CN113527131A - Polyamine with inhibition and solid phase cleaning functions, and preparation method and application thereof - Google Patents

Polyamine with inhibition and solid phase cleaning functions, and preparation method and application thereof Download PDF

Info

Publication number
CN113527131A
CN113527131A CN202011597042.XA CN202011597042A CN113527131A CN 113527131 A CN113527131 A CN 113527131A CN 202011597042 A CN202011597042 A CN 202011597042A CN 113527131 A CN113527131 A CN 113527131A
Authority
CN
China
Prior art keywords
polyamine
heating
intermediate product
solid phase
phase cleaning
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011597042.XA
Other languages
Chinese (zh)
Other versions
CN113527131B (en
Inventor
司西强
王中华
吕跃滨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petrochemical Corp
Sinopec Oilfield Service Corp
Sinopec Zhongyuan Petroleum Engineering Co Ltd
Drilling Engineering Technology Research Institute of Sinopec Zhongyuan Petroleum Engineering Co Ltd
Original Assignee
China Petrochemical Corp
Sinopec Oilfield Service Corp
Sinopec Zhongyuan Petroleum Engineering Co Ltd
Drilling Engineering Technology Research Institute of Sinopec Zhongyuan Petroleum Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petrochemical Corp, Sinopec Oilfield Service Corp, Sinopec Zhongyuan Petroleum Engineering Co Ltd, Drilling Engineering Technology Research Institute of Sinopec Zhongyuan Petroleum Engineering Co Ltd filed Critical China Petrochemical Corp
Priority to CN202311668604.9A priority Critical patent/CN117886713A/en
Priority to CN202011597042.XA priority patent/CN113527131B/en
Publication of CN113527131A publication Critical patent/CN113527131A/en
Application granted granted Critical
Publication of CN113527131B publication Critical patent/CN113527131B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/36—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/08—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
    • C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/14—Clay-containing compositions
    • C09K8/18—Clay-containing compositions characterised by the organic compounds
    • C09K8/22—Synthetic organic compounds
    • C09K8/24—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention provides polyamine with the functions of inhibition and solid phase cleaning, which has a structure shown in a formula (I); wherein m is an integer of 1 to 10, n is an integer of 1 to 5, and R is an alkylene group of C1 to C5. Compared with the prior art, the polyamine provided by the invention has a better inhibitor solid phase cleaning effect under a high temperature condition, has better compatibility in the drilling fluid, and can be applied to the drilling fluid, so that the problem of borehole wall instability of a strong water-sensitive shale stratum can be effectively solved, the problem of drilling fluid slurrying caused by drilling cuttings hydration can be effectively avoided, and the borehole wall stability is ensuredAnd (4) fixing and cleaning the drilling fluid.
Figure DDA0002866713650000011

Description

Polyamine with inhibition and solid phase cleaning functions, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of oilfield chemical drilling fluid treating agents, and particularly relates to polyamine with inhibiting and solid-phase cleaning functions, and a preparation method and application thereof.
Background
Along with the continuous expansion of the oil and gas exploration and development range, deep well ultra-deep wells, large-slope directional wells and long-section horizontal wells are more and more, complex strata such as high-temperature and high-activity shale, mudstone and mudstone interbed are more and more drilled, and the difficulty in stabilizing the well wall is more and more increased. Although the existing inhibitor can better solve the problem of borehole wall instability of a high-activity shale stratum, the borehole wall stability effect of a high-temperature high-activity shale stratum which is easy to collapse and the solid phase cleaning effect of a high-temperature drilling fluid are still to be improved. Therefore, the research and development of the high-temperature-resistant shale strong inhibitor and the drilling fluid solid-phase cleaning agent are imperative, meet the urgent need of the drilling field technology, and have great significance.
Disclosure of Invention
In view of the above, the present invention provides a polyamine with both inhibition and solid phase cleaning effects, and a preparation method and applications thereof.
The invention provides polyamine with both inhibition and solid phase cleaning effects, which has a structure shown in a formula (I):
Figure BDA0002866713630000011
wherein m is an integer of 1 to 10, n is an integer of 1 to 5, and R is an alkylene group of C1 to C5.
Preferably, n is 3; r is CH2Or C2H4。
The invention also provides a preparation method of the polyamine with the functions of inhibition and solid phase cleaning, which comprises the following steps:
s1) mixing and heating halogenated epoxide, water and an acid catalyst for reaction to obtain a halogenated alcohol solution;
s2) mixing the halohydrin solution with polyethylene polyamine, heating and reacting to obtain an intermediate product I;
s3) mixing the intermediate product I with dihalogenated ethane, and heating to react to obtain an intermediate product II;
s4) mixing the intermediate product II with polyethylene polyamine, heating and reacting to obtain an intermediate product III;
s5) adding acetic acid into the intermediate product III, heating to generate chain termination reaction, and obtaining the polyamine with the functions of inhibiting and cleaning solid phase.
Preferably, the halogenated epoxide is selected from chlorinated epoxides of C3-C7; the acid catalyst is selected from one or more of concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid and dodecylbenzene sulfonic acid; the polyethylene polyamine is selected from one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine; the dihaloethane is selected from dichloroethane.
Preferably, the halogenated epoxide is selected from epichlorohydrin and/or chloroepoxybutane; the polyethylene polyamine is selected from tetraethylenepentamine.
Preferably, the mass ratio of the halogenated epoxide to the water to the acidic catalyst is 38: (60-120): (4-8); the mass ratio of the polyethylene polyamine to the halogenated epoxide in the step S2) is (70-90): 38; the mass ratio of the dihalogenated ethane to the halogenated epoxide is (40-60): 38; in the step S4), the mass ratio of the polyethylene polyamine to the halogenated epoxide is (140-200): 38; the mass ratio of the acetic acid to the halogenated epoxide is (50-70): 38.
preferably, the heating reaction temperature in the step S1) is 85-95 ℃; the heating reaction time is 0.5-1 h;
the heating reaction temperature in the step S2) is 60-90 ℃; the heating reaction time is 1-2 h;
the heating reaction temperature in the step S3) is 80-105 ℃; the heating reaction time is 2-4 h;
the heating reaction temperature in the step S4) is 70-95 ℃; the heating reaction time is 2-4 h;
step S5), the temperature of the chain termination reaction is 50-70 ℃; the heating reaction time is 0.5-1 h.
Preferably, the reactions in steps S1) to S5) are all carried out under stirring; the rotating speed of the stirring is preferably 500-1000 r/min.
The invention also provides a drilling fluid which comprises the polyamine with the inhibiting and solid phase cleaning effects.
The invention provides polyamine with the functions of inhibition and solid phase cleaning, which has a structure shown in a formula (I); wherein m is an integer of 1 to 10, n is an integer of 1 to 5, and R is an alkylene group of C1 to C5. Compared with the prior art, the polyamine provided by the invention has a good solid-phase cleaning effect of an inhibitor under a high-temperature condition, and also has good compatibility in the drilling fluid, and when the polyamine is applied to the drilling fluid, the problem of borehole wall instability of a strong water-sensitive shale stratum can be effectively solved, the problem of drilling fluid slurrying caused by drilling cuttings hydration can be effectively avoided, and borehole wall stability and drilling fluid cleaning are ensured.
Drawings
FIG. 1 is an infrared spectrum of a polyamine having both inhibitory and solid-phase cleaning effects obtained in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides polyamine with both inhibition and solid phase cleaning effects, which has a structure shown in a formula (I):
Figure BDA0002866713630000031
wherein m is an integer of 1-10, n is an integer of 1-5, preferably an integer of 2-4, and more preferably 3; r is C1-C5 alkylene, preferably C1-C4 alkylene, more preferably C1-C3 alkylene, and still more preferably CH2Or C2H4。
The polyamine provided by the invention has a good solid phase cleaning effect of an inhibitor under a high temperature condition, has good compatibility in a drilling fluid, and can be applied to the drilling fluid, so that the problem of borehole wall instability of a strong water-sensitive shale stratum can be effectively solved, the problem of drilling fluid slurrying caused by drilling cuttings hydration can be effectively avoided, and borehole wall stability and drilling fluid cleaning are ensured.
The invention also provides a preparation method of the polyamine with the functions of inhibition and solid phase cleaning, which comprises the following steps: s1) mixing and heating halogenated epoxide, water and an acid catalyst for reaction to obtain a halogenated alcohol solution; s2) mixing the halohydrin solution with polyethylene polyamine, heating and reacting to obtain an intermediate product I; s3) mixing the intermediate product I with dihalogenated ethane, and heating to react to obtain an intermediate product II; s4) mixing the intermediate product II with polyethylene polyamine, heating and reacting to obtain an intermediate product III; s5) adding acetic acid into the intermediate product III, heating to generate chain termination reaction, and obtaining the polyamine with the functions of inhibiting and cleaning solid phase.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
Mixing halogenated epoxide, water and an acid catalyst, and heating for reaction to obtain a halogenated alcohol solution; the halogenated epoxide is preferably C3-C7 chlorinated epoxide, more preferably C3-C5 chlorinated epoxide, and is further preferably epichlorohydrin and/or epoxy chlorobutane; the acidic catalyst is preferably one or more of concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid and dodecylbenzene sulfonic acid; the mass ratio of the halogenated epoxide to water to the acidic catalyst is preferably 38: (60-120): (4-8); in some embodiments provided herein, the halogenated epoxide, water, and acidic catalyst are preferably present in a mass ratio of 38: 60: 4; in some embodiments provided herein, the halogenated epoxide, water, and acidic catalyst are preferably present in a mass ratio of 38: 80: 5; in some embodiments provided herein, the halogenated epoxide, water, and acidic catalyst are preferably present in a mass ratio of 38: 100: 7; in other embodiments provided herein, the halogenated epoxide, water and acidic catalyst are preferably present in a mass ratio of 38: 120: 8; the temperature of the heating reaction is preferably 85-95 ℃; the heating reaction time is preferably 0.5-1 h; in the present invention, the reaction is preferably carried out under stirring; the rotating speed of the stirring is preferably 500-1000 r/min; this step is carried out by hydrolysis to give a halohydrin solution, preferably a chlorohydrin solution.
Mixing the halogenated alcohol solution with polyethylene polyamine, heating and reacting to obtain an intermediate product I; the mass ratio of the polyethylene polyamine to the halogenated epoxide is preferably (70-90): 38; in some embodiments provided herein, the mass ratio of the polyethylenepolyamine to the haloepoxide is preferably 70: 38; in some embodiments provided herein, the mass ratio of the polyethylenepolyamine to the haloepoxide is preferably 80: 38; in other embodiments provided herein, the mass ratio of the polyethylenepolyamine to the haloepoxide is preferably 90: 38; the polyethylene polyamine is preferably one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine, and more preferably tetraethylene pentamine; in the step, the halogenated alcohol and the polyethylene polyamine are subjected to quaternization reaction; the temperature of the heating reaction is preferably 60-90 ℃; the heating reaction time is preferably 1-2 h; in the present invention, the reaction is preferably carried out under stirring; the rotating speed of the stirring is preferably 500-1000 r/min.
Mixing the intermediate product I with dihalogenated ethane, and heating for reaction to obtain an intermediate product II; the dihaloethane is preferably dichloroethane; the mass ratio of the dihaloethane to the halogenated epoxide is preferably (40-60): 38; in some embodiments provided herein, the mass ratio of dihaloethane to halogenated epoxide is preferably 40: 38; in some embodiments provided herein, the mass ratio of dihaloethane to halogenated epoxide is preferably 50: 38; in some embodiments provided herein, the mass ratio of dihaloethane to halogenated epoxide is preferably 60: 38; the temperature of the heating reaction is preferably 80-105 ℃; the heating reaction time is preferably 2-4 h; in the present invention, the reaction is preferably carried out under stirring; the rotating speed of the stirring is preferably 500-1000 r/min. By introducing the dihaloethane, the C atom can be directly connected with the N atom, the high-temperature stability of the molecule is increased, and the temperature resistance of the polyamine is further improved.
Mixing the intermediate product II with polyethylene polyamine, heating and reacting to obtain an intermediate product III; the mass ratio of the polyethylene polyamine to the halogenated epoxide is preferably (140-200): 38; in some embodiments provided herein, the mass ratio of the polyethylenepolyamine to the haloepoxide is preferably 140: 38; in some embodiments provided herein, the mass ratio of the polyethylenepolyamine to the haloepoxide is preferably 160: 38; in some embodiments provided herein, the mass ratio of the polyethylenepolyamine to the haloepoxide is preferably 180: 38; in other embodiments provided herein, the mass ratio of the polyethylenepolyamine to the haloepoxide is preferably 200: 38; the polyethylene polyamine is preferably one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine, and more preferably tetraethylene pentamine; the temperature of the heating reaction is preferably 70-95 ℃; the heating reaction time is preferably 2-4 h; in the present invention, the reaction is preferably carried out under stirring; the rotating speed of the stirring is preferably 500-1000 r/min.
Adding acetic acid into the intermediate product III, and heating to perform a chain termination reaction to obtain polyamine with the functions of inhibiting and cleaning a solid phase; the mass ratio of the acetic acid to the halogenated epoxide is preferably (50-70): 38; in some embodiments provided herein, the mass ratio of acetic acid to halogenated epoxide is preferably 50: 38; in some embodiments provided herein, the mass ratio of acetic acid to halogenated epoxide is preferably 60: 38; in other embodiments provided herein, the mass ratio of acetic acid to haloepoxide is preferably 70: 38; the temperature of the chain termination reaction is preferably 50-70 ℃; the heating reaction time is preferably 0.5-1 h; in the present invention, the reaction is preferably carried out under stirring; the rotating speed of the stirring is preferably 500-1000 r/min.
The preparation method provided by the invention has mild reaction conditions, takes water as a solvent, and has no waste water, waste gas and waste residue.
The invention also provides a drilling fluid which comprises the polyamine with the inhibiting and solid phase cleaning effects.
In order to further illustrate the present invention, the following examples are provided to describe the polyamine, the preparation method and the application thereof, which have both the inhibition and the solid phase cleaning effects.
The reagents used in the following examples are all commercially available.
Example 1
Adding 38g of epoxy chloropropane, 60g of water and 4g of concentrated sulfuric acid into a reaction kettle, controlling the stirring speed at 500r/min, and reacting at the temperature of 85 ℃ for 0.5h to obtain a chlorohydrin solution; adding 70g of tetraethylenepentamine into the chlorohydrin solution, and reacting at the temperature of 60 ℃ for 1.0h to obtain an intermediate product I; adding 40g of dichloroethane into the intermediate product I, and reacting at the temperature of 80 ℃ for 2.0h to obtain an intermediate product II; adding 140g of tetraethylenepentamine into the intermediate product II, and reacting for 2.0h at the temperature of 70 ℃ to obtain an intermediate product III; and adding 50g of acetic acid into the intermediate product III, reacting for 0.5h at the temperature of 50 ℃, and carrying out chain termination reaction to obtain a red brown viscous transparent liquid, namely the polyamine with the functions of inhibiting and solid phase cleaning. The product yield was 93.42%.
The polyamine with the inhibiting and solid phase cleaning functions prepared in the embodiment 1 of the invention has a structure shown in a formula 1:
Figure BDA0002866713630000071
in the formula 1, m is 1-10, n is 3, R is CH2。
The polyamine having both the inhibition and solid phase cleaning effects obtained in example 1 was analyzed by infrared spectroscopy, and the infrared spectrum thereof was as shown in FIG. 1.
Example 2
Adding 38g of epoxy chlorobutane, 80g of water and 5g of concentrated hydrochloric acid into a reaction kettle, controlling the stirring speed at 700r/min, and reacting at the temperature of 90 ℃ for 1.0h to obtain a chlorohydrin solution; adding 80g of tetraethylenepentamine into the chlorohydrin solution, and reacting at 70 ℃ for 2.0h to obtain an intermediate product I; adding 50g of dichloroethane into the intermediate product I, and reacting at the temperature of 90 ℃ for 3.0h to obtain an intermediate product II; adding 160g of tetraethylenepentamine into the intermediate product II, and reacting for 3.0h at the temperature of 80 ℃ to obtain an intermediate product III; adding 60g of acetic acid into the intermediate product III, reacting for 1.0h at the temperature of 60 ℃, and carrying out chain termination reaction to obtain a red brown viscous transparent liquid, namely the polyamine with the functions of inhibiting and solid phase cleaning. The product yield was 92.87%.
The polyamine prepared in example 2 of the present invention, which has both inhibitory and solid phase cleaning effects, has a structure represented by formula 2:
Figure BDA0002866713630000081
In the formula 2, m is 1-10, n is 3, R is C2H4。
Example 3
Adding 38g of epoxy chloropropane, 100g of water and 7g of p-toluenesulfonic acid into a reaction kettle, controlling the stirring speed at 900r/min, and reacting at the temperature of 95 ℃ for 1.0h to obtain a chlorohydrin solution; adding 90g of tetraethylenepentamine into the chlorohydrin solution, and reacting at the temperature of 80 ℃ for 2.0h to obtain an intermediate product I; adding 60g of dichloroethane into the intermediate product I, and reacting for 4.0h at the temperature of 100 ℃ to obtain an intermediate product II; adding 180g of tetraethylenepentamine into the intermediate product II, and reacting for 4.0h at the temperature of 90 ℃ to obtain an intermediate product III; and adding 70g of acetic acid into the intermediate product III, reacting for 1.0h at the temperature of 70 ℃, and carrying out chain termination reaction to obtain a reddish brown viscous transparent liquid, namely the polyamine with the functions of inhibiting and solid phase cleaning. The product yield was 92.65%.
The polyamine with the inhibiting and solid phase cleaning functions prepared in example 3 of the present invention has a structure shown in formula 3:
Figure BDA0002866713630000091
in the formula 3, m is 1-10, n is 3, R is CH2。
Example 4
Adding 38g of epoxy chloropropane, 120g of water and 8g of dodecylbenzene sulfonic acid into a reaction kettle, controlling the stirring speed at 1000r/min, and reacting at the temperature of 95 ℃ for 1.0h to obtain a chlorohydrin solution; adding 90g of tetraethylenepentamine into the chlorohydrin solution, and reacting at 90 ℃ for 2.0h to obtain an intermediate product I; adding 60g of dichloroethane into the intermediate product I, and reacting at 105 ℃ for 4.0h to obtain an intermediate product II; adding 200g of tetraethylenepentamine into the intermediate product II, and reacting for 4.0h at the temperature of 95 ℃ to obtain an intermediate product III; and adding 70g of acetic acid into the intermediate product III, reacting for 1.0h at the temperature of 70 ℃, and carrying out chain termination reaction to obtain a reddish brown viscous transparent liquid, namely the polyamine with the functions of inhibiting and solid phase cleaning. The product yield was 93.96%.
The polyamine with the inhibiting and solid phase cleaning functions prepared in the embodiment 4 of the invention has a structure shown in a formula 4:
Figure BDA0002866713630000101
in the formula 4, m is 1-10, n is 3, R is CH2。
The polyamine with the inhibition and solid phase cleaning effects prepared in the embodiments 1-4 of the invention is subjected to hot rolling for 16h at 200 ℃ in 4% soil slurry (the mass of the polyamine with the inhibition and solid phase cleaning effects is 1.0% of the mass of the soil slurry), and the apparent viscosity AV and the filter loss FL are tested, and the test results are shown in Table 1; the test results of 1.0% of the rock debris recovery rate of the polyamine with the inhibition and solid-phase cleaning effects (the polyamine with the inhibition and solid-phase cleaning effects is 1% of the mass of distilled water) and the relative inhibition rate of the calcium soil-based slurry (the polyamine with the inhibition and solid-phase cleaning effects is 1% of the mass of the calcium soil-based slurry), which are obtained by hot rolling for 16h at 200 ℃, are shown in table 2.
According to GB/T16783.1-2014, oil and gas industry drilling fluid field test part 1: and (4) testing the apparent viscosity and the filtration loss of the drilling fluid composition according to the standard of water-based drilling fluid.
The recovery rate of the rock debris of the polyamine with the inhibiting and solid phase cleaning effects is evaluated according to the following method, and the primary recovery rate and the relative recovery rate of the rock debris are tested, and the specific operation is as follows:
Pouring 350mL of distilled water into an aging tank, adding polyamine which has the inhibiting and solid phase cleaning effects and accounts for 1 percent of the mass of the distilled water, drying 2.0-5.0 mm of rock debris at 103 ℃ for 4 hours, cooling to room temperature, and weighing G0G, placing the rock debris into an aging tank, rolling for 16h at 200 ℃, taking out after cooling, recovering the rock debris by using a sieve with the aperture of 0.42mm, drying for 4h at 103 ℃, cooling to room temperature, weighing the mass of the recovered rock debris and recording as G1(ii) a Then putting the weighed and overweight recovered rock debris into clear water, rolling for 2h at 200 ℃, taking out after cooling, recovering the rock debris by using a sieve with the aperture of 0.42mm, drying for 4h at 103 ℃, cooling to room temperature, weighing the mass of the recovered rock debris and recording as G2(ii) a Respectively calculating the recovery rate R of the shale1Secondary shale recovery rate R2And relative shale recovery rate R:
R1＝G1/G0×100％；
R2＝G2/G0×100％；
R＝R2/R1×100％。
the relative inhibition rate of polyamine with the inhibition and solid phase cleaning effects on the calcareous soil-based slurry is evaluated according to the following method, and the specific method comprises the following steps: 350mL of distilled water was taken, 0.5% sodium carbonate was added and dissolvedThen adding 10% of calcium bentonite, stirring at a high speed for 20min, rolling at 200 ℃ for 16h, cooling and taking out to obtain calcium-soil-based slurry, stirring at a high speed for 5min, and measuring the 100r/min reading of the calcium-soil-based slurry as phi by using a six-speed rotary viscometer; adding 0.5 percent of sodium carbonate and 0.5 percent of polyamine sample which has the functions of inhibiting and solid phase cleaning into 350mL of distilled water, fully dissolving, adding 10 percent of calcium bentonite, stirring at a high speed for 20min, rolling for 16h at 200 ℃, cooling, taking out, stirring at a high speed for 5min, measuring the reading phi of 100r/min of calcium soil base slurry added with polyamine which has the functions of inhibiting and solid phase cleaning by using a six-speed rotational viscometer 1The relative inhibition ratio of the polyamine product with the inhibition and solid phase cleaning effects on the calcareous soil is calculated according to the following formula:
Figure BDA0002866713630000111
in the formula:
b-the relative inhibition ratio of polyamine with both inhibition and solid phase cleaning effects on the calcium soil-based slurry,%;
the reading is stabilized when the rotational speed of the rotational viscometer of the phi-calcareous soil base slurry is 100 r/min;
Ф1and the stable reading is obtained when the rotational speed of the calcareous soil-based slurry rotational viscometer is 100r/min by adding polyamine with the functions of inhibiting and solid phase cleaning.
TABLE 1 results of testing rheology of 4% slurry with polyamine samples having both inhibition and solid phase cleaning
Figure BDA0002866713630000112
Figure BDA0002866713630000121
TABLE 2 test results of rock debris recovery and relative inhibition rate of polyamine samples with both inhibition and solid phase cleaning
Figure BDA0002866713630000122
The data in the table 1 show that after aging at 200 ℃ for 16h, 1.0% of polyamine with the functions of inhibiting and cleaning solid phase has little influence on the apparent viscosity of 4% of soil slurry, and the change value of the apparent viscosity is less than or equal to 1.0 mPa.s; 1.0% of polyamine sample with the functions of inhibiting and solid phase cleaning has small influence on the filtration loss of 4% soil slurry, and the filtration loss change value is less than or equal to 0.6 mL; the polyamine with the functions of inhibiting and cleaning solid phase shows better compatibility with the soil slurry.
As can be seen from the data in Table 2, after aging at 200 ℃ for 16h, the primary recovery rate of 1.0% of the polyamine with the inhibiting and solid-phase cleaning effects is more than 97%, and the relative recovery rate of the rock debris is more than 99%; the relative inhibition rate of 1.0% of polyamine with the inhibition and solid phase cleaning effects on the calcareous soil-based slurry is more than 97%, which shows that the polyamine with the inhibition and solid phase cleaning effects shows excellent strong inhibition and anti-collapse capability on shale well walls and solid phase cleaning capability on drilling fluid.

Claims (9)

1. A polyamine having both inhibitory and solid phase cleaning effects, characterized by having a structure represented by formula (I):
Figure FDA0002866713620000011
wherein m is an integer of 1 to 10, n is an integer of 1 to 5, and R is an alkylene group of C1 to C5.
2. The polyamine of claim 1, the n is 3; r is CH2Or C2H4。
3. A method for preparing polyamine with inhibiting and solid phase cleaning effects, comprising:
s1) mixing and heating halogenated epoxide, water and an acid catalyst for reaction to obtain a halogenated alcohol solution;
s2) mixing the halohydrin solution with polyethylene polyamine, heating and reacting to obtain an intermediate product I;
s3) mixing the intermediate product I with dihalogenated ethane, and heating to react to obtain an intermediate product II;
s4) mixing the intermediate product II with polyethylene polyamine, heating and reacting to obtain an intermediate product III;
s5) adding acetic acid into the intermediate product III, heating to generate chain termination reaction, and obtaining the polyamine with the functions of inhibiting and cleaning solid phase.
4. The process according to claim 3, wherein the halogenated epoxide is selected from chlorinated epoxides of C3 to C7; the acid catalyst is selected from one or more of concentrated sulfuric acid, concentrated hydrochloric acid, p-toluenesulfonic acid and dodecylbenzene sulfonic acid; the polyethylene polyamine is selected from one or more of diethylenetriamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine; the dihaloethane is selected from dichloroethane.
5. The process according to claim 3, characterized in that said halogenated epoxide is selected from epichlorohydrin and/or chloroepoxybutane; the polyethylene polyamine is selected from tetraethylenepentamine.
6. The method according to claim 3, wherein the mass ratio of the halogenated epoxide to the water to the acidic catalyst is 38: (60-120): (4-8); the mass ratio of the polyethylene polyamine to the halogenated epoxide in the step S2) is (70-90): 38; the mass ratio of the dihalogenated ethane to the halogenated epoxide is (40-60): 38; in the step S4), the mass ratio of the polyethylene polyamine to the halogenated epoxide is (140-200): 38; the mass ratio of the acetic acid to the halogenated epoxide is (50-70): 38.
7. the preparation method according to claim 3, wherein the temperature of the heating reaction in the step S1) is 85 to 95 ℃; the heating reaction time is 0.5-1 h;
the heating reaction temperature in the step S2) is 60-90 ℃; the heating reaction time is 1-2 h;
the heating reaction temperature in the step S3) is 80-105 ℃; the heating reaction time is 2-4 h;
the heating reaction temperature in the step S4) is 70-95 ℃; the heating reaction time is 2-4 h;
Step S5), the temperature of the chain termination reaction is 50-70 ℃; the heating reaction time is 0.5-1 h.
8. The method according to claim 3, wherein the reactions in steps S1) -S5) are all carried out under stirring; the rotating speed of the stirring is preferably 500-1000 r/min.
9. A drilling fluid, which is characterized by comprising the polyamine with the inhibition and solid-phase cleaning effects according to any one of claims 1 to 2 or the polyamine with the inhibition and solid-phase cleaning effects prepared by the preparation method according to any one of claims 3 to 8.
CN202011597042.XA 2020-12-28 2020-12-28 Polyamine with inhibition and solid phase cleaning functions, and preparation method and application thereof Active CN113527131B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202311668604.9A CN117886713A (en) 2020-12-28 2020-12-28 Preparation method and application of polyamine with inhibition and solid phase cleaning functions
CN202011597042.XA CN113527131B (en) 2020-12-28 2020-12-28 Polyamine with inhibition and solid phase cleaning functions, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011597042.XA CN113527131B (en) 2020-12-28 2020-12-28 Polyamine with inhibition and solid phase cleaning functions, and preparation method and application thereof

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN202311668604.9A Division CN117886713A (en) 2020-12-28 2020-12-28 Preparation method and application of polyamine with inhibition and solid phase cleaning functions

Publications (2)

Publication Number Publication Date
CN113527131A true CN113527131A (en) 2021-10-22
CN113527131B CN113527131B (en) 2024-03-15

Family

ID=78094311

Family Applications (2)

Application Number Title Priority Date Filing Date
CN202011597042.XA Active CN113527131B (en) 2020-12-28 2020-12-28 Polyamine with inhibition and solid phase cleaning functions, and preparation method and application thereof
CN202311668604.9A Pending CN117886713A (en) 2020-12-28 2020-12-28 Preparation method and application of polyamine with inhibition and solid phase cleaning functions

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN202311668604.9A Pending CN117886713A (en) 2020-12-28 2020-12-28 Preparation method and application of polyamine with inhibition and solid phase cleaning functions

Country Status (1)

Country Link
CN (2) CN113527131B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103087691A (en) * 2011-10-28 2013-05-08 中国石油化工股份有限公司 Polyamine strong inhibitor for drilling fluid, and preparation method thereof
CN103936603A (en) * 2014-04-17 2014-07-23 杨锌荣 Alkyl polyamine quaternary ammonium salt and preparation method thereof
CN106279661A (en) * 2015-05-28 2017-01-04 中国石油化工股份有限公司 A kind of Cationic Polymers Containing Quaternary Ammonium Salts
CN107987808A (en) * 2016-10-26 2018-05-04 中石化石油工程技术服务有限公司 A kind of drilling fluid
CN109694473A (en) * 2017-10-23 2019-04-30 中石化石油工程技术服务有限公司 A kind of drilling fluid polyetheramine shale inhibitor and preparation method thereof and drilling fluid
CN109694697A (en) * 2017-10-23 2019-04-30 中石化石油工程技术服务有限公司 A kind of drilling fluid polyamine shale inhibitor and preparation method thereof and drilling fluid

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103087691A (en) * 2011-10-28 2013-05-08 中国石油化工股份有限公司 Polyamine strong inhibitor for drilling fluid, and preparation method thereof
CN103936603A (en) * 2014-04-17 2014-07-23 杨锌荣 Alkyl polyamine quaternary ammonium salt and preparation method thereof
CN106279661A (en) * 2015-05-28 2017-01-04 中国石油化工股份有限公司 A kind of Cationic Polymers Containing Quaternary Ammonium Salts
CN107987808A (en) * 2016-10-26 2018-05-04 中石化石油工程技术服务有限公司 A kind of drilling fluid
CN109694473A (en) * 2017-10-23 2019-04-30 中石化石油工程技术服务有限公司 A kind of drilling fluid polyetheramine shale inhibitor and preparation method thereof and drilling fluid
CN109694697A (en) * 2017-10-23 2019-04-30 中石化石油工程技术服务有限公司 A kind of drilling fluid polyamine shale inhibitor and preparation method thereof and drilling fluid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘均一: "高性能环保水基钻井液技术研究新进展", 《精细石油化工进展》, vol. 19, no. 06, pages 29 - 34 *

Also Published As

Publication number Publication date
CN117886713A (en) 2024-04-16
CN113527131B (en) 2024-03-15

Similar Documents

Publication Publication Date Title
US2890169A (en) Drilling fluid for wells
US2649160A (en) Method of cementing casings in oil wells
EP2603554B1 (en) Wellbore servicing fluid comprising a cellulose ether
CN106281263B (en) A kind of Ultra-low molecular weight intercalation inhibitor and preparation method thereof
EP3668939A1 (en) Thermally stable surfactants for oil based drilling fluids
CN109694473B (en) Polyether amine shale inhibitor for drilling fluid, preparation method of polyether amine shale inhibitor and drilling fluid
CN106350036B (en) A kind of synthetic method of alkyl tetramine, four amine product of alkyl and its shale control agent
US6303544B1 (en) Modified cellulose products
CN109761823A (en) Shale intercalation inhibitor made of a kind of low molecular weight branching quaternary ammonium salt
CN103958433A (en) Cementing composition comprising anionically- and hydrophobically-modified cellulose ethers and its use
US5783526A (en) Process to enhance removal of adhering solids from the surface of wellbores and sand control devices therein
CN106496048A (en) A kind of alkyl gemini quaternary ammonium salt and its synthetic method
CN106380407B (en) A kind of Ultra-low molecular weight dendroid alkyl hexamine shale control agent and its synthetic method
CN106854259A (en) A kind of water-base drilling fluid fluid loss additive and preparation method thereof
CN113527131A (en) Polyamine with inhibition and solid phase cleaning functions, and preparation method and application thereof
DK2844715T3 (en) rheology modifiers
CN109912428B (en) Preparation method of N-alkylated triamino star ultra-low molecular inhibitor
CN111763504B (en) Environment-friendly temperature-resistant ether amine shale inhibitor and water-based drilling fluid prepared from same
CN111542583B (en) Substituted sugars or glycosides and their use in drilling fluid compositions
US7595391B2 (en) Crosslinked polysaccharides and methods of making and using crosslinked polysaccharides
CN104629094B (en) A kind of hydrophobic starch-nano-calcium carbonate calcium complexes and preparation method
CN111320661A (en) Polyamino sulfonated alkyl glycoside, preparation method thereof and drilling fluid
US3493561A (en) Chemically oxidized starch dispersant
US3879298A (en) Controlling salt contaminated drilling fluids with ethylene dicarboxylic acid
CN104877651B (en) A kind of drilling fluid composition and drilling fluid and its application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant