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Patent Analysis of

Drilling fluid additive composition, and oil-based drilling fluid and use thereof

Updated Time 12 June 2019

Patent Registration Data

Publication Number

US10000684

Application Number

US15/466066

Application Date

22 March 2017

Publication Date

19 June 2018

Current Assignee

CHINA UNIVERSITY OF PETROLEUM (BEIJING)

Original Assignee (Applicant)

CHINA UNIVERSITY OF PETROLEUM (BEIJING)

International Classification

C09K8/32,C07C209/68

Cooperative Classification

C09K8/32,C07C209/68,C09K2208/34,C09K8/03,C10M141/06

Inventor

JIANG, GUANCHENG,PENG, SHUANGLEI,HE, YINBO,GAO, DELI,YANG, LILI,LIU, FAN,LI, XINLIANG,DENG, ZHENGQIANG,MA, GUANGCHANG,ZHAO, LI,SUN, HAIFANG,HAN, LIEXIANG

Patent Images

This patent contains figures and images illustrating the invention and its embodiment.

US10000684 Drilling fluid additive composition, 1 US10000684 Drilling fluid additive composition, 2 US10000684 Drilling fluid additive composition, 3
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Abstract

The present invention relates to the well drilling field in petroleum industry, in particular to a drilling fluid additive composition that contains a lubricant, an emulsifier, and a rheological modifier, wherein, the lubricant contains: graphite oxide and a biquaternary ammonium salt compound in which the cation part is represented by formula (1); the emulsifier is one or more of compounds represented by formula (I); the rheological modifier is a dimer acid-organic amine copolymer comprising structural units from dimer acid, structural units from alkylamine and structural units from arylamine. The present invention further provides an oil-based drilling fluid containing the composition and a use thereof. The oil-based drilling fluid containing the composition provided in the present invention obtains a lower lubrication coefficient, and favorable rheological property and thermostability, and is suitable for use in operation at a high temperature

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Claims

1. A drilling fluid additive composition comprising a lubricant, an emulsifier, and a rheological modifier, wherein: a) the lubricant comprises graphite oxide and a biquaternary ammonium salt compound, wherein the cation of the biquaternary ammonium salt compound is represented by formula (1): wherein the biquaternary ammonium salt compound adheres to the surface of the graphite oxide and also adheres to the graphite oxide between layers of the graphite oxide; wherein part of the biquaternary ammonium salt compound is linked to the graphite oxide in the form of a modifying group, wherein the cation of the modifying group is represented by formula (2): wherein each R1 group is independently selected from H, hydroxyl, halogen, C1-C6 alkyl, C1-C6 alkoxy, and C1-C6 hydroxyalkyl; each R2 group is independently selected from H and C1-C6 alkyl; and each R3 group is independently selected from n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, hendecyl, and dodecyl; wherein a weight ratio of the graphite oxide to the biquaternary ammonium salt compound is 1:48-250 b) the emulsifier is one or more of compounds represented by formula (I); wherein each of the two R1 groups is independently selected from C14-C30 alkyl optionally substituted by group Y and C14-C30 unsaturated alkyl optionally substituted by group Y, and the group Y is independently selected from the following: n is 1-8; wherein each X′ is independently selected from H and —C(O)—R2, and at least one X′ is —C(O)—R2, R2 is selected from carboxyl, C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkyl substituted by carboxyl, C3-C8 cycloalkyl substituted by carboxyl, C3-C8 cycloalkyl substituted by carboxyl and C1-C4 alkyl, C2-C6 unsaturated alkyl, C3-C8 unsaturated cycloalkyl, C2-C6 unsaturated alkyl substituted by carboxyl, and C3-C8 unsaturated cycloalkyl substituted by carboxyl and C1-C4 alkyl; c) the rheological modifier is a dimer acid-organic amine copolymer comprising structural units from dimer acid, structural units from an alkylamine, and structural units from an arylamine, wherein the dimer acid is a dimer of oleic acid and linoleic acid, the alkylamine is one or more of C10-C20 alkyl primary amines, and the arylamine is one or more of aniline and aniline substituted by C1-C3 alkyl at one or more sites on benzene ring; and wherein a weight ratio of the lubricant to the emulsifier to the rheological modifier is 100:300-800:50-200.

2. The composition according to claim 1, wherein the weight ratio of the lubricant to the emulsifier to the rheological modifier is 100:300-500:50-100.

3. The composition according to claim 1, wherein, in the lubricant, each R1 group is independently selected from H, hydroxyl, halogen, C1-C4 alkyl, C1-C4 alkoxy, and C1-C4 hydroxyalkyl.

4. The composition according to claim 3, wherein, in the lubricant, each R1 group is independently selected from H, hydroxyl, methyl, ethyl, methoxy, ethoxy, hydroxymethyl, and hydroxyethyl; each R2 group is independently selected from H, methyl, ethyl, n-propyl, and n-butyl.

5. The composition according to claim 3, wherein the cation of the biquaternary ammonium salt compound is selected from one or more of the following:

6. The composition according to claim 1, wherein the anion of the biquaternary ammonium salt compound is selected from one or more of Cl, Br, and I.

7. The composition according to claim 1, wherein the modifying group formed by the biquaternary ammonium salt compound is linked to the outer edge of the graphite oxide.

8. The composition according to claim 1, wherein the weight ratio of the graphite oxide to the biquaternary ammonium salt compound is 1:90-200.

9. The composition according to claim 1, wherein, in the emulsifier, each of the two R1 groups is independently selected from C14-C20 alkyl optionally substituted by group Y and C14-C20 unsaturated alkyl optionally substituted by group Y; n is 1-6; and R2 is selected from carboxyl, C1-C4 alkyl, C4-C6 cycloalkyl, C1-C4 alkyl substituted by carboxyl, C4-C6 cycloalkyl substituted by carboxyl, C4-C6 cycloalkyl substituted by carboxyl and methyl, C2-C4 unsaturated alkyl, C4-C6 unsaturated cycloalkyl, C2-C4 unsaturated alkyl substituted by carboxyl, and C4-C7 unsaturated cycloalkyl substituted by carboxyl and methyl.

10. The composition according to claim 9, wherein each of the two R1 groups is independently selected from C15-C18 alkyl optionally substituted by group Y and C15-C18 unsaturated alkyl optionally substituted by group Y; and n is 1-4.

11. The composition according to claim 1, wherein, in the rheological modifier, the alkylamine is one or more of dodecyl primary amine, tridecyl primary amine, tetradecyl primary amine, pentadecyl primary amine, hexadecyl primary amine, heptadecyl primary amine, and octodecyl primary amine; and the arylamine is one or more of aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-propylaniline, 3-propylaniline and 4-propyl aniline.

12. The composition according to claim 11, wherein a molar ratio of the structural units from the dimer acid, to the structural units from the alkylamine to the structural units from the arylamine is 1:0.3-1:0.2-1; wherein the dimer acid-organic amine copolymer has a weight-average molecular weight of 2,200-9,000 g/mol; and wherein the dimer acid-organic amine copolymer has an absolute viscosity of 20,000-150,000 cp.

13. The composition according to claim 12, wherein the molar ratio of the structural units from the dimer acid to the structural units from the alkylamine to the structural units from the arylamine is 1:0.3-0.8:0.2-0.7; wherein the weight-average molecular weight of the dimer acid-organic amine copolymer is 4,000-9,000 g/mol; and wherein the absolute viscosity of the dimer acid-organic amine copolymer is 100,000-150,000 cp.

14. An oil-based drilling fluid containing the composition according to claim 1.

15. The drilling fluid according to claim 14, wherein based on 100 part by weight of oil phase in the drilling fluid, the content of the composition is 2-10 part by weight.

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Claim Tree

  • 1
    1. A drilling fluid additive composition comprising a lubricant, an emulsifier, and a rheological modifier, wherein:
    • a) the lubricant comprises graphite oxide and a biquaternary ammonium salt compound, wherein the cation of the biquaternary ammonium salt compound is represented by formula (1): wherein the biquaternary ammonium salt compound adheres to the surface of the graphite oxide and also adheres to the graphite oxide between layers of the graphite oxide; wherein part of the biquaternary ammonium salt compound is linked to the graphite oxide in the form of a modifying group, wherein the cation of the modifying group is represented by formula (2): wherein each R1 group is independently selected from H, hydroxyl, halogen, C1-C6 alkyl, C1-C6 alkoxy, and C1-C6 hydroxyalkyl; each R2 group is independently selected from H and C1-C6 alkyl; and each R3 group is independently selected from n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, hendecyl, and dodecyl; wherein a weight ratio of the graphite oxide to the biquaternary ammonium salt compound is 1:48-250
    • b) the emulsifier is one or more of compounds represented by formula (I); wherein each of the two R1 groups is independently selected from C14-C30 alkyl optionally substituted by group Y and C14-C30 unsaturated alkyl optionally substituted by group Y, and the group Y is independently selected from the following: n is 1-8; wherein each X′ is independently selected from H and —C(O)—R2, and at least one X′ is —C(O)—R2, R2 is selected from carboxyl, C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkyl substituted by carboxyl, C3-C8 cycloalkyl substituted by carboxyl, C3-C8 cycloalkyl substituted by carboxyl and C1-C4 alkyl, C2-C6 unsaturated alkyl, C3-C8 unsaturated cycloalkyl, C2-C6 unsaturated alkyl substituted by carboxyl, and C3-C8 unsaturated cycloalkyl substituted by carboxyl and C1-C4 alkyl;
    • c) the rheological modifier is a dimer acid-organic amine copolymer comprising structural units from dimer acid, structural units from an alkylamine, and structural units from an arylamine, wherein the dimer acid is a dimer of oleic acid and linoleic acid, the alkylamine is one or more of C10-C20 alkyl primary amines, and the arylamine is one or more of aniline and aniline substituted by C1-C3 alkyl at one or more sites on benzene ring; and wherein a weight ratio of the lubricant to the emulsifier to the rheological modifier is 100:300-800:50-200.
    • 2. The composition according to claim 1, wherein
      • the weight ratio of the lubricant to the emulsifier to the rheological modifier is 100:300-500:50-100.
    • 3. The composition according to claim 1, wherein
      • , in the lubricant, each R1 group is independently selected from H, hydroxyl, halogen, C1-C4 alkyl, C1-C4 alkoxy, and C1-C4 hydroxyalkyl.
    • 6. The composition according to claim 1, wherein
      • the anion of the biquaternary ammonium salt compound is selected from one or more of Cl, Br, and I.
    • 7. The composition according to claim 1, wherein
      • the modifying group formed by the biquaternary ammonium salt compound is linked to the outer edge of the graphite oxide.
    • 8. The composition according to claim 1, wherein
      • the weight ratio of the graphite oxide to the biquaternary ammonium salt compound is 1:90-200.
    • 9. The composition according to claim 1, wherein
      • , in the emulsifier, each of the two R1 groups is independently selected from C14-C20 alkyl optionally substituted by group Y and C14-C20 unsaturated alkyl optionally substituted by group Y; n is 1-6; and R2 is selected from carboxyl, C1-C4 alkyl, C4-C6 cycloalkyl, C1-C4 alkyl substituted by carboxyl, C4-C6 cycloalkyl substituted by carboxyl, C4-C6 cycloalkyl substituted by carboxyl and methyl, C2-C4 unsaturated alkyl, C4-C6 unsaturated cycloalkyl, C2-C4 unsaturated alkyl substituted by carboxyl, and C4-C7 unsaturated cycloalkyl substituted by carboxyl and methyl.
    • 11. The composition according to claim 1, wherein
      • , in the rheological modifier, the alkylamine is one or more of dodecyl primary amine, tridecyl primary amine, tetradecyl primary amine, pentadecyl primary amine, hexadecyl primary amine, heptadecyl primary amine, and octodecyl primary amine; and the arylamine is one or more of aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-propylaniline, 3-propylaniline and 4-propyl aniline.
  • 14
    14. An oil-based drilling fluid containing
    • the composition according to claim 1.
    • 15. The drilling fluid according to claim 14, wherein
      • based on 100 part by weight of oil phase in the drilling fluid, the content of the composition is 2-10 part by weight.
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Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to Chinese Application No. 201610381991.1, filed on Jun. 1, 2016, entitled “Drilling Fluid Additive Composition and Use thereof, and Oil-Based Drilling Fluid and Use thereof”, which is specifically and entirely incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to the well drilling field in petroleum industry, in particular to a drilling fluid additive composition, a use of the drilling fluid additive composition, an oil-based drilling fluid, and a use of the oil-based drilling fluid.

BACKGROUND OF THE INVENTION

In a well drilling process, the rotating drilling stem inevitably comes into contact with the casing or rock well wall and thereby produces friction force, resulting in increased torque, decreased drilling rate, and abrasion of the drilling tool. If the friction force is too high, complex downhole conditions, such as difficulty in tripping operation, caving, or jamming of drilling tool, etc. may occur. Hence, often a lubricant has to be added into the drilling fluid to improve the lubricating property of the system during well drilling, reduce frictional resistance in the drilling process, prevent the occurrence of complex downhole conditions (e.g., jamming of drilling tool), and ensure safe and quick well drilling.

Presently, there are great varieties of lubricants for water-based drilling fluids, and these lubricants are widely applied, while researches on lubricants for oil-based drilling fluids and products of such lubricants are rare, owing to the excellent self-lubricating property of oil-based drilling fluids. However, as the drilling depth and difficulties increase, especially as more and more extra-deep wells, extended reach wells, horizontal wells and cluster wells are drilled, even oil-based drilling fluids can't solve the problem of high torque and severe wear in the drilling process; consequently, downhole accidents, such as caving and jamming of drilling tool, etc. occur frequently.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a drilling fluid additive composition applicable to oil-based drilling fluids, a use of the drilling fluid additive composition, an oil-based drilling fluid, and a use of the oil-based drilling fluid.

To attain the object described above, the present invention provides a drilling fluid additive composition comprising a lubricant, an emulsifier, and a rheological modifier, wherein the lubricant contains: graphite oxide and a biquaternary ammonium salt compound of which the cation part is represented by formula (1):

wherein, each R1 group is independently selected from H, hydroxyl, halogen, C1-C6 alkyl, C1-C6 alkoxy, and C1-C6 hydroxyalkyl; each R2 group is independently selected from H and C1-C6 alkyl; each R3 group is independently selected from H, C1-C20 alkyl, and C1-C20 hydroxyalkyl;

the emulsifier is one or more of compounds represented by formula (I):

in the formula (I), each of the two R1 groups is independently selected from C14-C30 alkyl optionally substituted by group Y and C14-C30 unsaturated alkyl with carbon-carbon double bonds optionally substituted by group Y, and the group Y is independently selected from the groups represented by the following formulae:

n is an integer in a range of 1-8;

n X′-es are independently selected from H and —C(O)—R2, and at least one X′ is —C(O)—R2, R2 is selected from carboxyl, C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkyl substituted by carboxyl, C3-C8 cycloalkyl substituted by carboxyl, C3-C8 cycloalkyl substituted by carboxyl and C1-C4 alkyl, C2-C6 unsaturated alkyl with a carbon-carbon double bond, C3-C8 unsaturated cycloalkyl with a carbon-carbon double bond, C2-C6 unsaturated alkyl with a carbon-carbon double bond substituted by carboxyl, and C3-C8 unsaturated cycloalkyl with a carbon-carbon double bond substituted by carboxyl and C1-C4 alkyl;

the rheological modifier is a dimer acid-organic amine copolymer comprising structural units from dimer acid, structural units from alkylamine and structural units from arylamine, of which the dimer acid is a dimer of oleic acid and linoleic acid, the alkylamine is one or more of C10-C20 alkyl primary amines, and the arylamine is one or more of aniline and aniline substituted by C1-C3 alkyl at one or more sites on benzene ring.

The present invention further provides a use of the composition as a drilling fluid additive in oil and gas drilling.

The present invention further provides an oil-based drilling fluid containing the composition described above.

The present invention further provides a use of the oil-based drilling fluid in oil and gas drilling.

The composition provided in the present invention contain an emulsifier, a rheological modifier, and a lubricant that can be comprehended as a nano-hybrid material, which can work with each other synergistically to improve the properties of drilling fluids. Thus, oil-based drilling fluids that contain the composition provided in the present invention have lower lubrication coefficient, favorable rheological property and excellent thermostability, and are suitable for use in operation at a high temperature.

Other features and advantages of the present invention will be further detailed in the embodiments hereunder.

BRIEF DESCRIPTION OF DRAWINGS

The accompanying drawings are provided here to facilitate further understanding on the present invention, and constitute a part of this document. They are used in conjunction with the following embodiments to explain the present invention, but shall not be comprehended as constituting any limitation to the present invention. In the figures:

FIG. 1 shows a 500×SEM image of the graphite oxide obtained in a preparation example in the present invention;

FIG. 2 shows a 10,000×SEM image of the graphite oxide obtained in a preparation example in the present invention;

FIG. 3 is a 250×SEM image of the lubricant obtained in example 1 of the present invention;

FIG. 4 is a 10,000×SEM image of the lubricant obtained in example 1 of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Hereunder some embodiments of the present invention will be detailed. It should be appreciated that the embodiments described here are only provided to describe and explain the present invention, but shall not be deemed as constituting any limitation to the present invention.

The ends points and any value in the ranges disclosed in the present invention are not limited to the exact ranges or values. Instead, those ranges or values shall be comprehended as encompassing values that are close to those ranges or values. For numeric ranges, the end points of the ranges, the end points of the ranges and the discrete point values, and the discrete point values can be combined to obtain one or more new numeric ranges, which shall be deemed as having been disclosed specifically in this document.

The present invention provides a drilling fluid additive composition comprising a lubricant, an emulsifier, and a rheological modifier, wherein the lubricant contains: graphite oxide and a biquaternary ammonium salt compound of which the cation part is represented by formula (1):

wherein, each R1 group is independently selected from H, hydroxyl, halogen, C1-C6 alkyl, C1-C6 alkoxy, and C1-C6 hydroxyalkyl; each R2 group is independently selected from H and C1-C6 alkyl; each R3 group is independently selected from H, C1-C20 alkyl, and C1-C20 hydroxyalkyl;

the emulsifier is one or more of compounds represented by formula (I):

in the formula (I), each of the two R1 groups is independently selected from C14-C30 alkyl optionally substituted by group Y and C14-C30 unsaturated alkyl with carbon-carbon double bonds optionally substituted by group Y, and the group Y is independently selected from the groups represented by the following formulae:

n is an integer in a range of 1-8;

n X′-es are independently selected from H and —C(O)—R2, and at least one X′ is —C(O)—R2, R2 is selected from carboxyl, C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkyl substituted by carboxyl, C3-C8 cycloalkyl substituted by carboxyl, C3-C8 cycloalkyl substituted by carboxyl and C1-C4 alkyl, C2-C6 unsaturated alkyl with a carbon-carbon double bond, C3-C8 unsaturated cycloalkyl with a carbon-carbon double bond, C2-C6 unsaturated alkyl with a carbon-carbon double bond substituted by carboxyl, and C3-C8 unsaturated cycloalkyl with a carbon-carbon double bond substituted by carboxyl and C1-C4 alkyl;

the rheological modifier is a dimer acid-organic amine copolymer comprising structural units from dimer acid, structural units from alkylamine and structural units from arylamine, of which the dimer acid is a dimer of oleic acid and linoleic acid, the alkylamine is one or more of C10-C20 alkyl primary amines, and the arylamine is one or more of aniline and aniline substituted by C1-C3 alkyl at one or more sites on benzene ring.

In the present invention, for example, the halogen comprises: F, Cl, Br, and I, etc.

For example, the C1-C6 alkyl may comprise: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and n-hexyl, etc. For example, the C1-C6 alkoxy may comprise: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, and n-hexyloxy, etc. For example, the C1-C6 hydroxyalkyl may comprise: hydroxymethyl, hydroxyethyl, hydroxylpropyl, hydroxylbutyl, hydroxylamyl, and hydroxylhexyl, etc. For example, the C1-C20 alkyl may comprise: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, hendecyl (i.e., n-hendecyl), dodecyl (i.e., n-dodecyl), tridecyl (i.e., n-tridecyl), tetradecyl (i.e., n-tetradecyl), pentadecyl (i.e., n-pentadecyl), hexadecyl (i.e., n-hexadecyl), heptadecyl (i.e., n-heptadecyl), octodecyl (i.e., n-octodecyl), nonadecyl (i.e., n-nonadecyl), eicosyl (i.e., n-eicosyl), etc. For example, the C1-C20 hydroxyalkyl may comprise: hydroxymethyl, hydroxyethyl, hydroxylpropyl, hydroxylbutyl, hydroxylamyl, hydroxylhexyl, hydroxylheptyl, hydroxyloctyl, hydroxylnonyl, hydroxyldecyl, hydroxylhendecyl, hydroxyldodecyl, hydroxyltridecyl, hydroxyltetradecyl, hydroxylpentadecyl, hydroxylhexadecyl, hydroxylheptadecyl, hydroxyloctodecyl, hydroxylnonadecyl, and hydroxyleicosyl, etc.

According to the present invention, to obtain a composition that has better lubricating property, lower impact on the rheological property of drilling fluid, and higher thermostability, preferably, in the formula (1), each R1 group is independently selected from H, hydroxyl, halogen, C1-C4 alkyl, C1-C4 alkoxy, and C1-C4 hydroxyalkyl; each R2 group is independently selected from H and C1-C4 alkyl; each R3 group is independently selected from H, C1-C15 alkyl, and C1-C15 hydroxyalkyl.

More preferably, each R1 group is independently selected from H, hydroxyl, methyl, ethyl, methoxy, ethyoxy, hydroxymethyl, and hydroxyethyl; each R2 group is independently selected from H, methyl, ethyl, n-propyl, and n-butyl; each R3 group is independently selected from H, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, hendecyl, and dodecyl.

Further preferably, each R1 group is independently selected from H, methyl and ethyl; each R2 group is independently selected from H, methyl, ethyl, n-propyl, and n-butyl; each R3 group is independently selected from ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

Optimally, each R1 group is H; each R2 group is independently selected from methyl and ethyl; each R3 group is independently selected from ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

In a preferred embodiment of the present invention, the cation part of the biquaternary ammonium salt compound is selected from one or more of cations represented by the following formulae:

There is no particular restriction on the anion part of the biquaternary ammonium salt compound in the present invention; namely, the anion may be any conventional anion in the art; however, preferably, the anion part of the biquaternary ammonium salt compound is selected from one or more of Cl, Br, and I, and more preferably is Cl.

In a preferred embodiment of the present invention, the biquaternary ammonium salt compound is selected from one or more of compounds represented by the following formulae:

According to the present invention, the graphite oxide and the biquaternary ammonium salt compound contained in the lubricant may exist at positions in any form in relation to each other; namely, they can exist in a separated from or in any hybrid form; however, to obtain a lubricant that has a better lubricating effect, preferably the biquaternary ammonium salt compound adheres to the surface of the graphite oxide; more preferably, the biquaternary ammonium salt compound also adheres to the graphite oxide between layers, so that the biquaternary ammonium salt compound and the graphite oxide form an organic-inorganic hybrid material, and the lubricant may be deemed as a nano-hybrid lubricant. In such a case, the surface of inorganic nanometer graphite oxide is wrapped by a layer of organic biquaternary ammonium salt, i.e., the biquaternary ammonium salt compound is distributed on the surface and between the layers of the graphite oxide; thus, the long alkyl chain provided by the biquaternary ammonium salt compound is highly compatible with oil, and thereby the obtained lubricant can be well dispersed in the oil-based drilling fluid, and the biquaternary ammonium salt part that has positive charge on the biquaternary ammonium salt compound can be well adsorbed to the drilling stem or well wall; the graphite oxide may have inter-layer gliding under very low shearing stress and thereby attain an excellent lubricating effect owing to its natural laminar structure; in addition, the graphite oxide may fill up the uneven surface of drilling stem or well wall, so that the contact surface is integral and smooth. Therefore, by virtue of the combined action of the organic part and inorganic part of the lubricant provided in the present invention, the lubricant can greatly decrease the friction coefficient (equivalent to lubrication coefficient) of oil-based drilling fluid, reduce complex downhole conditions such as abrasion of drilling tool, and jamming of drilling tool, etc., and ensure safe and quick well drilling.

In a particularly preferred embodiment of the present invention, the biquaternary ammonium salt compound part is linked with the graphite oxide in the form of a modifying group, of which the cation part is represented by formula (2):

The groups in the formula (2) are groups as defined above. It is seen that the modifying group is linked to the graphite oxide via the link with O indicated by a dotted line in the middle.

More preferably, the modifying group formed by the biquaternary ammonium salt compound is linked to the outer edge of the graphite oxide. The main reason is that the outer edge of graphite oxide has more aggregated carboxyl groups and hydroxyl groups, which are suitable to react with hydroxyl in the biquaternary ammonium salt compound to obtain graphite oxide linked with a modifying group for the cation represented by the formula (2).

According to the present invention, the contents of the graphite oxide and the biquaternary ammonium salt compound may vary within wide ranges; however, to give a better play to the synergetic effect between the graphite oxide and the biquaternary ammonium salt compound, preferably the weight ratio of the graphite oxide to the biquaternary ammonium salt compound is 1:30-300, more preferably is 1:40-280, even more preferably is 1:48-250, still more preferably is 1:90-200, and may be 1:180, for example.

According to the present invention, the graphite oxide can be prepared with a conventional method in the art. Preferably, the method for preparation of the graphite oxide comprises:

(a) subjecting graphite, potassium permanganate, and concentrated sulfuric acid to have a first oxidation reaction;

(b) subjecting the product of the first oxidation reaction to have a second oxidation reaction with hydrogen peroxide.

Wherein, in the step (a), the weight ratio of the graphite, the potassium permanganate and the concentrated sulfuric acid calculated by H2SO4 may be 100:250-300:400-450, for example. The graphite may be natural crystalline flake graphite that is available commercially. The concentration of the concentrated sulfuric acid may be 98 wt. % or higher, for example. Preferably, the conditions of the first oxidation reaction include: temperature of 40-60° C., time of 10-15 h. To control the first oxidation reaction in a better way, in the step (a), the graphite is mixed with the potassium permanganate before the first oxidation reaction is commenced, and then concentrated sulfuric acid is introduced to have the first oxidation reaction.

Wherein, in the step (b), preferably the weight ratio of the graphite to the hydrogen peroxide is 100:10-100. The hydrogen peroxide is provided in a form of water solution such as an aqueous hydrogen peroxide solution at 0.1-1 wt. % concentration may be used. The reaction temperature of the second oxidation reaction is −5° C. to 5° C., and the reaction process is quick, almost happens instantaneously, and the color of the suspension liquid changes from greyish green to golden yellow.

The graphite oxide can be obtained through the above-mentioned process. To extract the obtained graphite oxide, the process may further comprise: separating the product of the second oxidation reaction by solid-liquid separation (e.g., by filtering), washing the solid phase, and drying it (e.g., drying for 8-16 h at 80-100° C.).

According to the present invention, the contents of the graphite oxide and the biquaternary ammonium salt compound may vary within wide ranges; however, to give a better play to the synergetic effect between the graphite oxide and the biquaternary ammonium salt compound, preferably the weight ratio of the graphite oxide to the biquaternary ammonium salt compound is 1:30-300, more preferably is 1:40-280, even more preferably is 1:48-250, still more preferably is 1:90-200, and may be 1:180, for example.

The lubricant may be prepared with a variety of methods. Preferably, the method for preparation of the lubricant comprises: in the presence of an acid, subjecting one or more of the amine compounds represented by formula (3), one or more of epoxy compounds represented by formula (4) and the graphite oxide to have a contact reaction in a solvent, wherein:

where, each R1 group is independently selected from H, hydroxyl, halogen, C1-C6 alkyl, C1-C6 alkoxy, and C1-C6 hydroxyalkyl; each R2 group is independently selected from H and C1-C6 alkyl; R3 group is selected from H, C1-C20 alkyl, and C1-C20 hydroxyalkyl; X is halogen, preferably is Cl or Br.

According to the present invention, the groups in the compounds represented by formulae (3) and (4) may be selected as described above, and will not be detailed any more here.

Wherein, in a preferred embodiment of the present invention, the amine compound represented by the formula (3) is selected from one or more of N,N-dimethyl laurylamine, N,N-dimethyl tridecylamine, N,N-dimethyl tetradecylamine, N,N-dimethyl pentadecylamine, N,N-dimethyl hexadecylamine, N,N-dimethyl heptadecylamine, and N,N-dimethyl octadecylamine; the epoxy compound represented by formula (4) is epoxy chloropropane.

According to the present invention, the amine compound represented by formula (3) and the epoxy compound represented by formula (4) have a contact reaction with graphite oxide, so that the biquaternary ammonium salt compound described above is obtained through the reaction between the amine compound represented by formula (3) and the epoxy compound represented by formula (4); whereas, in the presence of graphite oxide, the graphite oxide may react with a part of the biquaternary ammonium salt compound to obtain graphite oxide that is partially linked with the modifying group provided by the biquaternary ammonium salt compound (see the groups shown in the above formula (2)); especially, the modifying group is linked to the outer edge of graphite oxide; more importantly, the biquaternary ammonium salt compound may be distributed between the layers of graphite oxide more easily, because the amine compound represented by formula (3) and the epoxy compound represented by formula (4), which are raw materials may be distributed between the layers of the graphite oxide in advance, so that reaction happens directly between the layers and thereby the biquaternary ammonium salt compound is obtained therein; thus, the biquaternary ammonium salt compound and the graphite oxide are dispersed more evenly. Thus, a nano-hybrid material is formed, and the obtained lubricant may be deemed as a nano-hybrid lubricant, which has outstanding lubricating property and heat-resistance property, and has lower impact on the rheological property of oil-based drilling fluid.

Wherein, the method for preparation of the graphite oxide has been described above, and will not be further detailed here; if applicable, the method for preparation of the lubricant may be deemed as including a preparation step of the graphite oxide.

According to the present invention, the dosage of the amine compound represented by formula (3) and the epoxy compound represented by formula (4) may vary within wide ranges; however, preferably, the molar ratio of the amine compound represented by formula (3) to the epoxy compound represented by formula (4) is 1.5-5:1, more preferably is 2-3:1.

Wherein, the dosage of the graphite oxide may vary within a wide range; however, to obtain a lubricant in which the graphite oxide and the biquaternary ammonium salt compound have a better synergistic effect between them, preferably, the weight ratio of the amount of the graphite oxide to the total amount of the amine compound represented by formula (3) and the epoxy compound represented by formula (4) is 1:30-350, more preferably is 1:40-310, even more preferably is 1:45-300, still more preferably is 1:65-280, and may be 1:100-250, for example.

According to the present invention, the acid not only can be used as a catalyst for catalyzing the contact reaction between the amine compound represented by formula (3) and the epoxy compound represented by formula (4), but also can provide anions to the obtained biquaternary ammonium salt compound. To that end, the acid may be selected properly according to the required anions. Preferably, the acid is one or more of hydrochloric acid, hydrobromic acid, and hydroiodic acid, and more preferably is hydrochloric acid. For example, hydrochloric acid at 35 wt. % or higher concentration, especially concentrated hydrochloric acid at 37 wt. % or higher concentration, may be used. There is no particular restriction on the dosage of the acid. For example, the molar ratio of the amine compound represented by formula (3) to the acid may be 0.5-4:1, and preferably is 1-3:1.

According to the present invention, the solvent may be any conventional solvent in the art; preferably, the solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-hexane, liquid paraffin, and methyl benzene. Wherein, there is no particular restriction on the amount of the solvent, as long as the amount of the solvent is enough to disperse the raw materials and promote the contact reaction. Preferably, the weight ratio of the graphite oxide to the solvent is 1:50-800, more preferably is 1:100-600, and even more preferably is 1:200-500.

According to the present invention, preferably, the conditions of the contact reaction include: temperature of 60-110° C. (preferably 80-100° C.) and time of 12-24 h (preferably 20-24 h). The above-mentioned substances are mixed (e.g., mixed by ultrasonic mixing for 30-100 min.) before the contact reaction is commenced, in order to make the reaction more complete and make the graphite oxide form a nanometer laminar structure.

According to the present invention, to extract the lubricant from the product of the contact reaction, the method may further comprise: removing the solvent from the product of the contact reaction (e.g., removing by reduced pressure distillation), and then drying, so as to obtain the lubricant.

The emulsifier is one or more of compounds represented by formula (I):

in the formula (I), each of the two R1 groups is independently selected from C14-C30 alkyl optionally substituted by group Y and C14-C30 unsaturated alkyl with carbon-carbon double bonds optionally substituted by group Y, and the group Y is independently selected from the groups represented by the following formulae:

n is an integer in a range of 1-8; n X′-es are independently selected from H and —C(O)—R2, and at least one X′ is —C(O)—R2, R2 is selected from carboxyl, C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 alkyl substituted by carboxyl, C3-C8 cycloalkyl substituted by carboxyl, C3-C8 cycloalkyl substituted by carboxyl and C1-C4 alkyl, C2-C6 unsaturated alkyl with a carbon-carbon double bond, C3-C8 unsaturated cycloalkyl with a carbon-carbon double bond, C2-C6 unsaturated alkyl with a carbon-carbon double bond substituted by carboxyl, and C3-C8 unsaturated cycloalkyl with a carbon-carbon double bond substituted by carboxyl and C1-C4 alkyl.

According to the present invention, the emulsifier is one or more of compounds represented by the formula (I). The compounds represented by formula represented by the formula (I) are compounds with a comb-like structure containing a long saturated and/or unsaturated alkyl chains at two ends and short alkyl chains in the middle. Through increasing membrane strength of emulsification interface and with the help of the the rheological modifier and the lubricant obtained in the present invention, such compounds with a comb-like structure can stabilize drilling fluid and make the drilling fluid have appropriate gel strength and density, thereby obtaining suspending power, and realizing the object of raising temperature resistance of drilling fluid under this case.

Wherein, preferably, in the formula (I), each of the two R1 groups is independently selected from C14-C20 alkyl optionally substituted by group Y and C14-C20 unsaturated alkyl with a carbon-carbon double bond optionally substituted by group Y (preferably with not more than 5 carbon-carbon double bonds, 1, 2 or 3 for example); n is an integer of 1-6; R2 is selected from carboxyl, C1-C4 alkyl, C4-C6 cycloalkyl, C1-C4 alkyl substituted by carboxyl, C4-C6 cycloalkyl substituted by carboxyl, C4-C6 cycloalkyl substituted by carboxyl and methyl, C2-C4 unsaturated alkyl with a carbon-carbon double bond (preferably with 1-3 carbon-carbon double bonds, 1, 2 or 3 for example), C4-C6 unsaturated cycloalkyl with a carbon-carbon double bond (preferably with not more than 5 carbon-carbon double bonds, 1, 2 or 3 for example), C2-C4 unsaturated alkyl with a carbon-carbon double bond substituted by carboxyl (preferably with 1-3 carbon-carbon double bonds, 1, 2 or 3 for example), and C4-C7 unsaturated cycloalkyl with a carbon-carbon double bond substituted by carboxyl and methyl (preferably with not more than 5 carbon-carbon double bonds, 1, 2 or 3 for example).

More preferably, in Formula (I), each of the two R1 groups is independently selected from C15-C18 alkyl optionally substituted by group Y and C15-C18 unsaturated alkyl with a carbon-carbon double bond optionally substituted by group Y; n is an integer of 1-4, for example 1, 2, 3 or 4.

According to the present invention, each of the two R1 groups can be selected respectively and independently, and the two R1 groups may be the same or different from each other, wherein, examples of the R1 group may include the following groups: —(CH2)7—CH═CH—(CH2)7—CH3, —(CH2)8—CH(Y)—(CH2)7—CH3, —(CH2)7—CH(Y)—(CH2)8—CH3, —(CH2)7—CH(Y)—CH(Y)—(CH2)7—CH3, —(CH2)16—CH3, —(CH2)7—CH═CH—CH2—CH═CH—(CH2)4—CH3, —(CH2)7—CH═CH—CH2—CH2—CH(Y)—(CH2)4—CH3, —(CH2)7—CH═CH—CH2—CH(Y)—(CH2)5—CH3, —(CH2)8—CH(Y)—CH2—CH═CH—(CH2)4—CH3, —(CH2)7—CH(Y)—CH2—CH2—CH═CH—(CH2)4—CH3, —(CH2)7—CH═CH—CH2—CH(Y)—CH(Y)—(CH2)4—CH3, —(CH2)7—CH(Y)—CH(Y)—CH2—CH═CH—(CH2)4—CH3, —(CH2)7—CH(Y)—CH(Y)—CH2—CH(Y)—(CH2)5—CH3, —(CH2)8—CH(Y)—CH2—CH(Y)—CH(Y)—(CH2)4—CH3, —(CH2)7—CH(Y)—CH2—CH2—CH(Y)—CH(Y)—(CH2)4—CH3, —(CH2)7—CH(Y)—CH(Y)—CH2—CH2—CH(Y)—(CH2)4—CH3, —(CH2)7—CH(Y)—CH(Y)—CH2—CH(Y)—CH(Y)—(CH2)4—CH3, —(CH2)14—CH3, —(CH2)13—CH3. where group Y, as described above, is selected from

The connecting dotted lines on these groups stand for linkage sites linking the carbon atoms on R1.

According to the present invention, examples of the group R2 may include: carboxyl, methyl, ethyl, propyl, cyclopentyl, cyclohexyl, —CH2—COOH (referring to C1 alkyl substituted by a carboxyl group), —(CH2)2—COOH (referring to C2 alkyl substituted by a carboxyl group), —CH(CH2—COOH)2 (referring to C3 alkyl substituted by two carboxyl groups),

According to the present invention, the foregoing emulsifier may be a product available in the market and may also be prepared by a conventional method of the art. Preferably, the method for preparing the emulsifier comprises: subjecting a polyamine compound represented by Formula (II) to take amidation reaction with one or more of carboxylic acids represented by Formula R1′—COOH, and contacting and reacting the reaction product with one or more of carboxylic acids R2—COOH and anhydrides thereof;

where R2 and n have been described above, so no necessary details will be given herein.

R1′ is selected from C14-C30 alkyl and C14-C30 unsaturated alkyl with a carbon-carbon double bond.

Wherein, examples of the carboxylic acid represented by formula R1′—COOH may include: COOH—(CH2)7—CH═CH—(CH2)7—CH3 (also referred to as oleic acid), COOH—(CH2)7—CH═CH—CH2—CH═CH—(CH2)4—CH3 (also referred to as linoleic acid), COOH—(CH2)16—CH3 (also referred to as octadecanoic acid), COOH—(CH2)14—CH3 (also referred to as hexadecanoic acid or palmitic acid), and COOH—(CH2)13—CH3 (also referred to as pentadecanoic acid).

Wherein, examples of the carboxylic acid represented by the formula R2-COOH and its anhydride may include: HOOC—COOH (oxalic acid), CH3—COOH (acetic acid), CH3—COO—CO—CH3 (acetic anhydride), HOOC—CH2—COOH (propandioic acid), HOOC—CH2—CH2—COOH (butanedioic acid), HOOC—CH2—CH(COOH)—CH2—COOH (tricarballylic acid),

According to the present invention, the embodiments of the polyamine represented by Formula (II) for example may include:

(called as diethylenetriamine),

(called as triethylenetetramine),

(called as tetraethylenepentamine),

(called as pentaethylenehexamine).

According to the present invention, the amidation reaction between the polyamine represented by foregoing Formula (II) and the carboxylic acid represented by R1′—COOH mainly refers to the amidation reaction between the primary amine of the polyamine represented by foregoing Formula (II) and the carboxylic group of the carboxylic acid represented by R1′—COOH, with water molecules removed to form amido bonds, thereby obtaining one or more of compounds with secondary amine not substituted in the middle of the chain as represented by

Preferably, the molar ratio of the polyamine compound represented by Formula (II) and the carboxylic acid represented by Formula R1′—COOH is 1:1.8 to 1:3, preferably 1:1.8 to 1:2.2.

According to the present invention, preferably, the conditions of the amidation reaction comprise: the temperature is a temperature of 220-230° C., pH value of 7-9 and a time of 3-5 h. In order to make amidation reaction more sufficient, this method may further comprise: firstly mixing the polyamine represented by Formula (II) with one or more of carboxylic acids represented by R1′—COOH for 10-30 min under a stirring rate of 80-300 r/min, then taking the amidation reaction under a stirring rate of 80-300 r/min, and water is trapped by water knockout trap during amidation reaction.

According to the present invention, the emulsifier of the present invention may be obtained through contacting and reacting the above reaction product of the amidation reaction with one or more of the carboxylic acids represented by R2—COOH and anhydrides thereof. The reaction product of amidation reaction may be purified to obtain the compound represented by

alternatively, the reaction product of amidation reaction without purification may directly contact and react with one or more of the carboxylic acids represented by R2—COOH and anhydrides thereof so as to link —C(O)—R2 substituent to the secondary amine between two amido bonds, thereby forming the compound with a comb-like structure represented by Formula (I). Preferably, the molar ratio of the polyamine compound represented by Formula (II) and the carboxylic acids represented by Formula R2—COOH and anhydrides thereof is 1:0.5 to 1:20. For example, the molar ratio of the polyamine compound represented by Formula (II) and the carboxylic acids represented by Formula R2—COOH and anhydrides thereof is 1:1.8 to 1:2.2, 1:3.6 to 1:4.4, 1:5.4 to 1:6.6, 1:7.2 to 1:8.8, 1:9 to 1:11, 1:10.8 to 1:13.2.

According to the present invention, when the carboxylic acid represented by R1′—COOH is an unsaturated carboxylic acid with a carbon-carbon double bond, and the carboxylic acids represented by Formula R2—COOH and anhydrides thereof adopted in the process of the contract reaction also contain a carbon-carbon double bond, then in the process of the contact reaction, addition reaction may also occur between the carbon-carbon double bond in the carboxylic acids represented by Formula R2—COOH (and anhydrides thereof) and the carbon-carbon double bond in the reaction product of the amidation reaction, thereby obtaining the compound with R1 (shown in Formula (I)) substituted by group Y. Although the present invention does not have particular limitation to this, the compound obtained under this case is also included in the emulsifier described in the present invention.

According to the present invention, preferably, the conditions of the contact reaction comprise: a temperature of 75-90° C., pH value of 7-9 and a time of 6-10 h. In order to make contact reaction more sufficient, this method may further comprise: contacting and reacting the reaction product of the amidation reaction with one or more of the carboxylic acids represented by Formula R2—COOH and anhydrides thereof under a stirring rater of 200-500 r/min, and water is trapped by water knockout trap during the contact reaction.

According to the present invention, it should be noted that the emulsifier of the present invention may be one of the compounds represented by Formula (I), but if the foregoing preparation method is adopted, the emulsifier may also be one of the compounds represented by Formula (I) obtained through purifying and separating the product obtained by the foregoing preparation method. However, as more effective operation, the emulsifier of the present invention may be more of the compounds represented by Formula (I), i.e.: if the foregoing preparation method is adopted, the emulsifier may be a product directly obtained by the foregoing preparation method and is uses without purification. In other words, it may be understood that the emulsifier of the present invention is a product obtained by the foregoing method without purification.

According to the present invention, the rheological modifier preferably is a dimer acid-organic amine copolymer comprising structural units from dimer acid, structural units from alkylamine, and structural units from arylamine, wherein, the dimer acid is a dimer of oleic acid and linoleic acid, the alkylamine is one or more of C10-C20 alkyl primary amines, the arylamine is aniline and aniline substituted by C1-C3 alkyl at one or more sites on benzene ring. More preferably, the rheological modifier is the dimer acid-organic amine copolymer. Wherein, the dimer acid is a dimer fatty acid containing two carboxyl groups, which is a dimer of oleic acid (CH3(CH2)7CH═CH(CH2)7COOH) and linoleic acid (CH3(CH2)4CH═CHCH2CH═CH(CH2)7COOH). Such a dimer acid may be obtained with a conventional method according to the present invention, such as the method described in the article “Shulin Zhang, Synthesis and Application of Dimer Acid, Fine Petrochemical Industry, 1995”, or may be a commercial product (preferably the purity is 98 wt. % or higher). Preferably, the alkylamine is one or more of dodecyl primary amine, tridecyl primary amine, tetradecyl primary amine, pentadecyl primary amine, hexadecyl primary amine, heptadecyl primary amine, and octodecyl primary amine, more preferably is dodecyl primary amine and/or octodecyl primary amine. Preferably, the arylamine is one or more of aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2-propylaniline, 3-propylaniline, and 4-propylaniline, and more preferably is one or more of aniline, 2-methylaniline, 3-methylaniline, and 4-methylaniline.

In a preferred embodiment of the present invention, the dimer acid is a dimer of oleic acid and linoleic acid, the alkylamine is dodecyl primary amine or octodecyl primary amine, and the arylamine is aniline or 3-methylaniline.

According to the present invention, preferably, the molar ratio of the structural units from dimer acid to the structural units from alkylamine to the structural units from the dimer acid, structural units from the alkylamine and structural units from the arylamine is 1:0.3-1:0.2-1, more preferably 1:0.3-0.8:0.2-0.7, further more preferably 1:0.4-0.7:0.3-0.6.

Preferably, the weight-average molecular weight of the dimer acid-organic amine copolymer is 2,200-9,000 g/mol, and the absolute viscosity thereof is 20,000-150,000 cp p. Considering from the perspective of obtaining a composition more suitable for raising suspending power and temperature resistance of clay-free whole-oil-based drilling fluid, more preferably, the weight-average molecular weight of the dimer acid-organic amine copolymer is 4,000-9,000 g/mol, and the absolute viscosity thereof is 100,000-150,000 cp. More preferably, the weight-average molecular weight of the dimer acid-organic amine copolymer is 5,000-9,000 g/mol, and the absolute viscosity thereof is 100,000-150,000 cp. In the present invention, weight-average molecular weight is measured by GPC (gel permeation chromatography), and absolute viscosity is measured by Brookfield viscometer.

According to the present invention, the dimer acid-organic amine copolymer as rheological modifier may be prepared by a conventional method of the ar. For example, the method for preparing the dimer acid-organic amine copolymer comprises: copolymerizing the dimer acid, the alkylamine and the arylamine. In this method, the dimer acid, alkylamine and arylamine have been described above, so no necessary details will be given herein.

According to the present invention, the foregoing copolymerization reaction among dimer acid, alkylamine and arylamine is mostly dehydration condensation reaction between carboxylic acids and amines. By copolymerization reaction among dimer acid, alkylamine and arylamine in the present invention alone, a dimer acid-organic amine copolymer with good performance may be obtained as a rheological modifier of whole-oil-based drilling fluid, but in order to obtain a rheological modifier with absolute viscosity and molecular weight more suitable for whole-oil-based drilling fluid, the molar ratio of the dimer acid, alkylamine and arylamine is preferably 1:0.3-1:0.2-1, more preferably 1:0.3-0.8:0.2-0.7, further more preferably 1:0.4-0.7:0.3-0.6.

According to the present invention, the copolymerization reaction may adopt a conventional method of the art as long as a dimer acid-organic amine copolymer that may be used as a rheological modifier of the composition can be obtained. Preferably, before copolymerization of dimer acid, alkylamine and arylamine, they are mixed to obtain a monomer mixture; then with the existence of concentrated sulfuric acid, the obtained monomer mixture takes copolymerization reaction.

According to the present invention, if the dimer acid, alkylamine and arylamine are mixed at first to obtain monomer mixture, the monomers can more sufficiently contact each other in the subsequent polymerization reaction. As the foregoing monomer mixture is sticky, preferably the mixing is conducted at higher temperature, and particularly preferably the adopted mixing conditions include: a temperature of 100-130° C. and a time of 20-30 min.

According to the present invention, when the foregoing concentrated sulfuric acid is used as a catalyst of the copolymerization reaction in the present invention, there is no particular limitation to its dose as long as it can catalyze the copolymerization reaction in the present invention. Preferably, based on the total weight of the dimer acid, alkylamine and arylamine, the dose of the concentrated sulfuric acid is 0.3-1 wt. %. The concentrated sulfuric acid may be a sulfuric acid solution with sulfuric acid concentration of 95 wt. % or above (preferably 98 wt. %).

According to the present invention, preferably, the conditions of the copolymerization reaction comprise: a temperature of 150-180° C. and a time of 2-6 h. More preferably, the conditions of the copolymerization reaction comprise: a temperature of 155-175° C. and a time of 2-6 h. Further more preferably, the conditions of the copolymerization reaction comprise: a temperature of 160-170° C. and a time of 2-6 h.

In order to promote the copolymerization reaction, byproduct water of copolymerization reaction may be removed from the reaction system. The method for removing byproduct water is a conventional method of the art, so no necessary details will be given here.

When the foregoing method is adopted to prepare dimer acid-organic amine copolymer, the rheological modifier may be either the dimer acid-organic amine copolymer prepared by the foregoing method, or a 50-70 wt. % solution obtained by directly using a diluent to dilute the dimer acid-organic amine copolymer prepared by the foregoing method (in other words, based on the total weight of the dimer acid-organic amine copolymer solution after dilution, the content of dimer acid-organic amine copolymer is 50-70 wt. %), or a rheological modifier of the present invention obtained by other methods well known in the art and containing the dimer acid-organic amine copolymer.

Those skilled in the art should understand that the product of copolymerization reaction is not separated in general and it is believed that all the adopted monomers basically take complete reaction and the product of copolymerization reaction is directly used as copolymer. Therefore, for the sake of convenience, the diluent may be directly added to the products of the copolymerization reaction after the copolymerization reaction in the method for preparing the foregoing dimer acid-organic amine copolymer is completed, and there is no need to purify and separate the dimer acid-organic amine copolymer in it. In a general sense, the dimer acid-organic amine copolymer referred to in the present invention is also the product of the copolymerization reaction without purification and separation, or the product of copolymerization reaction obtained after only byproduct water is removed as described above.

The diluent for example may be a diluent conventionally adopted in the art, such as: tall oil and/or tall oil fatty acid.

According to the present invention, in order to give a better play to the synergistic effect among the components in the composition, preferably, the weight ratio of the lubricant, the emulsifier and the rheological modifier is 100:300-800:50-200, and more preferably is 100:300-500:50-100.

The present invention further provides a use of the composition as a drilling fluid additive in oil and gas drilling.

The present invention further provides an oil-based drilling fluid containing the composition described above.

According to the present invention, the oil-based drilling fluid that contains the composition in the present invention has greatly decreased lubrication coefficient, improved lubricating property, favorable rheological property and thermostability, and is suitable for use in operation at a high temperature.

Preferably, based on 100 part by weight of oil phase in the drilling fluid, the content of the composition is 2-10 part by weight. In this case, preferably, based on 100 part by weight of oil phase in the drilling fluid, the content of the lubricant is 5 part by weight or lower, preferably is 0.5-2 part by weight, such as 1 part by weight. Preferably, based on 100 part by weight of oil phase in the drilling fluid, the amount of the rheological modifier is 1-5 part by weight. Preferably, based on 100 part by weight of oil phase in the drilling fluid, the amount of the emulsifier is 1-5 part by weight.

According to the present invention, the oil phase in the drilling fluid may be any conventional oil phase in the art, such as one or more of diesel oil and white oil (e.g., white oil 3# (220° C. flash point, 3 mm2/s kinematic viscosity at 40° C., and specific gravity=0.85), or white oil 5# (220° C. flash point, 3.5 mm2/s kinematic viscosity at 40° C., and specific gravity=0.85). In addition, CaCl2 water solution (preferably CaCl2 water solution at 20-40 wt. % CaCl2 concentration) in appropriate amount is added in the oil-based drilling fluid; for example, based on 100 part by weight of oil phase in the drilling fluid, the amount of the CaCl2 water solution is 15-40 part by weight.

According to the present invention, the oil-based drilling fluid may further contain conventional additives used in oil-based drilling fluids; preferably, the oil-based drilling fluid contains one or more of wetting agent, filtrate reducer, alkalinity regulator, and weighting agent.

Wherein, the wetting agent can improve the wetting property of drilling fluid, and prevent complex downhole conditions, such as jamming of drilling tool, etc.; for example, the wetting agent may be one or more of modified phospholipid (e.g., FHGT-G modified phospholipid from Shanghai Youchuang Industrial Co., Ltd.) and a mixture of fatty glyceride and surfactant (e.g., FK-1), and preferably is FHGT-G modified phospholipid. More preferably, based on 100 part by weight of oil phase in the drilling fluid, the amount of the lubricant is 0.5-2 part by weight.

Wherein, the filtrate reducer can improve the fluid loss control and wall-building properties of drilling fluid; for example, the filtrate reducer may be one or more of oxidized asphalt, modified humic acid, and polymeric oil-based filtrate reducer (e.g., sulphonated polystyrene), and preferably is modified humic acid and/or polymeric oil-based filtrate reducer. Preferably, based on 100 part by weight of oil phase in the drilling fluid, the amount of the filtrate reducer is 1-3 part by weight.

Wherein, the alkalinity regulator has effects of stabilizing the emulsion and improving emulsion-breaking voltage; for example, the alkalinity regulator may be CaO. Preferably, based on 100 part by weight of oil phase in the drilling fluid, the amount of the alkalinity regulator is 2-5 part by weight.

Wherein, the weighting agent has an effect of adjusting the density of drilling fluid to desired density; for example, the weighting agent may be barite (e.g., barite with 90 wt. % or higher barium sulfate content), etc. Preferably, based on 100 part by weight of oil phase in the drilling fluid, the amount of the weighting agent is 400-500 part by weight.

The above-mentioned additives may be commercial products, or may be prepared with conventional methods in the art. They will not be further detailed here.

According to the present invention, by adding the composition obtained in the present invention, the obtained oil-based drilling fluid with 2.6 g/cm3 density may have a greatly decreased lubrication coefficient after hot aging at 200° C.; preferably the lubrication coefficient is decreased by 40% or more, particularly preferably decreased by 55% or more, more preferably decreased by 60% or more; in addition, the drilling fluid maintains favorable rheological property and has high thermostability, and is suitable for use in operation at a high temperature.

The present invention further provides an application of the oil-based drilling fluid in oil and gas drilling.

Hereunder the present invention will be detailed in embodiments.

In the following examples and comparative examples:

The infrared spectrums are measured with a MAGNA-IR 560 Fourier transform infrared spectrometer from SpectraLab Scientific.

The 1H-NMR spectrums and 13C-NMR spectrums are measured with an AVANCE 400 NMR spectrometer from Bruker.

The SEM spectrums are measured with a SU-8010 SEM analyzer from Hitachi.

The TEM spectrums are measured with a JEM-2100 TEM analyzer from JEOL.

Graphite Oxide Preparation Example 1

423 g concentrated sulfuric acid (at 98 wt. % concentration) is added into a mixture of 10 g graphite (325 mesh natural crystalline flake graphite from Qingdao Santong Graphite Co., Ltd.) and 30 g potassium permanganate at room temperature (approx. 25° C.), and then the materials are stirred and heated up to 50° C., and held at the temperature for reaction for 12 h while stirring; the reaction product is cooled to room temperature (approx. 25° C.), poured into 400 g of 0.4 wt. % aqueous hydrogen peroxide solution (ice water solution, at 0° C. temperature); now the mixed solution changes from greyish green color to golden yellow color. The product is filtered and washed, till the filtrate is neutral, then the product is dried at 100° C. for about 10 h; thus, 10 g graphite oxide is obtained, a 500×SEM image of the graphite oxide is shown in FIG. 1, and a 10,000×SEM image is shown in FIG. 2.

Emulsifier Preparation Example 1

(1) The reactants are mixed at a molar ratio of tetraethylene pentamine to linoleic acid=1:2.2 (i.e., the molar ratio of tetraethylene pentamine calculated by primary amine group to linoleic acid is 1:1.1), and stirred for 40 min at 250 r/min stirring rate, then the pH of the obtained mixture is adjusted to 9, and the mixture is kept at 230° C. for reaction for 3 h, while water is separated with a water separator in the process, next, the product is cooled to room temperature;

(2) The reaction product in the step (1) is mixed with propandioic acid (the molar ratio of the tetraethylene pentamine to the propandioic acid is 1:0.6), then the pH of the obtained mixture is adjusted to 8, next, the mixture is stirred at 400 r/min. at 90° C. for reaction for 6 h; thus, an emulsifier A1 is obtained. Detected and analyzed by infrared spectroscopy, 1H-NMR spectroscopy, and 13C-NMR spectroscopy, the emulsifier A1 contains amido groups, unsaturated double bonds, and carboxyl groups, and is in a comb structure.

Rheological Modifier Preparation Example 1

(1) Dimer acid (Pripol 1013 from Shanghai Heribit Chemical Co., Ltd., the same below), dodecyl primary amine, and aniline are added at 1:0.5:0.5 molar ratio into a reaction vessel, and the materials are stirred at 120±2° C. for 30 min.; thus, a homogeneous mixture of monomers is obtained;

(2) Concentrated sulfuric acid (at 98 wt. % concentration, the added amount is 0.5 wt. % of the weight of the mixture of monomers) is added by dropwise into the mixture of monomers (within about 2 min.), with a condensate drain device deployed, the mixture is kept at 160±5° C. for reaction for 2 h; the obtained reaction product is dimer acid-organic amine copolymer, which has 6,500 g/mol weight-average molecular weight and 125,000 cp absolute viscosity.

Tall oil diluent (tall oil F1 from Jinan Jinquan Chemical Co., Ltd, the same below) is added into the dimer acid-organic amine copolymer, to dilute the dimer acid-organic amine copolymer to 50 wt. % concentration; thus, a rheological modifier B1 described in the present invention is obtained, and the rheological modifier liquid is orange liquid.

Lubricant Preparation Example 1

17.1 g (80 mmol) N,N-dimethyl lauryl amine, 4 g concentrated hydrochloric acid (at 37 wt. % concentration), 3.4 g (36.4 mmol) epoxy chloropropane, and 0.1 g graphite oxide are added into 50 g ethanol, and the materials are mixed by ultrasonic mixing for 1 h; then, the homogeneous solution is kept at 80° C. for reaction for 24 h in reflux mode; next, the solvent is removed by reduced pressure distillation, and the product is cooled and dried; thus, 18 g lubricant L1 is obtained, in which the weight ratio of graphite oxide to biquaternary ammonium salt compound is 1:180.

Analyzed by infrared spectrometry, NMR spectrometry, and mass spectrometry, the lubricant L1 contains a biquaternary ammonium salt compound represented by the formula (1-1-1), which is chemically linked with graphite oxide as modifying group represented by the formula (2) (R1 is H, R2 is methyl, and R3 is n-butyl); analyzed by SEM and TEM, in the lubricant L1, the biquaternary ammonium salt compound adheres to the graphite oxide on the surface and between the layers, wherein, a 250×SEM image is shown in FIG. 3, and a 10,000×SEM image is shown in FIG. 4.

Lubricant Preparation Example 2

According to the method described in the lubricant preparation example 1, the difference is that 19.3 g (80 mmol) N,N-dimethyl tetradecylamine is used to replace the N,N-dimethyl laurylamine, the product is cooled and dried, and thus 20 g lubricant L2 is obtained, wherein, the weight ratio of the graphite oxide to the biquaternary ammonium salt compound is 1:200.

Analyzed by infrared spectrometry, NMR spectrometry, and mass spectrometry, the lubricant L2 contains a biquaternary ammonium salt compound represented by the formula (1-3-1), which is chemically linked with the graphite oxide as modifying group represented by the formula (2) (R1 is H, R2 is methyl, and R3 is n-hexyl); analyzed by SEM and TEM, in the lubricant L2, the biquaternary ammonium salt compound adheres to the graphite oxide on the surface and between layers.

Lubricant Preparation Example 3

According to the method described in the lubricant preparation example 1, the difference is that 21.6 g (80 mmol) N,N-dimethyl hexadecylamine is used to replace the N,N-dimethyl laurylamine, the product is cooled and dried, and thus 23 g lubricant L3 is obtained, wherein, the weight ratio of the graphite oxide to the biquaternary ammonium salt compound is 1:220.

Analyzed by infrared spectrometry, NMR spectrometry, and mass spectrometry, the lubricant L3 contains a biquaternary ammonium salt compound represented by the formula (1-5-1), which is chemically linked with the graphite oxide as modifying group represented by the formula (2) (R1 is H, R2 is methyl, and R3 is n-octyl); analyzed by SEM and TEM, in the lubricant L3, the biquaternary ammonium salt compound adheres to the graphite oxide on the surface and between layers.

Lubricant Preparation Example 4

According to the method described in the lubricant preparation example 1, the difference is that 23.8 g (80 mmol) N,N-dimethyl octadecylamine is used to replace the N,N-dimethyl laurylamine, the product is cooled and dried, and thus 24 g lubricant L4-1 is obtained, wherein, the weight ratio of the graphite oxide to the biquaternary ammonium salt compound is 1:240.

Analyzed by infrared spectrometry, NMR spectrometry, and mass spectrometry, the lubricant L4-1 contains a biquaternary ammonium salt compound represented by the formula (1-7-1), which is chemically linked with the graphite oxide as modifying group represented by the formula (2) (R1 is H, R2 is methyl, and R3 is n-decyl); analyzed by SEM and TEM, in the lubricant L4-1, the biquaternary ammonium salt compound adheres to the graphite oxide on the surface and between layers.

Lubricant Preparation Example 5

23.8 g (80 mmol) N,N-dimethyl octadecylamine, 5.4 g concentrated hydrochloric acid (at 37 wt. % concentration), 2.5 g (26.7 mmol) epoxy chloropropane, and 0.2 g graphite oxide are added into 50 g ethanol, and the materials are mixed by ultrasonic mixing for 40 min.; then, the homogeneous solution is kept at 85° C. for reaction for 22 h in reflux mode; next, the solvent is removed by reduced pressure distillation, and the product is cooled and dried; thus, 18 g lubricant L4-2 is obtained, in which the weight ratio of graphite oxide to biquaternary ammonium salt compound is 1:90.

Analyzed by infrared spectrometry, NMR spectrometry, and mass spectrometry, the lubricant L4-2 contains a biquaternary ammonium salt compound represented by the formula (1-7-1), which is chemically linked with the graphite oxide as modifying group represented by the formula (2) (R1 is H, R2 is methyl, and R3 is n-decyl); analyzed by SEM and TEM, in the lubricant L4-2, the biquaternary ammonium salt compound adheres to the graphite oxide on the surface and between layers.

Lubricant Preparation Example 6

23.8 g (80 mmol) N,N-dimethyl octadecylamine, 2.7 g concentrated hydrochloric acid (at 37 wt. % concentration), 3.7 g (40 mmol) epoxy chloropropane, and 0.4 g graphite oxide are added into 80 g ethanol, and the materials are mixed by ultrasonic mixing for 40 min.; then, the homogeneous solution is kept at 90° C. for reaction for 20 h in reflux mode; next, the solvent is removed by reduced pressure distillation, and the product is cooled and dried; thus, 24 g lubricant L4-3 is obtained, in which the weight ratio of graphite oxide to biquaternary ammonium salt compound is 1:60.

Analyzed by infrared spectrometry, NMR spectrometry, and mass spectrometry, the lubricant L4-3 contains a biquaternary ammonium salt compound represented by the formula (1-7-1), which is chemically linked with the graphite oxide as modifying group represented by the formula (2) (R1 is H, R2 is methyl, and R3 is n-decyl); analyzed by SEM and TEM, in the lubricant L4-3, the biquaternary ammonium salt compound adheres to the graphite oxide on the surface and between layers.

Lubricant Preparation Example 7

According to the method described in the lubricant preparation example 4, the difference is that the amount of N,N-dimethyl octadecylamine is 26.8 g (90 mmol), and the epoxy chloropropane is 3.8 g (41 mmol); thus, 28 g lubricant L4-4 is obtained, wherein, the weight ratio of the graphite oxide to the biquaternary ammonium salt compound is 1:280.

Lubricant Preparation Example 8

According to the method described in the lubricant preparation example 4, the difference is that 0.6 g graphite oxide is used; thus, 24 g lubricant L4-4 is obtained, wherein, the weight ratio of the graphite oxide to the biquaternary ammonium salt compound is 1:40.

Drilling Fluid Example 1

This example is provided to describe the composition and the drilling fluid in the present invention.

The formation is: 100 part by weight of diesel oil (diesel oil 0# from Beijing Jinbaoli, the same below), 20 part by weight of CaCl2 water solution (the CaCl2 concentration in the solution is 30 wt. %), 1 part by weight of lubricant L1, 3 part by weight of emulsifier A1, 2 part by weight of rheological modifier B1, 1 part by weight of modified phospholipid wetting agent (e.g., FHGT-G modified phospholipid from Shanghai Youchuang Industrial Co., Ltd., the same below), 2 part by weight of polymeric oil-based filtrate reducer (HFLO oil-based filtrate reducer from Sichuan Honghua), 3 part by weight of CaO, 450 part by weight of barite (from Sichuan Zhengrong, the same below); thus, a drilling fluid X1 is prepared, and the density of it is 2.6 g/cm3.

Drilling Fluid Examples 2-8

These examples are provided to describe the composition and the drilling fluid in the present invention.

According to the formation used in the drilling fluid example 1, the difference is that the lubricant L2-L3 and L4-1 to L4-4 are used respectively to replace the lubricant L1; thus, drilling fluids X2-X8 are obtained, and the density is 2.6 g/cm3.

Comparative Example 1

According to the formation used in the drilling fluid example 1, the difference is that the lubricant L1 is not added; thus, a drilling fluid DX1 is prepared.

Comparative Example 2

According to the formation used in the drilling fluid example 1, the difference is that the graphite oxide obtained in the preparation example 1 is used to replace the lubricant L1; thus, a drilling fluid DX2 is prepared.

Comparative Example 3

According to the formation used in the drilling fluid example 1, the difference is that an EZ-MUL emulsifier from Halliburton is used to replace the emulsifier A1; thus, a drilling fluid DX3 is prepared.

Comparative Example 4

According to the formation used in the drilling fluid example 1, the difference is that a VER-MUL emulsifier from Jingzhou Jiahua Technology Co., Ltd. is used to replace the emulsifier A1; thus, a drilling fluid DX4 is prepared.

Comparative Example 5

According to the formation used in the drilling fluid example 1, the difference is that the rheological modifier B1 is not added; thus, a drilling fluid DX5 is prepared.

Test Example

The drilling fluids X1-X8 and DX1-DX5 are tested at room temperature without hot aging and after hot aging at 200° C. for 16 h respectively, to test their plastic viscosity (PV), apparent viscosity (AV), yield point (YP), emulsion-breaking voltage and lubrication coefficient (K), and calculate reduced rate (Rk) of lubrication coefficient. The results are shown in Table 1, wherein:

The plastic viscosity (PV) is measured with a FANN six-speed viscosity meter with the method specified in the national standard GB/T29170-2012, in unit of mPa·s,

PV=θ600−θ300.

The apparent viscosity (AV) is measured with a FANN six-speed viscosity meter with the method specified in the national standard GB/T29170-2012, in unit of mPa·s,

AV=12θ600.

The yield point (YP) is measured with a FANN six-speed viscosity meter with the method specified in the national standard GB/T29170-2012 YP=0.5(2θ300−θ600), in unit of Pa.

The lubrication coefficient K refers to the ratio of the friction force between two friction surfaces to the normal load, and is measured with an E-P extreme pressure lubricity tester with the method specified in the petroleum industry standard SY/T6094-1994.

The reduced rate Rk of lubrication coefficient refers to the reduced rate of lubrication coefficient of a drilling fluid after lubricant is added in relation to the lubrication coefficient of the drilling fluid without lubricant. The calculation formula is:

Rk=[(K0−K)/K0]×100%,

wherein, Rk means reduced rate of lubrication coefficient, %; K0 means lubrication coefficient of the drilling fluid without lubricant (i.e., the lubrication coefficient of the drilling fluid DX1); K means the lubrication coefficient of the drilling fluid after a nano-hybrid lubricant is added.

The emulsion-breaking voltage is measured with an electrical stability tester (Model D90-300 from Qingdao Jiaonan Analytical Instrument Factory, the same below), and it refers to the voltage when water-in-oil mud begins to break, and reflects the electrical stability of the water-in-oil mud. A higher emulsion-breaking voltage indicates that the mud can maintain in emulsion state in a wider range and has higher stability; a lower emulsion-breaking voltage indicates the mud has lower stability. In the testing process, electrodes are inserted into the emulsion mud to be tested, an applicable step voltage multiplier is selected, and the voltage across the electrodes is increased gradually, till the electrical stability tester indicates that the emulsion mud has broken; then, the voltage reading when the emulsion mud begins to break is logged.


TABLE 1
Drilling
AV
PV
YP
Emulsion-Breaking
Rk
Fluid
Condition
mPa · s
mPa · s
Pa
Voltage V
K
%
X1
Before hot aging
84
76
8
1141
0.102
42.7%
After hot aging
80
71
9
978
0.111
41.9%
X2
Before hot aging
88
79
9
1174
0.090
49.4%
After hot aging
82
72
10
987
0.096
49.7%
X3
Before hot aging
95
84
11
1264
0.074
58.4%
After hot aging
85
75
10
1043
0.082
57.1%
X4
Before hot aging
106
99
7
1298
0.068
61.8%
After hot aging
96
90
6
1097
0.073
61.8%
X5
Before hot aging
104
96
8
1475
0.076
57.3%
After hot aging
92
84
8
1198
0.079
58.6%
X6
Before hot aging
98
89
9
1584
0.081
54.5%
After hot aging
90
81
9
1285
0.085
55.5%
X7
Before hot aging
96
88
8
1223
0.111
37.6%
After hot aging
92
83
9
1089
0.123
35.6%
X8
Before hot aging
108
98
10
1312
0.119
35.1%
After hot aging
104
93
11
1076
0.128
33.9%
DX1
Before hot aging
100
92
8
1197
0.178
/
After hot aging
87
80
7
1036
0.191
/
DX2
Before hot aging
102
93
9
1069
0.121
32.0%
After hot aging
92
81
11
923
0.132
30.1%
DX3
Before hot aging
93
82
11
541
0.117
34.2%
After hot aging
115
97
18
520
0..132
30.1%
DX4
Before hot aging
98
90
8
378
0.120
32.5%
After hot aging
123
111
12
366
0.132
30.1%
DX5
Before hot aging
78
75
3
693
0.120
32.5%
After hot aging
76
75
1
527
0.131
31.4%
Note:
“/” represents without data.

It is seen from the data in Table 1: the composition provided in the present invention can effectively improve the lubricating property of the obtained drilling fluid; thus, the lubrication coefficient of the obtained drilling fluid is greatly decreased, preferably the reduced rate of the lubrication coefficient is 40% or higher, particularly preferably is 55% or higher, more preferably is 60% or higher. Especially, the above-mentioned lubricating effect varies little before and after hot aging at 200° C., indicating that the composition provided in the present invention has a favorable temperature resistance property, and is suitable for use in operation at a high temperature. Furthermore, compared with the drilling fluid DX1 (blank sample), the rheological property (i.e., plastic viscosity (PV), apparent viscosity (AV), and yield point (YP)) of the drilling fluid in the present invention before and after hot aging have no significant difference, which indicates the composition provided in the present invention maintains a good rheological property. In addition, the emulsion-breaking voltage is high; hence, an outstanding oil-based drilling fluid can be formed (the oil-based drilling fluid may also be considered as a water-in-oil inverse emulsion drilling fluid).

While some preferred embodiments of the present invention are described above, the present invention is not limited to the details in those embodiments. Those skilled in the art can make modifications and variations to the technical scheme of the present invention, without departing from the spirit of the present invention. However, all these modifications and variations shall be deemed as falling into the protected scope of the present invention.

In addition, it should be noted that the specific technical features described in above embodiments can be combined in any appropriate form, provided that there is no conflict. To avoid unnecessary repetition, the possible combinations are not described specifically in the present invention.

Moreover, different embodiments of the present invention can be combined freely as required, as long as the combinations don't deviate from the ideal and spirit of the present invention. However, such combinations shall also be deemed as falling into the scope disclosed in the present invention.

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Citation

Patents Cited in This Cited by
Title Current Assignee Application Date Publication Date
Organic compounds FIDELITY UNION BANK (FORMERLY KNOWN AS FIDELITY UNION TRUST COMPANY) EXECUTIVE TRUSTEE UNDER SANDOZ TRUST OF MAY 4, 1955 25 March 1983 26 February 1985
钻井液的添加剂组合物和抗高温无土相全油基钻井液 中国石油大学(北京) 02 February 2016 01 June 2016
一种基于化工副产物制备钻井用矿物复合固体润滑剂技术 中国地质大学(北京) 23 March 2010 28 September 2011
一种油基钻井液用固体乳化剂及制备方法以及在油基钻井液的应用 中石化石油工程技术服务有限公司,中石化胜利石油工程有限公司,钻井工程技术公司 22 April 2014 13 August 2014
主乳化剂及其制备方法以及乳化剂组合物及其应用和油基钻井液 中国石油大学(北京) 15 February 2015 30 March 2016
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