BIOLOGICAL AND CHEMICAL COMPOSITE BLOCKAGE REMOVING AGENT AND PREPARATION PROCESS AND USE THEREOF

Abstract

The present invention relates to a biological and chemical composite blockage removing agent and preparation process and use thereof, and mainly solves the problems that the existing blockage removing agents have poor blockage removal effect on organic blockages, cause damage to formations and oil-wells, produce serious environmental pollution, and corrode the equipment, pipelines, and the like. The problems can be well solved by using a technical solution of a biological and chemical composite blockage removing agent, which contains the following components in parts by mass: A. 10-50 parts of a biosurfactant; B. 5-20 parts of a chemical surfactant; wherein the chemical surfactant is an anionic-nonionic surfactant, and said technical solution can be used in the industrial production for removing the blockage in the oilfield, and reducing the injection pressure and increasing the injection.

Claims

1. A biological and chemical (B&C) composite blockage removing agent, which comprises the following components in parts by mass: A. 10-50 parts of a biosurfactant; B. 5-20 parts of a chemical surfactant; wherein the chemical surfactant is an anionic-nonionic surfactant; the anionic-nonionic surfactant is a hydrocarbyl polyoxyethylene polyoxypropylene ether acid salt.

2. The B&C composite blockage removing agent according to claim 1, wherein the biosurfactant is at least one selected from lipopeptide, rhamnolipid, trehalose lipid, sophorolipid, gramicidin, alkyl polyglycoside, saponin, and cyclodextrin.

3. The B&C composite blockage removing agent according to claim 1, wherein the biosurfactant is at least one selected from lipopeptide, rhamnolipid, and trehalose lipid.

4. The B&C composite blockage removing agent according to claim 1, wherein in the hydrocarbyl polyoxyethylene polyoxypropylene ether acid salt, the ethylene oxide unit (EO unit) number and the propylene oxide unit (PO unit) number are each independently an arbitrary number in the range of 0-60 and are not both 0 at the same time, the carbon atom number of the hydrocarbyl moiety except the carbon atom number in the EO unit, the PO unit, and the acid group is 6 50.

5. The B&C composite blockage removing agent according to claim 1, wherein the hydrocarbyl polyoxyethylene polyoxypropylene ether acid salt has a general formula in the following structure: ##STR00002## wherein R.sub.1 is an optionally substituted C.sub.4-40 linear or branched alkyl, an optionally substituted C.sub.4-40 monocyclic or polycyclic cycloalkyl, an optionally substituted C.sub.4-40 linear or branched alkenyl, an optionally substituted C.sub.6-40 aryl, R.sub.2 is an optionally substituted C.sub.1-20 linear or branched alkylene, an optionally substituted C.sub.4-40 monocyclic or polycyclic cycloalkylene, an optionally substituted C.sub.4-40 linear or branchedalkenylene, an optionally substituted C.sub.6-40 arylene, the “optionally substituted” refers to optionally substituted by one or more substituents selected from hydroxyl, C.sub.1-20 linear or branched alkyl, C.sub.5-10 monocyclic or polycyclic cycloalkyl, C.sub.2-20 linear or branched alkenyl and C.sub.6-20 aryl, the sum of the carbon atom number in R.sub.1 and the carbon atom number in R.sub.2 is 6-50; m and n are each an arbitrary number in the range of 0-60 and are not both 0 at the same time, X is one of carboxylate radical, sulfate radical, phosphate radical, and sulfonate radical, Y is a counter ion, a is the absolute value of the X's valence, b is the absolute value of the Y's valence.

6. The B&C composite blockage removing agent according to claim 1, wherein the B&C composite blockage removing agent further comprises component C, in parts by mass: 1-30 parts of a synergist selected from C.sub.2-C.sub.6 polyols.

7. The B&C composite blockage removing agent according to claim 1, wherein the B&C composite blockage removing agent further comprises component D, in parts by mass: 0-84 parts of water; in the B&C composite blockage removing agent, relative to the total mass of the composite blockage removing agent, the content of the biosurfactant is 10%-50%; the content of the chemical surfactant is 5%-20%; the content of the synergist is 1%-30%; the content of water is 0%-84%.

8. A process for preparing the B&C composite blockage removing agent according to claim 1, which comprises the following steps: mixing a biosurfactant, a chemical surfactant, optionally a synergist, and optionally water to obtain the B&C composite blockage removing agent.

9. A method for removing the blockage of crude oil, comprising utilizing the B&C composite blockage removing agent according to claim 1.

10. The method according to claim 9, wherein, in terms of the total mass concentration of the biosurfactant and the chemical surfactant, the concentration of the B&C composite blockage removing agent when in use is 0.001%-5%.

11. The method according to claim, wherein at first, any one of the biosurfactant and the chemical surfactant is added, and then another one is added, or the biosurfactant and the chemical surfactant are both added at the same time.

12. A blockage removing agent composition, which contains the B&C composite blockage removing agent according to claim 1 and a solvent, relative to the total mass of the composition, in terms of the total mass concentration of the biosurfactant and the chemical surfactant, the concentration of the B&C composite blockage removing agent is 0.001%-5%.

13. The blockage removing agent composition according to claim 12, wherein the solvent is selected from organic solvents and water.

14. The method for removing the blockage of crude oil, comprising utilizing the blockage removing agent composition according to claim 12.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0015] FIG. 1 is a schematic diagram of the physical simulation experiment apparatus.

DETAILED DESCRIPTION OF THE INVENTION

[0016] Reference will now be made in detail to the present embodiments of the present invention, but it should be understood that the scope of the invention is not limited by the embodiments, but is defined by the appended claims.

[0017] All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by those skilled in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

[0018] When the specification derives a material, a substance, a process, a step, a device, an element, and the like with the expression such as “known to those skilled in the art”, “prior art”, or a synonym thereof, it is intended that the objects derived by such a prefix encompasses those having been conventionally used in the art at the time of filing this application, but also includes those which may not be so commonly used at present, but will become known in the art as being suitable for a similar purpose.

[0019] In the context of this specification, except for what is explicitly stated, any item or matter not mentioned is directly applicable to those known in the art without any changes. Moreover, any of the embodiments described herein can be freely combined with one or more other embodiments described herein, and the resulting technical solutions or technical ideas are regarded as part of the original disclosure or the original record of the present invention, and should not be regarded as new content that has not been disclosed or anticipated in this specification unless those skilled in the art believe that the combination is unreasonable.

[0020] In the present specification, the C.sub.4-40 linear or branched alkyl represents a group obtained by removing one hydrogen atom from a linear or branched alkane having 4-40 carbon atoms without violating the valence, and preferably a group obtained by removing one hydrogen atom attached to one terminal carbon atom from the alkane. The C.sub.4-40 linear or branched alkyl may include C.sub.5-30 linear or branched alkyl, and may also include C.sub.6-20 linear or branched alkyl. As the specific examples of these alkyl groups, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, hexadecyl, octadecyl, eicosyl, docosyl, and isomers of these groups and the like can be enumerated, but not limited thereto. On the other hand, C.sub.1-20 linear or branched alkyl and C.sub.1-10 linear or branched alkyl are defined in the same way as the above-mentioned alkyl, except that the carbon atom numbers thereof are 1-20 and 1-10 respectively.

[0021] In the present specification, the C.sub.4-40 monocyclic or polycyclic cycloalkyl represents a group obtained by removing one hydrogen atom from a monocyclic or polycyclic cycloalkane having 4-40 carbon atoms without violating the valence. It should be noted that the C.sub.4-40 monocyclic or polycyclic cycloalkyl group includes the case where all carbon atoms are ring-forming carbon atoms, and also includes the case where an alkyl group or a cycloalkyl group is bonded to the cycloalkyl group as a substituent, provided that there is a monocyclic or polycyclic alkyl group in the group structure and the total carbon atom number is 4-40. The C.sub.4-40 monocyclic or polycyclic cycloalkyl may include C.sub.5-30 monocyclic or polycyclic cycloalkyl, and may also include C.sub.6-20 monocyclic or polycyclic cycloalkyl, C.sub.5-10 monocyclic or polycyclic cycloalkyl, C.sub.5-8 monocyclic or polycyclic cycloalkyl, C.sub.5-7 monocyclic or polycyclic cycloalkyl. As the specific examples of these monocyclic or polycyclic cycloalkyl groups, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, octylcyclohexyl, and the like can be enumerated, but not limited thereto.

[0022] In the present invention, the C.sub.4-40 linear or branched alkenyl refers to a group obtained by having at least one olefinic double bond, preferably having one double bond, in the above-mentioned C.sub.4-40 linear or branched alkyl. The C.sub.4-40 linear or branched alkenyl may include C.sub.5-30 linear or branched alkenyl, and may also include C.sub.6-10 linear or branched alkenyl. As the specific examples of these alkenyl groups, butenyl, 2-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, isomers of these groups and the like can be enumerated, but not limited thereto. On the other hand, C.sub.2-10 linear or branched alkenyl and C.sub.2-10 linear or branched alkenyl are defined in the same way as the above-mentioned alkenyl, except that the carbon atom numbers thereof are 2-20 and 2-10 respectively.

[0023] In the present specification, the C.sub.6-40 aryl represents a group obtained by removing one hydrogen atom from an aromatic hydrocarbon having 6-40 carbon atoms without violating the valence. It should be noted that the C.sub.6-40 aryl group includes the case where all carbon atoms are ring-forming carbon atoms of the aromatic ring, and also includes the case where an alkyl group or a cycloalkyl group is bonded to the aromatic ring as a substituent, provided that there is an aromatic ring in the group structure and the total carbon atom number is 6-40. The C.sub.6-40 aryl may include C.sub.6-30 aryl, and may also include C.sub.6-20 aryl or C.sub.6-10 aryl. As the specific examples of these aryl groups, phenyl, naphthyl, methylphenyl, dimethylphenyl, ethylphenyl, methylnaphthyl, 2-methylnaphthyl, 2-ethylnaphthyl and the like can be enumerated, but not limited thereto.

[0024] In the present invention, C.sub.1-20 linear or branched alkylene represents a group obtained by removing two hydrogen atoms from a linear or branched alkane having 1-20 carbon atoms without violating the valence, and preferably a group obtained by removing each hydrogen atom attached to two terminal carbon atoms of the alkane. The C.sub.1-20 linear or branched alkylene may include C.sub.1-10 linear or branched alkylene, and may also include C.sub.1-8 linear or branched alkylene. As the specific examples of these alkylene groups, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, isomers of these groups and the like can be enumerated, but not limited thereto.

[0025] In the present invention, the C.sub.4-40 monocyclic or polycyclic cycloalkylene represents a group obtained by removing two hydrogen atoms from a monocyclic or polycyclic cycloalkane having 4-40 carbon atoms without violating the valence. Preferred is a group obtained by removing each hydrogen atom from two different carbon atoms. It should be noted that the C.sub.4-40 monocyclic or polycyclic cycloalkylene group includes the case where all carbon atoms are ring-forming carbon atoms, and also includes the case where an alkyl group or a cycloalkyl group is bonded to the cycloalkyl group as a substituent, provided that there is a monocyclic or polycyclic alkyl group in the group structure and the total carbon atom number is 4-40. In addition, two bonding bonds can both be located at the monocyclic or polycyclic moiety, or both at the substituent of the monocyclic or polycyclic moiety, or one at the monocyclic or polycyclic moiety and the other at the substituent. The C.sub.4-40 monocyclic or polycyclic cycloalkylene may include C.sub.5-30 monocyclic or polycyclic cycloalkylene, and may also include C.sub.6-20 monocyclic or polycyclic cycloalkylene. As the specific examples of these monocyclic or polycyclic cycloalkyl groups, 1,2-cyclopentanediyl, 1,2-cyclohexanediyl, 1,4-cycloheptanediyl, 1,4-cyclooctanediyl, 3 -methylcyclohexane-1,2-diyl, 3 -ethylcyclohexane-1,2-diyl, 3-propylcyclohexane-1,2-diyl and the like can be enumerated, but not limited thereto.

[0026] In the present invention, the C.sub.4-40 linear or branched alkenylene refers to a group obtained by having at least one olefinic double bond, preferably having one double bond, in the above-mentioned C.sub.4-40 linear or branched alkylene. The C.sub.4-40 linear or branched alkenylene may include C.sub.5-30 linear or branched alkenylene, and may also include C.sub.6-20 linear or branched alkenylene. As the specific examples of these alkenylene groups, 2-butene-1,4-diyl, 2-pentene-1,4-diyl, 3-hexylene-1,6-diyl, 3-heptylene-1,7-diyl, 4-octylene-1,8-diyl, isomers of these groups and the like can be enumerated, but not limited thereto.

[0027] In the present specification, the C.sub.6-40 arylene represents a group obtained by removing two hydrogen atoms from an aromatic hydrocarbon having 6-40 carbon atoms without violating the valence. It should be noted that the C.sub.6-40 arylene group includes the case where all carbon atoms are ring-forming carbon atoms of the aromatic ring, and also includes the case where an alkyl group or a cycloalkyl group is bonded to the aromatic ring as a substituent, provided that there is an aromatic ring in the group structure and the total carbon atom number is 6-40. In addition, two bonding bonds can both be located at the aromatic ring, or both at the substituent of the aromatic ring, or one at the aromatic ring and the other at the substituent. The C.sub.6-40 arylene may include C.sub.6-30 arylene, and may also include C.sub.6-20 arylene. As the specific examples of these aryl groups, 1,4-phenylene, 1,4-naphthylene, 2-methyl-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 2-ethyl-1,4-phenylene and the like can be enumerated, but not limited thereto.

[0028] In the present invention, “optionally substituted” refers to optionally substituted by one or more substituents selected from hydroxyl, C.sub.1-20 (preferably C.sub.1-10) linear or branched alkyl, C.sub.5-10 (preferably C.sub.5-8 or C.sub.5-7) monocyclic or polycyclic cycloalkyl (such as cyclohexyl), C.sub.2-20 (preferably C.sub.2-10) linear or branched alkenyl and C.sub.6-20 (preferably C.sub.6-10) aryl.

[0029] In the present invention, the number of substituents that “optionally substitute” can be 0, or 1, 2, 3, 4, 5, 6, 7, or 8, subject to the upper limit of the number of the substituted groups that can be substituted.

[0030] Specifically, the present invention provides the following technical solutions.

[0031] A B&C composite blockage removing agent, which contains the following components in parts by mass: A. 10-50 parts of a biosurfactant; and B. 5-20 parts of a chemical surfactant; wherein the chemical surfactant is an anionic-nonionic surfactant.

[0032] In the present invention, the biosurfactant commonly used in the art can be used. It may be a commercial product, or it may be obtained by specific bacterial fermentation. In one embodiment of the present invention, the biosurfactant is at least one of lipopeptide, rhamnolipid, trehalose lipid, sophorolipid, gramicidin, alkylpolyglycoside, saponin, and cyclodextrin. In one embodiment of the present invention, the biosurfactant is preferably at least one of lipopeptide, rhamnolipid, and trehalose lipid.

[0033] In the blockage removing agent of the present invention, the chemical surfactant is selected from anionic-nonionic surfactants.

[0034] In one embodiment of the present invention, as the anionic-nonionic surfactant, it is preferably a hydrocarbyl polyoxyethylene polyoxypropylene ether acid salt.

[0035] In the present invention, the acid salt as the anionic part of the chemical surfactant is not particularly limited, and those commonly used in the art can be used. In one embodiment of the present invention, the acid salt is at least one of carboxylate salt, sulfate salt, phosphate salt, and sulfonate salt.

[0036] In one embodiment of the present invention, in the hydrocarbyl polyoxyethylene polyoxypropylene ether acid salt, the ethylene oxide unit (EO unit) number and the propylene oxide unit (PO unit) number are each independently an arbitrary number in the range of 0-60 and are not both 0 at the same time. That is, in the hydrocarbyl polyoxyethylene polyoxypropylene ether acid salt, at least one alkylene oxide unit is present. In one embodiment of the present invention, preferably the ethylene oxide unit (EO unit) number and the propylene oxide unit (PO unit) number are each independently 1-50, more preferably 1-40.

[0037] In one embodiment of the present invention, in the hydrocarbyl polyoxyethylene polyoxypropylene ether acid salt, the carbon atom number of the hydrocarbyl moiety except that the carbon atom number in the EO unit, the PO unit, and the acid group is 6-50, preferably 6-40, more preferably 6-30.

[0038] In one embodiment of the present invention, the hydrocarbyl polyoxyethylene polyoxypropylene ether acid salt has a general formula in the following structure:

##STR00001##

[0039] wherein R.sub.1 is an optionally substituted C.sub.4-40 (or C.sub.5-30, or C.sub.6-20) linear or branched alkyl, an optionally substituted C.sub.4-40 (or C.sub.5-30, or C.sub.6-20)monocyclic or polycyclic cycloalkyl, an optionally substituted C.sub.4-40 (or C.sub.5-30, or C.sub.6-20) linear or branched alkenyl, an optionally substituted C.sub.6-40 (or C.sub.6-30, or C.sub.6-20)aryl, R.sub.2 is an optionally substituted C.sub.1-20 (or C.sub.1-10, or C.sub.1-8) linear or branched alkylene, an optionally substituted C.sub.4-40 (or C.sub.5-30, or C.sub.6-20) monocyclic or polycyclic cycloalkylene, an optionally substituted C.sub.4-40 (or C.sub.5-30, or C.sub.6-20) linear or branchedalkenylene, an optionally substituted C.sub.6-40 (or C.sub.6-30, or C.sub.6-20) arylene, the “optionally substituted” refers to optionally substituted by one or more substituents selected from hydroxyl, C.sub.1-20 (preferably C.sub.1-10) linear or branched alkyl, C.sub.5-10 (preferably C.sub.5-8 or C.sub.5-7) monocyclic or polycyclic cycloalkyl (such as cyclohexyl), C.sub.2-10 (preferably C.sub.2-10) linear or branched alkenyl and C.sub.6-20 (preferably C.sub.6-10) aryl, the sum of the carbon atom number in R.sub.1 and the carbon atom number in R.sub.2 is 6-50, preferably 6-40, more preferably 6-30; m and n are each an arbitrary number in the range of 0-60 and are not both 0, X is one of carboxylate radical, sulfate radical, phosphate radical, and sulfonate radical, Y is a counter ion, a is the absolute value of the X's valence, b is the absolute value of the Y's valence.

[0040] In one embodiment of the present invention, the R.sub.1 group is preferably an optionally substituted C.sub.4-40 (or C.sub.5-30, or C.sub.6-20) linear or branched alkyl, an optionally substituted C.sub.6-40 (or C.sub.6-30, or C.sub.6-20) aryl.

[0041] In one embodiment of the present invention, the R.sub.2 group is preferably an optionally substituted C.sub.1-20 (or C.sub.1-10, or C.sub.1-8) linear or branched alkylene, an optionally substituted C.sub.6-40 (or C.sub.6-30, or C.sub.6-20) arylene.

[0042] In one embodiment of the present invention, “optionally substituted” preferably refers to being optionally substituted by one or two substituents selected from C.sub.1-20 (preferably C.sub.1-10) linear or branched alkyl, C.sub.6-20 (preferably C.sub.6-10) aryl.

[0043] In one embodiment of the present invention, in the hydrocarbyl polyoxyethylene polyoxypropylene ether acid salt, since EO units and PO units can be represented by average numbers, the numbers of m and n may be non-integers. At this time, m and n for example can be 0, 0.5, 1.2, 2.0, 2.5, 3.0, 3.5, 5.4, 7.5, 10.0, 15.0, 25.0, 30.2, 35.0, 40.0, 45.5, 50.5 or like. In the present invention, the counter ions commonly used in the art can be used as Y. In one embodiment of the present invention, Y is preferably any one of Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+, and NH.sub.4.sup.+.

[0044] In the present invention, as the anionic-nonionic surfactant, a commercial product can be used, or it may be obtained through the synthesis with the methods well known in the art.

[0045] In one embodiment of the present invention, in parts by mass, preferably the biosurfactant comprises 20-50 parts, and the chemical surfactant comprises 5-15 parts, more preferably the biosurfactant comprises 30-50 parts, and the chemical surfactant comprises 5-15 parts.

[0046] In one embodiment of the present invention, in parts by mass, the B&C composite blockage removing agent further contains the component C: 1-30 parts, preferably 10-20 parts of a synergist.

[0047] In one embodiment of the present invention, the synergist is preferably a C.sub.2-C.sub.6 polyol; more preferably at least one of ethylene glycol, propylene glycol, and glycerol.

[0048] In one embodiment of the present invention, in parts by mass, the B&C composite blockage removing agent further can contain the component D: 0-84 parts by mass, preferably the balance of water.

[0049] In an embodiment of the present invention, the B&C composite blockage removing agent may further comprise other additives commonly used in the art, including but not limited to microorganisms that degrade the oil pollution.

[0050] In an embodiment of the present invention, the B&C composite blockage removing agent may further comprise other additives commonly used in the art, but comprise no microorganisms that degrade the oil pollution.

[0051] In one embodiment of the present invention, in the B&C composite blockage removing agent, relative to the total mass of the composite blockage removing agent, the content of the biosurfactant is 10%-50% (preferably 20%-50%, more preferably 30%-50%); the content of the chemical surfactant is 5%-20% (preferably 5%-15%); the content of the synergist is 1%-30% (preferably 10%-20%); the content of water is 0%-84% (preferably the balance). In one embodiment of the present invention, the blockage removing agent of the present invention has no special requirements for water when it is formulated, and the water can be deionized water or water containing inorganic minerals, and the water containing inorganic minerals can be tap water, oilfield formation water or oilfield injection water.

[0052] The present invention also provides a process for preparing the above-mentioned B&C composite blockage removing agent, which comprises the following steps: mixing a biosurfactant, a chemical surfactant, optionally a synergist, and optionally water to obtain the B&C composite blockage removing agent. In one embodiment of the present invention, in the above-mentioned preparation process of the B&C composite blockage removing agent, a part of the required water can be used as a solvent to dissolve the biosurfactant, the chemical surfactant, and optionally the synergist, and then the rest of water is added.

[0053] In one embodiment of the present invention, the preparation process is preferably performed in the following steps:

[0054] first, the required amount of the anionic-nonionic surfactant is added to water and completely dissolved by stirring; the required amount of the synergist is added to the completely dissolved anionic-nonionic surfactant solution, and mixed evenly by stirring; then the required amount of the biosurfactant is added, and mixed evenly by stirring; optionally the remaining water is supplemented to reach the required amount of water, and mixed evenly by stirring to obtain the B&C composite blockage removing agent.

[0055] The present invention also provides a blockage removing agent composition, which comprises a solvent and the above-mentioned B&C composite blockage removing agent of the present invention, wherein relative to the total mass of the composition, in terms of the total mass concentration of the biosurfactant and the chemical surfactant, the concentration of the B&C composite blockage removing agent is 0.001%-5%, preferably 0.005%-2%.

[0056] In one embodiment of the present invention, the solvent is selected from crude oil, organic compounds, or water. The solvent is preferably water.

[0057] The present invention also provides the use of the B&C composite blockage removing agent of the present invention for removing the blockage of crude oil.

[0058] In one embodiment of the present invention, in said use, in terms of the total mass concentration of the biosurfactant and the chemical surfactant, the concentration of the B&C composite blockage removing agent when in use is 0.001%-5%, preferably 0.005%-2%.

[0059] In one embodiment of the present invention, the use is not particularly limited and can be utilized by those skilled in the art according to the existing blockage removal technology. For example, a solution of the B&C composite blockage removing agent is formulated according to the weight percentage of the raw material components, diluted with water to an effective concentration (in terms of the total mass of two components, the biosurfactant, and the chemical surfactant) of 0.001%-5%, preferably 0.005%-2%, and then a certain amount of the resulting solution is injected into a water-well or an oil-well, but not limited thereto.

[0060] In one embodiment of the present invention, in the use of the blockage removing agent of the present invention, at first, any one of the biosurfactant and the chemical surfactant is added, and then another one is added. For example, at first, the biosurfactant can be added to a water-well or an oil-well, and then the chemical surfactant is added; or at first, the chemical surfactant can be added to a water-well or an oil-well, and then the biosurfactant is added. In one embodiment of the present invention, the biosurfactant and the chemical surfactant are added at the same time in the use of the blockage removing agent of the present invention.

[0061] In the B&C composite blockage removing agent of the present invention, a combination of the biosurfactant and the chemical surfactant is used. Further, the present invention provides a combination of the biosurfactant, the chemical surfactant, and the synergist. All of these combinations produce a good synergistic effect. The interaction between components makes the blockage removing agent effectively solubilize the crude oil, reduce the oil-water interfacial tension to an ultra-low level, and significantly reduce the oil-water interface interaction, thereby reducing the oil-water flow resistance in the formation, and playing a good role in removing the blockage and being able to effectively reduce the injection pressure.

[0062] The B&C composite blockage removing agent of the present invention can be used for the blockage removing construction in oilfields. After injecting the blockage removing agent, the residual oil in the water-well or the oil-well can be effectively solubilized. The solubilization parameter can reach 20 or higher, and the oil-water interfacial tension can be reduced to the order of magnitude of about 10.sup.−4 mN/m, significantly reducing the oil-water interface interaction, thereby reducing the oil-water flow resistance in the formation. With the solubilization of the residual oil and the ultra-low interfacial tension, the effect on the development by the water injection of the oilfield can be effectively improved. The physical simulation experiment proves that the blockage removing agent of the present invention can reduce the injection pressure by 20% or higher, or even 30% or higher, and has achieved a relatively good technical effect.

[0063] In one embodiment of the present invention, the main components of the B&C composite blockage removing agent of the present invention can be analyzed and detected by the following method.

[0064] The lipopeptide can be analyzed by the combined use of high-performance liquid chromatography-mass spectrometry: the reversed C.sub.18 chromatographic separation column is used as the chromatographic column; the mobile phase is subjected to gradient elution with acetonitrile (A)-0.05% aqueous trifluoroacetic acid solution (B), the conditions for the gradient elution comprise 0-20 min, 80% A-100% A, and 20-30 min, 100% A; the ESI+ ion mode is used for the mass spectrometry, and the scanning range is 150-1500.

[0065] The hydrocarbyl polyoxyethylene polyoxypropylene ether acid salt can be analyzed by the combined use of high-performance liquid chromatography-mass spectrometry: the reversed C.sub.18 chromatographic separation column is used as the chromatographic column; the mobile phase is eluted with methanol-water-acetic acid ammonium acetate buffer salt, the mass fractions of three components in the mobile phase are 65%, 35%, and 5%, respectively; the ESI+ ion mode is used for the mass spectrometry, and the scanning range is 150-1500.

[0066] The rhamnolipid can be analyzed by the combined use of high-performance liquid chromatography-mass spectrometry: the reversed C.sub.18 chromatographic separation column is used as the chromatographic column; the mobile phase is subjected to gradient elution with acetonitrile (A)-acetic acid (B), the conditions for the gradient elution comprise 0-3 min, 50% B, 3-12 min, 50% B-0% B, 12-16 min, 0% B, 16-17 min, 0% B-50% B, 17-20 min, 50% B; the ESI+ ion mode is used for the mass spectrometry, and the scanning range is 150-1500.

[0067] The rhamnolipid can be analyzed by the combined use of high-performance liquid chromatography-mass spectrometry: the reversed C.sub.18 chromatographic separation column is used as the chromatographic column; the mobile phase is subjected to gradient elution with 0.5% aqueous formic acid solution (A)-acetonitrile (B), the conditions for the gradient elution comprise 0-5 min, 50% B, 5-30 min, 50% B-60% B, 30-60 min, 60% B-100% B; the ESI+ ion mode is used for the mass spectrometry, and the scanning range is 150-1500.

EXAMPLES

[0068] To better understand the present invention, the content of the present invention is further described below in conjunction with the examples, but the content of the present invention is not limited to the following examples.

Example 1

[0069] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0070] A. lipopeptide: 30 g, commercially available from KANEKA CORPORATION JAPAN;

[0071] B. Sodium dodecyl polyoxyethylene polyoxypropylene ether carboxylate (C.sub.12H.sub.25O(PO).sub.12(EO).sub.24CH.sub.2COONa): 10 g, self-manufactured;

[0072] C. Ethylene glycol: 10 g;

[0073] D. the balance of water.

[0074] Preparation process: to a beaker was added a predetermined amount of sodium dodecyl polyoxyethylene polyoxypropylene ether carboxylate, then added a half of a predetermined amount of the make-up water, and the resulting mixture was completely dissolved by stirring; to the completely dissolved surfactant solution was added a predetermined amount of ethylene glycol, and the resulting mixture was mixed evenly by stirring; a predetermined amount of lipopeptide was added and the resulting mixture was stirred evenly; another half of the make-up water that was remained was supplemented, and the resulting mixture was mixed evenly by stirring.

[0075] Effect evaluation:

[0076] Interfacial tension: A TX-500C spinning drop interfacial tensiometer was used to measure the oil-water interfacial tensions of the crude oil samples from the Shengli Oil Production Plant of Shengli Oilfield with the blockage removing agents having effective mass concentrations of 0.005%, 0.05%, 0.5%, and 2% respectively. The measuring temperature was 80° C., the water was the simulated formation water, and the mineralization degree was 29000 mg/L. The oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were: 9×10.sup.−4 mN/m, 5×10.sup.−4 mN/m, 2×10.sup.−4 mN/m, and 1×10.sup.−4 mN/m.

[0077] Solubilization parameters: 2 mL of blockage removing agents having effective concentrations of 0.1%, 0.5%, 1.0%, and 2.0% respectively were placed in straight screw glass tubes. 2 mL of crude oil samples were added respectively. The lids were tightened up. The contents in the glass tubes were mixed evenly, and placed in a constant temperature air bath at 80° C. to stand for 7 days for equilibration. The crude oil solubilization parameters were calculated to be 28, 29, 33, and 35 respectively. The crude oil solubilization parameter was the mass of the crude oil solubilized by the unit mass of surfactant. In the experiment, due to the presence of the surfactant in the blockage removing agent system, the crude oil could be solubilized into the aqueous phase. By measuring the volume change of the crude oil phase before and after the experiment, the mass of the crude oil solubilized into the aqueous phase was obtained, and then the crude oil solubilization parameter was obtained by calculation.

[0078] Physical simulation experiment: The schematic diagram of the experimental apparatus is shown in FIG. 1. The core for the physical simulation experiment was firstly saturated with formation water, and then water in the core was displaced with crude oil until no water was driven out to obtain the saturated core for the physical simulation experiment. In the experiment, the oil in the saturated cores was firstly displaced with formation water until no crude oil was driven out, and the injection pressure and the core permeability data were recorded at this time; then 1PV of the blockage removing agent solutions having different concentrations were injected, and the cores were aged at the oil reservoir temperature for 4 days; finally, the oil in the cores was displaced with formation water until no crude oil was driven out; the injection pressure and the permeability were recorded. The water injection pressures of the oil-saturated cores before and after the injection of the blockage removing agent solutions were measured, and the reductions in the water injection pressures after injecting the blockage removing agent solutions were calculated. In case the effective concentrations of the blockage removing agents were 0.1%, 0.5%, 1.0%, and 2.0% respectively, the water injection pressure reduction proportions were 33%, 39%, 40%, and 43% respectively.

Example 2

[0079] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0080] A. lipopeptide: 30 g, commercially available from KANEKA CORPORATION JAPAN;

[0081] B. C.sub.16H.sub.33O(PO).sub.22(EO).sub.36CH.sub.2COOK: 10 g, self-manufactured;

[0082] C. propylene glycol: 10 g;

[0083] D. the balance of water.

[0084] The preparation process was identical to that in Example 1

[0085] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 8×10.sup.−4 mN/m, 5×10.sup.−4 mN/m, 3×10.sup.−4 mN/m, and 2×10.sup.−4 mN/m respectively; the crude oil solubilization parameters were 22, 25, 30, and 33 respectively; and the water injection pressure reduction ratios were 31%, 33%, 36%, and 42% respectively.

Example 3

[0086] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0087] A. lipopeptide: 30 g, commercially available from KANEKA CORPORATION JAPAN;

[0088] B. C.sub.22H.sub.45O(PO).sub.30(EO).sub.60C.sub.2H.sub.4COONH.sub.4: 10 g, self-manufactured;

[0089] C. glycerol: 10 g;

[0090] D. the balance of water.

[0091] The preparation process was identical to that in Example 1

[0092] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 9×10.sup.−4 mN/m, 6×10.sup.−4 mN/m, 4×10.sup.−4 mN/m, and 2×10.sup.−4 mN/m respectively; the crude oil solubilization parameters were 24, 26, 30, and 31 respectively; and the water injection pressure reduction ratios were 30%, 30%, 32%, and 33% respectively.

Example 4

[0093] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0094] A. lipopeptide: 30 g, commercially available from KANEKA CORPORATION JAPAN;

[0095] B. C.sub.12H.sub.25O(PO).sub.6(EO).sub.18C.sub.5H.sub.10SO.sub.4Na: 10 g, self-manufactured;

[0096] C. ethylene glycol: 1 g;

[0097] D. the balance of water.

[0098] The preparation process was identical to that in Example 1

[0099] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 9×10.sup.−4 mN/m, 7×10.sup.−4 mN/m, 5×10.sup.−4 mN/m, and 3 ×10.sup.−4 mN/m respectively; the crude oil solubilization parameters were 20, 22, 27, and 30 respectively; and the water injection pressure reduction ratios were 30%, 33%, 36%, and 36% respectively.

Example 5

[0100] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0101] A. lipopeptide: 30 g, commercially available from KANEKA CORPORATION JAPAN;

[0102] B. C.sub.12H.sub.25O(PO).sub.1(EO).sub.28CH.sub.2SO.sub.3Na: 10 g, self-manufactured;

[0103] C. ethylene glycol: 30 g;

[0104] D. the balance of water.

[0105] The preparation process was identical to that in Example 1

[0106] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 9×10.sup.−4 mN/m, 6×10.sup.−4 mN/m, 4×10.sup.−4 mN/m, and 3 ×10.sup.−4 mN/m respectively; the crude oil solubilization parameters were 24, 25, 29, and 30 respectively; and the water injection pressure reduction ratios were 31%, 32%, 35%, and 35% respectively.

Example 6

[0107] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0108] A. lipopeptide: 10 g, commercially available from KANEKA CORPORATION JAPAN;

[0109] B. C.sub.12H.sub.25O(PO).sub.16C.sub.10H.sub.20OONa: 10 g, self-manufactured;

[0110] C. ethylene glycol: 10 g;

[0111] D. the balance of water.

[0112] The preparation process was identical to that in Example 1

[0113] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 9×10.sup.−4 mN/m, 8×10.sup.−4 mN/m, 6×10.sup.−4 mN/m, and 6×10.sup.−4 mN/m respectively; the crude oil solubilization parameters were 20, 21, 25, and 26 respectively; and the water injection pressure reduction ratios were 30%, 30%, 31%, and 32% respectively.

Example 7

[0114] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0115] A. lipopeptide: 50 g, commercially available from KANEKA CORPORATION JAPAN;

[0116] B. C.sub.12H.sub.25O(EO).sub.22C.sub.3H.sub.6COONa: 10 g, self-manufactured;

[0117] C. ethylene glycol: 10 g;

[0118] D. the balance of water.

[0119] The preparation process was identical to that in Example 1

[0120] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 8×10.sup.−4 mN/m, 7×10.sup.−4 mN/m, 7×10.sup.−4 mN/m, and 6×10.sup.−4 mN/m respectively; the crude oil solubilization parameters were 26, 26, 29, and 30 respectively; and the water injection pressure reduction ratios were 30%, 31%, 33%, and 34% respectively.

Example 8

[0121] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0122] A. lipopeptide: 30 g, commercially available from KANEKA CORPORATION JAPAN;

[0123] B. C.sub.12H.sub.25O(PO).sub.8(EO).sub.16CH.sub.2COONa: 5 g, self-manufactured;

[0124] C. ethylene glycol: 10 g;

[0125] D. the balance of water.

[0126] The preparation process was identical to that in Example 1

[0127] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 8×10.sup.−4 mN/m, 6×10.sup.−4 mN/m, 2×10.sup.−4 mN/m, and 2×10.sup.−4 mN/m respectively; the crude oil solubilization parameters were 23, 25, 30, and 33 respectively; and the water injection pressure reduction ratios were 32%, 33%, 37%, and 40% respectively.

Example 9

[0128] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0129] A. lipopeptide: 30 g, commercially available from KANEKA CORPORATION JAPAN;

[0130] B. C.sub.12H.sub.25O(PO).sub.36(EO).sub.48CH.sub.2COONa: 20 g, self-manufactured;

[0131] C. ethylene glycol: 10 g;

[0132] D. the balance of water.

[0133] The preparation process was identical to that in Example 1

[0134] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 8×10.sup.−4 mN/m, 4×10.sup.−4 mN/m, 3 ×10.sup.−4 mN/m, and 2×10.sup.−4 mN/m respectively; the crude oil solubilization parameters were 25, 28, 33, and 34 respectively; and the water injection pressure reduction ratios were 34%, 36%, 38%, and 38% respectively.

Example 10

[0135] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0136] A. lipopeptide: 30 g, commercially available from KANEKA CORPORATION JAPAN;

[0137] B. C.sub.12H.sub.25(C.sub.6H.sub.4)O(PO).sub.12(EO).sub.24CH.sub.2COONa: 10 g, self-manufactured;

[0138] C. ethylene glycol: 10 g;

[0139] D. the balance of water.

[0140] The preparation process was identical to that in Example 1

[0141] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 6×10.sup.−4 mN/m, 3 ×10.sup.−4 mN/m, 1×10.sup.−4 mN/m, and 1×10.sup.−4 mN/m respectively; the crude oil solubilization parameters were 30, 33, 35, and 36 respectively; and the water injection pressure reduction ratios were 35%, 38%, 42%, and 45% respectively.

Example 11

[0142] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0143] A. lipopeptide: 30 g, commercially available from KANEKA CORPORATION JAPAN;

[0144] B. C.sub.12H.sub.25(PO).sub.12(EO).sub.24(C.sub.6H.sub.4)CH.sub.2COONa: 10 g, self-manufactured;

[0145] C. ethylene glycol: 10 g;

[0146] D. the balance of water.

[0147] The preparation process was identical to that in Example 1

[0148] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 8×10.sup.−4 mN/m, 3 ×10.sup.−4 mN/m, 2×10.sup.−4 mN/m, and 1×10.sup.−4 mN/m respectively; the crude oil solubilization parameters were 28, 31, 33, and 34 respectively; and the water injection pressure reduction ratios were 30%, 33%, 38%, and 39% respectively.

Example 12

[0149] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0150] A. rhamnolipid: 30 g, commercially available from Evonik Industries AG;

[0151] B. C.sub.12H.sub.25O(PO).sub.12(EO).sub.24CH.sub.2COONa: 10 g;

[0152] C. ethylene glycol: 10 g;

[0153] D. the balance of water.

[0154] The preparation process was identical to that in Example 1

[0155] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 9×10.sup.−4 mN/m, 6×10.sup.−4 mN/m, 4×10.sup.−4 mN/m, and 3 ×10.sup.−4 mN/m respectively; the crude oil solubilization parameters were 20, 21, 24, and 29 respectively; and the water injection pressure reduction ratios were 30%, 31%, 33%, and 36% respectively.

Example 13

[0156] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0157] A. trehalose lipid: 30 g, commercially available from Xi'an Brilliant Chemical Engineering Co. Ltd.;

[0158] B. C.sub.12H.sub.25O(PO).sub.12(EO).sub.24CH.sub.2COONa: 10 g;

[0159] C. ethylene glycol: 10 g;

[0160] D. the balance of water.

[0161] The preparation process was identical to that in Example 1

[0162] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 9×10.sup.−4 mN/m, 7×10.sup.−4 mN/m, 5×10.sup.−4 mN/m, and 5×10.sup.−4 mN/m respectively; the crude oil solubilization parameters were 20, 20, 24, and 30 respectively; and the water injection pressure reduction ratios were 30%, 30%, 34%, and 35% respectively.

Example 14

[0163] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0164] A. lipopeptide: 30 g, commercially available from KANEKA CORPORATION JAPAN;

[0165] B. C.sub.12H.sub.25O(PO).sub.12(EO).sub.24CH.sub.2COONa: 10 g, self-manufactured;

[0166] C. the balance of water.

[0167] The preparation process was identical to that in Example 1

[0168] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 4×10.sup.−3 mN/m, 1×10.sup.−3 mN/m, 8×10.sup.−4 mN/m, and 7×10.sup.−4 mN/m respectively; the crude oil solubilization parameters were 24, 25, 25, and 28 respectively; and the water injection pressure reduction ratios were 21%, 26%, 29%, and 30% respectively.

Comparative Example 1

[0169] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0170] A. lipopeptide: 40 g, commercially available from KANEKA CORPORATION JAPAN;

[0171] B. ethylene glycol: 10 g;

[0172] C. the balance of water.

[0173] The preparation process was identical to that in Example 1

[0174] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 9×10.sup.−2 mN/m, 6×10.sup.−2 mN/m, 4×10.sup.−2 mN/m, and 3 ×10.sup.−2 mN/m respectively; the crude oil solubilization parameters were 9, 12, 13, and 15 respectively; and the water injection pressure reduction ratios were 11%, 12%, 14%, and 15% respectively.

Comparative Example 2

[0175] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0176] A. C.sub.12H.sub.25O(PO).sub.12(EO).sub.24CH.sub.2COONa: 40 g, self-manufactured;

[0177] B. ethylene glycol: 10 g;

[0178] C. the balance of water.

[0179] The preparation process was identical to that in Example 1

[0180] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 5×10.sup.−2 mN/m, 2×10.sup.−2 mN/m, 9×10.sup.−3 mN/m, and 9×10.sup.−3 mN/m respectively; the crude oil solubilization parameters were 11, 11, 12, and 12 respectively; and the water injection pressure reduction ratios were 10%, 13%, 14%, and 14% respectively.

Comparative Example 3

[0181] According to the following weight percentages, 100 g of a blockage removing agent was prepared:

[0182] A. lipopeptide: 30 g, commercially available from KANEKA CORPORATION JAPAN;

[0183] B. dodecyl polyoxyethylene polyoxypropylene ether C.sub.12H.sub.25O(PO).sub.12(EO)24H: 5 g, self-manufactured;

[0184] C. sodium dodecylbenzene sulfonate: 5 g, commercially available from Shanghai Aladdin Biochemical Technology Co., Ltd;

[0185] D. ethylene glycol: 10 g;

[0186] E. the balance of water.

[0187] The preparation process was identical to that in Example 1

[0188] The effect evaluation method was identical to that in Example 1: the oil-water interfacial tensions of different concentrations of the blockage removing agents and the crude oil were 1×10.sup.−2 mN/m, 1×10.sup.−2 mN/m, 9×10.sup.−3 mN/m, and 8×10.sup.−3 mN/m respectively; the crude oil solubilization parameters were 13, 15, 16, and 16 respectively; and the water injection pressure reduction ratios were 13%, 15%, 17%, and 18% respectively.

[0189] It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary, and various other substitutions, changes, and improvements may be made within the scope of the present invention. Therefore, the present invention is not limited to the above-described embodiments, but only by the claims.