CN113403046A - Shrinkage-expansion agent for preventing borehole wall instability in oil extraction and drilling processes of high-argillaceous oil reservoirs and preparation method thereof - Google Patents

Shrinkage-expansion agent for preventing borehole wall instability in oil extraction and drilling processes of high-argillaceous oil reservoirs and preparation method thereof Download PDF

Info

Publication number
CN113403046A
CN113403046A CN202110514070.9A CN202110514070A CN113403046A CN 113403046 A CN113403046 A CN 113403046A CN 202110514070 A CN202110514070 A CN 202110514070A CN 113403046 A CN113403046 A CN 113403046A
Authority
CN
China
Prior art keywords
quaternary ammonium
ammonium salt
shrinkage
argillaceous
agent
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
CN202110514070.9A
Other languages
Chinese (zh)
Other versions
CN113403046B (en
Inventor
侯影飞
王刚
郭宁
冷晓燕
蒋驰
王明
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 University of Petroleum East China
Original Assignee
China University of Petroleum East China
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 University of Petroleum East China filed Critical China University of Petroleum East China
Priority to CN202110514070.9A priority Critical patent/CN113403046B/en
Publication of CN113403046A publication Critical patent/CN113403046A/en
Application granted granted Critical
Publication of CN113403046B publication Critical patent/CN113403046B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504Compositions based on water or polar solvents
    • C09K8/506Compositions based on water or polar solvents containing organic compounds
    • C09K8/508Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/5086Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/121Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from organic halides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10Definition of the polymer structure
    • C08G2261/14Side-groups
    • C08G2261/142Side-chains containing oxygen
    • C08G2261/1422Side-chains containing oxygen containing OH groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10Definition of the polymer structure
    • C08G2261/16End groups
    • C08G2261/164End groups comprising organic end groups
    • C08G2261/1644End groups comprising organic end groups comprising other functional groups, e.g. OH groups, NH groups, COOH groups or boronic acid
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/12Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Epoxy Compounds (AREA)

Abstract

The invention provides a shrinkage-expansion agent for preventing borehole wall instability in the oil extraction and drilling process of a high-argillaceous oil reservoir and a preparation method thereof, and relates to the technical field of drilling fluids. The shrinking and swelling agent is prepared from a quaternary ammonium salt, a calcium chloride solution and an acrylic acid solution, wherein the mass ratio of the quaternary ammonium salt to the calcium chloride to the acrylic acid is 1: 2: and 2, wherein the quaternary ammonium salt consists of bimolecular quaternary ammonium salt and a long-chain quaternary ammonium salt polymer, the bimolecular quaternary ammonium salt is synthesized by N, N-dimethyl dodecyl tertiary amine and 1, 3-dibromopropane in an ethanol solution, and the quaternary ammonium salt long-chain polymer is synthesized by N, N-dimethyl dodecyl tertiary amine and epichlorohydrin in the ethanol solution by taking azodiisobutyronitrile as an initiator. The swelling and shrinking agent prepared by the invention has good water solubility, can firmly adsorb clay particles, has obvious swelling and shrinking effect, can reach more than 40% when the mass fraction is 2%, effectively solves various problems caused by the expansion of the shale, makes up the vacancy of high-efficiency swelling and shrinking agent in domestic market, and is beneficial to the development of oil extraction industry.

Description

Shrinkage-expansion agent for preventing borehole wall instability in oil extraction and drilling processes of high-argillaceous oil reservoirs and preparation method thereof
Technical Field
The invention relates to the technical field of drilling fluid, in particular to a shrinkage-expansion agent for preventing borehole wall instability in the oil extraction and drilling process of a high-argillaceous oil reservoir and a preparation method thereof.
Background
In the oil production drilling process, drilling fluid must be injected into a well in order to carry, suspend drill cuttings and lubricate and protect a drill bit, and because the underground formation environment is very complex, the injection of the drilling fluid can cause a series of problems of well wall instability. And as the drilling depth deepens, the borehole wall instability can cause a series of problems, and safety accidents can be caused besides the great reduction of the production efficiency. By analyzing the borehole wall instability, the borehole wall instability is generally considered to be caused by the hydration expansion of the shale.
The currently adopted swelling shrinkage agent is a new generation of shale inhibitor, and compared with a conventional clay stabilizer, the swelling shrinkage agent has better expansibility, and also has certain sand inhibition and swelling shrinkage effects, so that the acidification and blockage removal of a water injection well are facilitated to be improved, and the anti-swelling effective period of a drilling well is greatly shortened. The swelling agent can recover the permeability of an oil and gas reservoir to a certain extent by reducing the volume of the swelled clay as the name suggests, so that the water injection pressure is reduced, and the oil recovery rate is improved.
The research finds that the shrinking and swelling mechanism of the shrinking and swelling agent acting on the montmorillonite is generally four:
(1) a compressed double layer mechanism; the cation in the swelling agent neutralizes the negative charge on the surface of the montmorillonite crystal, so that the Zeta potential is reduced, the double electric layer is compressed, and the volume of the clay is macroscopically shrunk. (2) A water molecule removal mechanism; the strong oxidizing substance carried in the swelling shrinking agent acts on the clay crystal to remove water molecules adsorbed in the montmorillonite crystal, shrink the volume of the clay and restore the permeability of the reservoir. (3) An ion exchange mechanism; each kind of cation has different hydration energy, the swelling of the montmorillonite crystal is caused by the ion with larger hydration energy, the particle with larger hydration energy can absorb more water molecules, so the low hydration energy cation carried in the swelling shrinking agent can be utilized to replace the ion with high hydration energy, thereby reducing the volume of the montmorillonite crystal, and the cation can also play the role of preventing swelling when being absorbed on the crystal surface. (4) A multi-point adsorption mechanism; the long-chain swelling and shrinking agent molecules are adopted, the bridging effect of the swelling and shrinking agent molecules is exerted through multi-point adsorption, and dispersed clay crystals are adsorbed together, so that the dispersion and the transportation of a part of the clay crystals are prevented, and the aims of improving the permeability of an oil and gas reservoir and improving the oil extraction efficiency are finally fulfilled.
For example, patent document CN 107338036 a proposes "a shrinkage-swelling type solidfree workover fluid and a preparation method thereof", which is prepared by compounding potassium chloride, sodium sulfite, cationic quaternary ammonium salt, a nonionic surfactant, a silicone surface, polysorbate and xanthan gum in a certain ratio, and can greatly improve the effective permeability of the fluid in a laboratory, and the shrinkage-swelling rate measured in a laboratory reaches 82%. However, the preparation process of the shrinkage-expansion type solid-free workover fluid in the patent is complex, the flow is complicated, and the shrinkage-expansion type solid-free workover fluid is not suitable for large-scale production.
In addition, patent document CN 111607375 a proposes "a swelling and swelling preventing agent for low permeability sensitive oil reservoir and a preparation method thereof", which is prepared by polymerizing methacryloyloxyethyl trimethyl ammonium chloride and 3-allyloxy-2-hydroxy-1-propanesulfonic acid, wherein the swelling preventing rate can reach more than 98% and the swelling shrinkage rate is 40% at a concentration of 500 ppm. However, the swelling agent synthesized by the method disclosed by the patent has the problems of too large molecular weight, poor control of polymerization degree, complicated reaction process and deviation of water solubility, and the process of preparing the drilling fluid is time-consuming and is not beneficial to actual field construction.
Disclosure of Invention
Aiming at the phenomenon of borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil reservoir, the invention provides the shrinkage-expansion agent for preventing borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil reservoir and the preparation method thereof, so that various problems caused by mud shale expansion are effectively solved, the vacancy of the high-efficiency shrinkage-expansion agent in the domestic market is made up, and the development of the oil extraction industry is facilitated.
The invention adopts the following technical scheme:
a shrinkage-expansion agent for preventing borehole wall instability in the oil extraction and drilling process of a high-argillaceous oil reservoir is prepared from a quaternary ammonium salt, a calcium chloride solution and an acrylic acid solution, wherein the calcium chloride solution and the acrylic acid solution play a role in synergistic shrinkage-expansion, and the quaternary ammonium salt consists of a bimolecular quaternary ammonium salt and a long-chain quaternary ammonium salt polymer; the bimolecular quaternary ammonium salt is synthesized by N, N dimethyl dodecyl tertiary amine and 1,3 dibromopropane in ethanol solution, and NH with lower hydration energy is utilized4 +High-hydration-energy cations in the clay crystal are replaced, water molecules absorbed in the crystal are released, and the effect of ion replacement is achieved; the quaternary ammonium salt long-chain polymer is synthesized by N, N dimethyl dodecyl tertiary amine and epoxy chloropropane in an ethanol solution by taking azodiisobutyronitrile as an initiator, plays a role in multi-point adsorption, and prevents the dispersion and the transportation of clay particles by bridging and connecting the clay particles dispersed in water;
the reaction equation is:
Figure BDA0003061387190000021
preferably, the mass ratio of the quaternary ammonium salt, the calcium chloride and the acrylic acid in the swelling shrinking agent is 1: (1.9-2.1): (1.9-2.1) and the total mass fraction is 2-4%.
Preferably, the mass ratio of the quaternary ammonium salt, the calcium chloride and the acrylic acid in the swelling shrinking agent is 1: 2: 2, the total mass fraction is 2%.
Preferably, the mass fraction of the initiator azobisisobutyronitrile is 0.2-0.4%, and the molar ratio of 1, 3-dibromopropane to epichlorohydrin is (3.5-4.5): 1.
preferably, the mass fraction of the ethanol solution is 60%, the mass fraction of the initiator azobisisobutyronitrile is 0.2%, and the molar ratio of the 1, 3-dibromopropane to the epichlorohydrin is 4: 1.
the preparation method of the shrinkage-expansion agent for preventing the borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil reservoir comprises the following steps:
a. sequentially adding an ethanol solution and N, N-dimethyl dodecyl tertiary amine into a three-neck flask to obtain an amine solution, stirring the amine solution, raising the temperature of a system to 55-65 ℃ of a preheating temperature, slowly dripping 1, 3-dibromopropane into the system at a dripping speed of 0.5-1 ml/min, after the dripping of the 1, 3-dibromopropane is completed, raising the temperature of the system to 75-80 ℃ of a reaction temperature for quaternization, and preparing a bimolecular quaternary ammonium salt compound;
b. reducing the temperature of the system to 55-65 ℃ of preheating temperature, adding initiator azobisisobutyronitrile and epoxy chloropropane into a three-neck flask, then increasing the temperature of the system to 80-85 ℃ of reaction temperature for ring-opening addition polymerization, maintaining the temperature constant, after the reaction is finished, putting the three-neck flask into a vacuum oven, and drying the solvent in the system, wherein the shrinkage-expansion agent is used for preventing the instability of a well wall in the oil production and drilling process of a high-argillaceous oil reservoir.
Preferably, in the step a, the time of the quaternization reaction is 10-12 h.
Preferably, in the step b, the time of the ring-opening addition polymerization reaction is 6-8 h.
Preferably, in the step b, the temperature of the vacuum oven is 60 ℃, and the drying time is 5-7 h.
The invention has the beneficial effects that:
the swelling shrinking agent provided by the invention adopts bimolecular quaternary ammonium salt cations, and the efficiency of ion exchange is greatly improved by utilizing high-density cations, so that the swelling shrinking efficiency of clay is improved.
Secondly, the swelling and shrinking agent provided by the invention has good water solubility, is convenient for field construction, greatly improves the working efficiency, has low raw material cost and simple synthesis process, and is suitable for large-scale production.
The shrinking and swelling agent provided by the invention can be firmly adsorbed on the surface of the clay mineral, the action time is long, the effect is stable, and the shrinking and swelling rate can reach more than 40% when the mass fraction of the shrinking and swelling agent is 2%.
Drawings
FIG. 1 is an infrared spectrum of bimolecular quaternary ammonium salt in the swelling shrinking agent.
FIG. 2 is an infrared spectrum of a quaternary ammonium salt long-chain polymer in the swelling shrinking agent.
Detailed Description
The invention is described in detail below with reference to the following figures and examples:
the shrinkage-expansion agent for preventing the borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil reservoir is prepared from 2 mass percent of calcium chloride solution, 3 mass percent of acrylic acid solution and 1 mass ratio of quaternary ammonium salt, calcium chloride and acrylic acid: (1.9-2.1): (1.9-2.1), wherein the total mass fraction is 2% -4%, the quaternary ammonium salt consists of bimolecular quaternary ammonium salt and long-chain quaternary ammonium salt polymer, the bimolecular quaternary ammonium salt is synthesized by N, N dimethyl dodecyl tertiary amine and 1,3 dibromopropane in ethanol solution, and an infrared spectrogram of the bimolecular quaternary ammonium salt is shown in figure 1; the quaternary ammonium salt long-chain polymer is synthesized by taking azobisisobutyronitrile with the mass fraction of 0.2-0.4% as an initiator in an ethanol solution from N, N dimethyl dodecyl tertiary amine and epichlorohydrin, wherein the molar ratio of 1, 3-dibromopropane to epichlorohydrin is (3.5-4.5): 1, FIG. 2 shows an infrared spectrogram of a quaternary ammonium salt long-chain polymer, wherein the mass fraction of an ethanol solution adopted in the preparation process is 60%.
The preparation method of the shrinkage-expansion agent for preventing the borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil reservoir comprises the following steps:
a. adding an ethanol solution and N, N-dimethyl dodecyl tertiary amine into a three-neck flask in sequence to obtain an amine solution, stirring the amine solution, raising the temperature of a system to 55-65 ℃ of a preheating temperature, slowly dripping 1, 3-dibromopropane into the system at a dripping speed of 0.5-1 ml/min, after the dripping of the 1, 3-dibromopropane is completed, raising the temperature of the system to 75-80 ℃ of a reaction temperature, and carrying out quaternization for 10-12 h to obtain the bimolecular quaternary ammonium salt compound.
b. Reducing the temperature of the system to 55-65 ℃ of preheating temperature, adding initiator azodiisobutyronitrile and epoxy chloropropane into a three-neck flask, raising the temperature of the system to 80-85 ℃ of reaction temperature for ring-opening addition polymerization reaction for 6-8 h, maintaining the temperature constant, after the reaction is finished, putting the three-neck flask into a vacuum oven at 60 ℃ for drying for 5-7 h, and drying the solvent in the system to obtain the swelling shrinkage agent for preventing borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil reservoir.
Example 1
The swelling shrinking agent is prepared from a quaternary ammonium salt, a calcium chloride solution and an acrylic acid solution, wherein the mass fraction of the calcium chloride solution is 2%, the mass fraction of the acrylic acid solution is 3%, and the mass ratio of the quaternary ammonium salt to the calcium chloride to the acrylic acid is 1: 1.9: 1.9, the total mass fraction is 2%, wherein the quaternary ammonium salt is composed of bimolecular quaternary ammonium salt and long-chain quaternary ammonium salt polymer, the bimolecular quaternary ammonium salt is synthesized by N, N-dimethyl dodecyl tertiary amine and 1, 3-dibromopropane in ethanol solution, the quaternary ammonium salt long-chain polymer is synthesized by N, N-dimethyl dodecyl tertiary amine and epichlorohydrin in ethanol solution by taking azobisisobutyronitrile with the mass fraction of 0.2% as an initiator, and the molar ratio of 1, 3-dibromopropane to epichlorohydrin is 3.5: 1, the mass fraction of the ethanol solution is 60 percent.
The preparation method of the swelling agent comprises the following steps:
a. adding an ethanol solution and N, N-dimethyl dodecyl tertiary amine into a three-neck flask in sequence to obtain an amine solution, stirring the amine solution by using a magnetic stirrer, raising the temperature of a system to 55 ℃ of a preheating temperature, slowly dripping 1, 3-dibromopropane into the system at a dripping speed of 0.5-1 ml/min, after the dripping of the 1, 3-dibromopropane is completed, raising the temperature of the system to 75 ℃ of a reaction temperature, and carrying out quaternization for 10 hours to obtain the bimolecular quaternary ammonium salt compound.
b. Reducing the temperature of the system to 55 ℃ of preheating temperature, adding initiators of azodiisobutyronitrile and epichlorohydrin into a three-neck flask, increasing the temperature of the system to 80 ℃ of reaction temperature for 6 hours of ring-opening addition polymerization reaction, maintaining the temperature constant, and after the reaction is finished, putting the three-neck flask into a vacuum oven at 60 ℃ for drying for 5 hours to obtain the shrinkage-expansion agent for preventing the instability of the well wall in the oil extraction and drilling process of the high-argillaceous oil reservoir.
Example 2
The swelling shrinking agent is prepared from a quaternary ammonium salt, a calcium chloride solution and an acrylic acid solution, wherein the mass fraction of the calcium chloride solution is 2%, the mass fraction of the acrylic acid solution is 3%, and the mass ratio of the quaternary ammonium salt to the calcium chloride to the acrylic acid is 1: 2: and 2, the total mass fraction is 3%, wherein the quaternary ammonium salt consists of bimolecular quaternary ammonium salt and long-chain quaternary ammonium salt polymer, the bimolecular quaternary ammonium salt is synthesized by N, N-dimethyl dodecyl tertiary amine and 1, 3-dibromopropane in an ethanol solution, the quaternary ammonium salt long-chain polymer is synthesized by N, N-dimethyl dodecyl tertiary amine and epoxy chloropropane in an ethanol solution by taking azobisisobutyronitrile with the mass fraction of 0.3% as an initiator, and the molar ratio of 1, 3-dibromopropane to epoxy chloropropane is 4: 1, the mass fraction of the ethanol solution is 60 percent.
The preparation method of the swelling agent comprises the following steps:
a. adding an ethanol solution and N, N-dimethyl dodecyl tertiary amine into a three-neck flask in sequence to obtain an amine solution, stirring the amine solution by using a magnetic stirrer, raising the temperature of a system to a preheating temperature of 60 ℃, slowly dripping 1, 3-dibromopropane into the system at a dripping speed of 0.5-1 ml/min, raising the temperature of the system to a reaction temperature of 75 ℃ after the dripping of the 1, 3-dibromopropane is completed, and carrying out quaternization for 11 hours to prepare the bimolecular quaternary ammonium salt compound.
b. Reducing the temperature of the system to 60 ℃ of preheating temperature, adding initiators of azodiisobutyronitrile and epichlorohydrin into a three-neck flask, then increasing the temperature of the system to 85 ℃ of reaction temperature to carry out ring-opening addition polymerization reaction for 7 hours, maintaining the temperature constant, and after the reaction is finished, putting the three-neck flask into a vacuum oven at 60 ℃ to dry for 6 hours to obtain the shrinkage-expansion agent for preventing the instability of the well wall in the oil extraction and drilling process of the high-argillaceous oil reservoir.
Example 3
The swelling shrinking agent is prepared from a quaternary ammonium salt, a calcium chloride solution and an acrylic acid solution, wherein the mass fraction of the calcium chloride solution is 2%, the mass fraction of the acrylic acid solution is 3%, and the mass ratio of the quaternary ammonium salt to the calcium chloride to the acrylic acid is 1: 2.1: 2.1, the total mass fraction is 4%, wherein the quaternary ammonium salt consists of bimolecular quaternary ammonium salt and long-chain quaternary ammonium salt polymer, the bimolecular quaternary ammonium salt is synthesized by N, N-dimethyl dodecyl tertiary amine and 1, 3-dibromopropane in ethanol solution, the quaternary ammonium salt long-chain polymer is synthesized by N, N-dimethyl dodecyl tertiary amine and epichlorohydrin in ethanol solution by taking azobisisobutyronitrile with the mass fraction of 0.4% as an initiator, and the molar ratio of 1, 3-dibromopropane to epichlorohydrin is 4.5: 1, the mass fraction of the ethanol solution is 60 percent.
The preparation method of the swelling agent comprises the following steps:
a. adding an ethanol solution and N, N-dimethyl dodecyl tertiary amine into a three-neck flask in sequence to obtain an amine solution, stirring the amine solution by using a magnetic stirrer, raising the temperature of a system to a preheating temperature of 65 ℃, slowly dripping 1, 3-dibromopropane into the system at a dripping speed of 0.5-1 ml/min, after the dripping of the 1, 3-dibromopropane is completed, raising the temperature of the system to a reaction temperature of 80 ℃ for quaternization reaction for 11 hours, and preparing the bimolecular quaternary ammonium salt compound.
b. Reducing the temperature of the system to 65 ℃ of preheating temperature, adding initiators of azodiisobutyronitrile and epichlorohydrin into a three-neck flask, increasing the temperature of the system to 80 ℃ of reaction temperature for ring-opening addition polymerization reaction for 8 hours, maintaining the temperature constant, and after the reaction is finished, putting the three-neck flask into a vacuum oven at 60 ℃ for drying for 7 hours to obtain the shrinkage-expansion agent for preventing the instability of the well wall in the oil extraction and drilling process of the high-argillaceous oil reservoir.
In order to further measure the performance of the swelling and shrinking agent prepared in the examples 1-3, the swelling and shrinking effect of the swelling and shrinking agent is measured by adopting the following methods respectively aiming at the swelling and shrinking agent prepared in each example, and the method comprises the following steps:
(1) placing a proper amount of clay into a beaker, placing the beaker into a blowing type constant temperature drying oven with the temperature of 105 ℃ for drying for 3 hours, respectively weighing 0.5g of dried clay, placing the dried clay into 10ml centrifuge tubes with the numbers 1 and 2, respectively adding equal amount of kerosene into the centrifuge tube with the number 1, respectively adding equal amount of water into the centrifuge tube with the number 2, respectively adding equal amount of kerosene and water, shaking uniformly, standing for 2 hours, and processing at 1500 r.min-1Is centrifuged for 15min, and the volume of the liquid in the centrifuge tube with the record number 1 is V0Number 2 the volume of the liquid in the centrifuge tube is V1
(2) Pouring out water in the centrifuge tube with the number 2, adding a swelling and shrinking agent with a fixed mass fraction, shaking up the mixture slightly, standing the mixture for 2 hours at 1500 r.min-1Is centrifuged for 15min, and the volume of the liquid in the centrifuge tube with the number 2 is recorded as V2Calculating the shrinkage and expansionThe shrinkage-expansion ratio of the agent is shown as follows:
Figure BDA0003061387190000061
wherein P represents an expansion ratio.
The shrinkage-expansion ratio of the swelling agent prepared in each example was experimentally measured, the clay before and after the treatment with the swelling agent of the present invention was observed under a microscope, the contact angles of the clay before and after the treatment were compared, and the shrinkage-expansion effect of the swelling agent was expressed by the shrinkage-expansion ratio, as shown in Table 1.
TABLE 1 the effect of the examples on the expansion and contraction of the expansion and contraction agent
Figure BDA0003061387190000062
From the table 1, the shrinkage-expansion rate of the swelling shrinkage agent prepared by the invention is more than 40%, the maximum shrinkage-expansion rate of the swelling shrinkage agent prepared in the example 2 is 44.1%, the swelling shrinkage agent is suitable for solving the problem of borehole wall instability of a high-argillaceous oil reservoir in drilling operation, the defects that the existing clay stabilizer is poor in effect and does not have the function of reducing expanded clay are effectively overcome, and the swelling shrinkage-expansion agent has important engineering application value.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art may make modifications, alterations, additions or substitutions within the spirit and scope of the present invention.

Claims (9)

1. The shrinkage-expansion agent for preventing the borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil reservoir is characterized by being prepared from a quaternary ammonium salt, a calcium chloride solution and an acrylic acid solution, wherein the quaternary ammonium salt consists of a bimolecular quaternary ammonium salt and a long-chain quaternary ammonium salt polymer, the bimolecular quaternary ammonium salt is synthesized from N, N-dimethyl dodecyl tertiary amine and 1, 3-dibromopropane in an ethanol solution, and the quaternary ammonium salt long-chain polymer is synthesized from N, N-dimethyl dodecyl tertiary amine and epichlorohydrin in the ethanol solution by taking azobisisobutyronitrile as an initiator.
2. The shrinkage-expansion agent for preventing the borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil deposit according to claim 1, wherein the mass ratio of the quaternary ammonium salt, the calcium chloride and the acrylic acid in the shrinkage-expansion agent is 1: (1.9-2.1): (1.9-2.1) and the total mass fraction is 2-4%.
3. The shrinkage-expansion agent for preventing the borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil deposit according to claim 2, wherein the mass ratio of the quaternary ammonium salt, the calcium chloride and the acrylic acid in the shrinkage-expansion agent is 1: 2: 2, the total mass fraction is 2%.
4. The shrinkage-expansion agent for preventing the borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil deposit according to claim 2 or 3, characterized in that the mass fraction of the initiator azobisisobutyronitrile is 0.2-0.4%, and the molar ratio of 1, 3-dibromopropane to epichlorohydrin is (3.5-4.5): 1.
5. the shrinkage-swelling agent for preventing the borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil deposit according to claim 4, wherein the mass fraction of the ethanol solution is 60%, the mass fraction of the initiator azobisisobutyronitrile is 0.2%, and the molar ratio of 1, 3-dibromopropane to epichlorohydrin is 4: 1.
6. the preparation method of the swelling shrinkage agent for preventing the borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil deposit according to the claims 1-5, characterized by comprising the following steps:
a. sequentially adding an ethanol solution and N, N-dimethyl dodecyl tertiary amine into a three-neck flask to obtain an amine solution, stirring the amine solution, raising the temperature of a system to 55-65 ℃ of a preheating temperature, slowly dripping 1, 3-dibromopropane into the system at a dripping speed of 0.5-1 ml/min, after the dripping of the 1, 3-dibromopropane is completed, raising the temperature of the system to 75-80 ℃ of a reaction temperature for quaternization, and preparing a bimolecular quaternary ammonium salt compound;
b. reducing the temperature of the system to 55-65 ℃ of preheating temperature, adding initiator azobisisobutyronitrile and epoxy chloropropane into the three-neck flask, then increasing the temperature of the system to 80-85 ℃ of reaction temperature for ring-opening addition polymerization reaction, maintaining the temperature constant, and after the reaction is finished, putting the three-neck flask into a vacuum oven for drying to obtain the shrinkage-expansion agent for preventing the borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil reservoir.
7. The preparation method of the swelling shrinking agent for preventing the borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil deposit according to claim 6, wherein in the step a, the quaternization reaction time is 10-12 hours.
8. The preparation method of the swelling shrinking agent for preventing the borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil deposit according to claim 6, wherein in the step b, the time of the ring-opening addition polymerization reaction is 6-8 hours.
9. The preparation method of the swelling shrinking agent for preventing the borehole wall instability in the oil extraction and drilling process of the high-argillaceous oil deposit according to claim 7 or 8, characterized in that in the step b, the temperature of the vacuum oven is 60 ℃, and the drying time is 5-7 hours.
CN202110514070.9A 2021-05-12 2021-05-12 Shrinkage-expansion agent for preventing borehole wall instability in oil production and drilling processes of high-argillaceous oil reservoirs and preparation method of shrinkage-expansion agent Active CN113403046B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110514070.9A CN113403046B (en) 2021-05-12 2021-05-12 Shrinkage-expansion agent for preventing borehole wall instability in oil production and drilling processes of high-argillaceous oil reservoirs and preparation method of shrinkage-expansion agent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110514070.9A CN113403046B (en) 2021-05-12 2021-05-12 Shrinkage-expansion agent for preventing borehole wall instability in oil production and drilling processes of high-argillaceous oil reservoirs and preparation method of shrinkage-expansion agent

Publications (2)

Publication Number Publication Date
CN113403046A true CN113403046A (en) 2021-09-17
CN113403046B CN113403046B (en) 2023-01-06

Family

ID=77678396

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110514070.9A Active CN113403046B (en) 2021-05-12 2021-05-12 Shrinkage-expansion agent for preventing borehole wall instability in oil production and drilling processes of high-argillaceous oil reservoirs and preparation method of shrinkage-expansion agent

Country Status (1)

Country Link
CN (1) CN113403046B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1556169A (en) * 2004-01-12 2004-12-22 高芒来 Use of single moleule quarternary ammonium salt compound as clay stabilizing, antiexpanding and deblocking extender
CN105198757A (en) * 2015-10-15 2015-12-30 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 Small cationic bisquaternary ammonium salt clay stabilizer and preparation method thereof
CN107434971A (en) * 2016-05-27 2017-12-05 中国石油天然气股份有限公司 A kind of water injection well Swelling-resistant shrinking and swelling agent and its preparation method and application
CN108715755A (en) * 2018-06-27 2018-10-30 长江大学 A kind of Swelling-resistant shrinking and swelling agent and preparation method thereof
US20200071602A1 (en) * 2018-08-29 2020-03-05 Ecolab Usa Inc. Use of multiple charged cationic compounds derived from polyamines for clay stabilization in oil and gas operations

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1556169A (en) * 2004-01-12 2004-12-22 高芒来 Use of single moleule quarternary ammonium salt compound as clay stabilizing, antiexpanding and deblocking extender
CN105198757A (en) * 2015-10-15 2015-12-30 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 Small cationic bisquaternary ammonium salt clay stabilizer and preparation method thereof
CN107434971A (en) * 2016-05-27 2017-12-05 中国石油天然气股份有限公司 A kind of water injection well Swelling-resistant shrinking and swelling agent and its preparation method and application
CN108715755A (en) * 2018-06-27 2018-10-30 长江大学 A kind of Swelling-resistant shrinking and swelling agent and preparation method thereof
US20200071602A1 (en) * 2018-08-29 2020-03-05 Ecolab Usa Inc. Use of multiple charged cationic compounds derived from polyamines for clay stabilization in oil and gas operations

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
乌效鸣: "《钻井液与岩土工程浆材》", 31 July 2014, 中国地质大学出版社 *
董军: "阳离子聚合物和双季铵盐粘土稳定剂的合成及性能研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技I辑》 *

Also Published As

Publication number Publication date
CN113403046B (en) 2023-01-06

Similar Documents

Publication Publication Date Title
US4462718A (en) Oil well treating method and composition
US4374739A (en) Oil well treating method and composition
US4366074A (en) Oil well treating method and composition
US4366072A (en) Oil well treating method and composition
US4366071A (en) Oil well treating method and composition
US4366073A (en) Oil well treating method and composition
EP0197684B1 (en) Reduction of water permeability of subterranean formation
US20050194142A1 (en) Compositions and methods for controlling unconsolidated particulates
CN103897121B (en) AM/AA/N β CD polymer ions liquid [bquin] BF4 compound clays stabilizers and its synthetic method
CN112457838B (en) Novel acid-resistant and salt-resistant shrinking and swelling agent and preparation method thereof
CN108102099B (en) Preparation method of high-temperature clay stabilizer for oil field
US11987749B2 (en) Polymers and nanoparticles for flooding
US4497596A (en) Method of minimizing fines migration in a subterranean formation
CN103539902A (en) Preparation method of high temperature resistant contraction-expansion system for promoting stratum clay modification
CN108841366B (en) High-temperature leakage-proof plugging agent and preparation method and application thereof
CN113403046B (en) Shrinkage-expansion agent for preventing borehole wall instability in oil production and drilling processes of high-argillaceous oil reservoirs and preparation method of shrinkage-expansion agent
CN114350330B (en) High-strength strong-adsorption plugging agent and oil-based drilling fluid
CN105754579A (en) Clay anti-swelling and swelling shrinkage agent and preparation method thereof
CN108239523A (en) A kind of ionic liquid shale control agent
CN112196503A (en) Method for improving injectability of oil displacement polymer
CN107338036B (en) Shrinkage-expansion type solid-free workover fluid and preparation method thereof
CN115260404A (en) High-temperature-resistant hydrophobic nano plugging agent for water-based drilling fluid and preparation method and application thereof
CN115273997A (en) Temporary plugging acidification design method utilizing temperature response type temporary plugging agent
CN115286750A (en) Self-degradation temporary plugging agent and preparation method and application thereof
CN111925477B (en) Preparation method of fluorine-containing thickening agent capable of thickening hydrochloric acid solution

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