation process and application of viscosity-reducing oil displacement agent for petroleum exploitation |
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