CN112375555B - Preparation method of organic aluminum crosslinking agent capable of crosslinking with W/O inverse emulsion type drag reducer - Google Patents
Preparation method of organic aluminum crosslinking agent capable of crosslinking with W/O inverse emulsion type drag reducer Download PDFInfo
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- CN112375555B CN112375555B CN202011249440.2A CN202011249440A CN112375555B CN 112375555 B CN112375555 B CN 112375555B CN 202011249440 A CN202011249440 A CN 202011249440A CN 112375555 B CN112375555 B CN 112375555B
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- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
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Abstract
The invention relates to a preparation method of an organic aluminum cross-linking agent capable of being cross-linked with a W/O inverse emulsion type drag reducer, which comprises the following steps: (1) Dissolving organic aluminum in water in a reaction kettle, stirring until the organic aluminum is completely dissolved, and preparing a mixed solution I, wherein the mass fraction of a first organic aluminum in the mixed solution I is 6-7%, and the mass fraction of a second organic aluminum in the mixed solution I is 1-2%; (2) Heating the mixed solution I obtained in the step (1) to 50-90 ℃, and dropwise adding an organic complexing ligand into the mixed solution I while stirring to obtain a mixed solution II, wherein the mass fraction of an organic matter serving as the complexing ligand in the mixed solution II is 5-6%; (3) And (3) reacting the mixed solution II in the step (2) at a constant temperature of 50-90 ℃ for 3-5h, and cooling to room temperature to obtain a light yellow uniform transparent clear liquid, namely the organic aluminum crosslinking agent. The invention can realize the on-line mixing of the glue solution, reduce the fracturing modification difficulty of the shale oil-gas reservoir and improve the modification efficiency.
Description
Technical Field
The invention relates to the technical field of fracturing modification of oil and gas reservoirs, in particular to a preparation method of an organic aluminum crosslinking agent capable of crosslinking with a W/O inverse emulsion type drag reducer.
Background
Along with the increase of the shale gas burial depth and the horizontal segment length, the use amount of the fracturing fluid is increased in the reservoir transformation process, the fracturing fluid is required to be simply prepared and injected immediately, and the fracturing fluid is required to have the performance of changing viscosity in real time so as to meet the process requirements of different sand adding and the like. At present, shale gas exploitation mainly adopts a sand fracturing mode of 'preposed acid + slickwater + glue solution', wherein the preposed acid is less in use amount and prepared by an acid pry and used for relieving near-well pollution and reducing fracture pressure, slickwater mainly adopts W/O (W/O) inverse emulsion type drag reducer to realize online mixing, viscosity can be changed by adjusting the drag reducer, and the viscosity of the slickwater is generally not more than 20mPa & s in consideration of economy. The glue solution is pre-mixed in a liquid tank by mainly adopting a powder thickening agent, is pumped to the bottom of a well by a sand mixer during fracturing, and is difficult to realize on-line mixing. Therefore, the organic aluminum cross-linking agent capable of being cross-linked with the W/O inverse emulsion type drag reducer disclosed by the invention can realize that the whole process of 'slick water + glue solution' can be mixed with the fracturing fluid on line, namely the W/O inverse emulsion type drag reducer realizes the on-line preparation of the slick water and the glue solution to achieve the purpose of real-time viscosity change of the fracturing fluid, thereby simplifying the fluid preparation process, reducing the labor intensity of workers and realizing cost reduction and efficiency improvement.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of an organic aluminum crosslinking agent capable of crosslinking with a W/O inverse emulsion type drag reducer, which can realize on-line blending of glue solution, reduce the fracturing modification difficulty of shale oil and gas reservoirs and improve the modification efficiency.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method of making an organoaluminium crosslinker crosslinkable with a W/O inverse emulsion drag reducer is constructed comprising the steps of:
(1) Dissolving organic aluminum in water in a reaction kettle, stirring until the organic aluminum is completely dissolved to prepare a mixed solution I, wherein the mass fraction of the first organic aluminum in the mixed solution I is 6-7%, and the mass fraction of the second organic aluminum in the mixed solution I is 1-2%;
(2) Heating the mixed solution I obtained in the step (1) to 50-90 ℃, dropwise adding an organic complexing ligand into the mixed solution I while stirring to obtain a mixed solution II, wherein the mass fraction of an organic matter serving as the complexing ligand in the mixed solution II is 5-6%;
(3) And (3) reacting the mixed solution II in the step (2) at a constant temperature of 50-90 ℃ for 3-5h, and cooling to room temperature to obtain a light yellow uniform transparent clear liquid, namely the organic aluminum crosslinking agent.
In the above scheme, the first organic aluminum is polyaluminum chloride, and the second organic aluminum is aluminum hypoacetate.
In the scheme, the organic matter serving as the complexing ligand is one or more of citric acid, sodium gluconate, sodium acetate and triethanolamine.
In the scheme, water in the mixed solution I is inorganic salt water, the mass fraction of the inorganic salt is 1-3%, and the inorganic salt is one or a mixture of sodium chloride, potassium chloride and ammonium chloride.
In the above scheme, the W/O inverse emulsion type drag reducer is carboxyl-containing inverse emulsion polymerization type modified polyacrylamide.
The organic aluminum cross-linking agent capable of being cross-linked with the W/O inverse emulsion type drag reducer, prepared by the invention, comprises an organic aluminum which is polyaluminum chloride and aluminum hypophosphite, provides aluminum ions, and an organic matter which is one or more of citric acid, sodium gluconate, sodium acetate and triethanolamine and serves as a ligand, and organic complex reaction is carried out at the temperature of 50-90 ℃. The crosslinking agent prepared by the invention can be crosslinked with the W/O inverse emulsion type drag reducer for three reasons: firstly, a cross-linking agent provides a plurality of stable organic ligands, and can be cross-linked with a plurality of cross-linkable functional groups such as hydroxyl, carboxyl, acylamino, carbonyl and the like in the W/O emulsion drag reducer, wherein polyaluminum chloride is composed of a plurality of polyhydroxy complexes, is an aluminum-containing organic complex, and is further complexed by adopting the organic ligands to form a stable multi-ligand complex; the aluminum hypoacetate is complexed with one or more organic ligand species to form a plurality of stable complex ligand species, further enhancing the probability of cross-linking the complex ligand species with the cross-linkable functional group. And secondly, the polyaluminium chloride is excessive in the complexing reaction process, and the polyaluminium chloride which does not participate in the complexing reaction has positive charges, so that the polyaluminium chloride can preferentially adsorb components such as white oil, diesel oil and the like in the W/O inverse emulsion type drag reducer, and the reaction probability of other complexing ligands and the crosslinkable functional group is increased. And thirdly, the complexing reaction is carried out in monovalent inorganic saline, monovalent metal ions can attract negative charges ionized from carboxyl, and the crosslinking effect is improved.
The preparation method of the organic aluminum crosslinking agent capable of crosslinking with the W/O inverse emulsion type drag reducer has the following beneficial effects:
(1) The cross-linking agent can be cross-linked with the W/O inverse emulsion type drag reducer, so that the on-line mixing of the glue solution can be realized, namely the W/O inverse emulsion type drag reducer realizes the on-line preparation of slick water and the glue solution to achieve the purpose of real-time viscosity change of the fracturing fluid, thereby simplifying the fluid preparation process, reducing the labor intensity of workers and realizing cost reduction and efficiency improvement;
(2) The cross-linking agent can be cross-linked with the W/O inverse emulsion type drag reducer and various modified polyacrylamide thickening agents at normal temperature, and the defect that the conventional cross-linking agent is not cross-linked at normal temperature is overcome;
(3) The cross-linking agent is neutral, can be cross-linked with the W/O inverse emulsion type drag reducer under the neutral condition, does not need to use a pH regulator to regulate the pH of the prepared liquid water in the using process, and is convenient for field operation.
Drawings
The invention will be further described with reference to the following drawings and examples, in which:
FIG. 1 is a cross-linking rheological curve of a cross-linking agent and a W/O inverse emulsion drag reducer of the present invention;
FIG. 2 shows the cross-linking rheological curve of the cross-linking agent and the powder type modified polyacrylamide thickener.
Detailed Description
For a more clear understanding of the technical features, objects and effects of the present invention, embodiments of the present invention will now be described in detail with reference to the accompanying drawings.
Example 1:
a method of preparing an organic aluminum crosslinking agent crosslinkable with a W/O inverse emulsion drag reducer, comprising the steps of:
(1) Dissolving 6g of polyaluminum chloride and 2g of aluminum diacetate in 92g of 1% potassium chloride salt water in a reaction kettle, and stirring until the solutions are completely dissolved to prepare a mixed solution I;
(2) Heating the mixed solution I obtained in the step (1) to 80 ℃, and slowly adding 6g of sodium gluconate into the mixed solution I while stirring to obtain a mixed solution II;
(3) And (3) reacting the mixed solution II obtained in the step (2) at a constant temperature of 80 ℃ for 3 hours, and cooling to room temperature to obtain a light yellow uniform transparent clear liquid, namely the organic aluminum crosslinking agent.
The polyaluminium chloride and the aluminum subacetate in the preparation method are organic aluminum, and provide chloride ions; the sodium gluconate is an organic matter and provides a ligand; the adopted aqueous solution is a potassium chloride aqueous solution with the mass fraction of 1%.
Example 2:
a method of preparing an organic aluminum crosslinking agent crosslinkable with a W/O inverse emulsion drag reducer, comprising the steps of:
(1) Dissolving 5g of polyaluminum chloride and 1g of aluminum diacetate in 94g of sodium chloride brine with the mass fraction of 1% in a reaction kettle, and stirring until the polyaluminum chloride and the aluminum diacetate are completely dissolved to prepare a mixed solution I;
(2) Heating the mixed solution I obtained in the step (1) to 90 ℃, and slowly adding 5g of sodium gluconate and 1g of triethanolamine into the mixed solution I while stirring to obtain a mixed solution II;
(3) And (3) reacting the mixed solution II obtained in the step (2) at a constant temperature of 90 ℃ for 4 hours, and cooling to room temperature to obtain a light yellow uniform transparent clear liquid, namely the organic aluminum crosslinking agent.
The polyaluminum chloride and the aluminum hypoacetate in the preparation method are organic aluminum and provide chloride ions; sodium gluconate and triethanolamine are used as organic matters to provide ligands; the adopted aqueous solution is sodium chloride aqueous solution with the mass fraction of 1%.
Example 3:
a method of preparing an organic aluminum crosslinking agent crosslinkable with a W/O inverse emulsion drag reducer, comprising the steps of:
(1) Dissolving 6g of polyaluminum chloride and 2g of aluminum diacetate in 92g of potassium chloride salt water with the mass fraction of 2% in a reaction kettle, and stirring until the polyaluminum chloride and the aluminum diacetate are completely dissolved to prepare a mixed solution I;
(2) Heating the mixed solution I obtained in the step (1) to 80 ℃, and slowly adding 5g of sodium gluconate, 1g of triethanolamine and 1g of sodium acetate into the mixed solution I while stirring to obtain a mixed solution II;
(3) And (3) reacting the mixed solution II obtained in the step (2) at a constant temperature of 80 ℃ for 3 hours, and cooling to room temperature to obtain a light yellow uniform transparent clear liquid, namely the organic aluminum crosslinking agent.
The polyaluminum chloride and the aluminum hypoacetate in the preparation method are organic aluminum and provide chloride ions; sodium gluconate, triethanolamine and sodium acetate are used as organic matters to provide ligands; the adopted aqueous solution is a potassium chloride aqueous solution with the mass fraction of 2%.
Experimental example 1:
FIG. 1 is a rheological profile of crosslinking with a W/O inverse emulsion drag reducer using an organoaluminum crosslinking agent described in this invention. The specific experimental steps are as follows: weighing 0.4g of self-made W/O inverse emulsion type drag reducer (carboxyl-containing inverse emulsion polymerization type modified polyacrylamide), slowly adding 99.3g of clear water while stirring to prepare uniform fracturing fluid base fluid (the viscosity of the base fluid is 27mPa & s); 0.3g of the organic aluminum crosslinking agent prepared by the invention is weighed and added into the fracturing fluid base fluid, and the crosslinking fluid is obtained after uniform stirring. 43mL of the crosslinking solution was taken and subjected to rheological test in a Haake rheometer bowl for 170s -1 Shearing at 85 deg.C for 1 hr, and viscosity of fracturing fluid>50 mPas. Experimental results show that the organic aluminum cross-linking agent prepared by the invention is cross-linked with the W/O inverse emulsion type drag reducer to form a stable cross-linked gel system, and has better temperature resistance, shear resistance and viscoelasticity.
Experimental example 2:
FIG. 2 is a rheological profile of crosslinking with a powder-type modified polyacrylamide thickener using an organoaluminum crosslinking agent as described in this invention. Tool for measuringThe experimental procedure was as follows: weighing 0.25g of self-made powder type modified polyacrylamide thickening agent, and slowly adding 99.45g of clear water while stirring to prepare uniform fracturing fluid base fluid (the viscosity of the base fluid is 36mPa & s); 0.3g of the organic aluminum crosslinking agent prepared by the invention is weighed and added into the fracturing fluid base fluid, and the crosslinking fluid is obtained after uniform stirring. 43mL of the crosslinking solution was taken and subjected to rheological test in a Haake rheometer bowl for 170s -1 Shearing at 85 deg.C for 1 hr, and viscosity of fracturing fluid>50 mPas. Experimental results show that the organic aluminum cross-linking agent prepared by the invention is cross-linked with the powder type modified polyacrylamide thickening agent to form a stable cross-linked gel system, and the cross-linked gel system has better temperature resistance, shear resistance and viscoelasticity.
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative and not restrictive, and it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (1)
1. A method for preparing an organic aluminum crosslinking agent crosslinkable with a W/O inverse emulsion type drag reducer, comprising the steps of:
(1) Dissolving organic aluminum in water in a reaction kettle, stirring until the organic aluminum is completely dissolved to prepare a mixed solution I, wherein the mass fraction of the first organic aluminum in the mixed solution I is 6-7%, and the mass fraction of the second organic aluminum in the mixed solution I is 1-2%;
(2) Heating the mixed solution I obtained in the step (1) to 50-90 ℃, dropwise adding an organic complexing ligand into the mixed solution I while stirring to obtain a mixed solution II, wherein the mass fraction of an organic matter serving as the complexing ligand in the mixed solution II is 5-6%;
(3) Reacting the mixed solution II obtained in the step (2) at a constant temperature of 50-90 ℃ for 3-5h, and cooling to room temperature to obtain a light yellow uniform transparent clear liquid, namely the organic aluminum crosslinking agent;
the first organic aluminum is polyaluminum chloride, and the second organic aluminum is aluminum hypophosphite; the organic matter serving as the complexing ligand is one or more of citric acid, sodium gluconate, sodium acetate and triethanolamine;
the water in the mixed solution I is inorganic salt water, the mass fraction of the inorganic salt is 1-3%, and the inorganic salt is one or more of sodium chloride, potassium chloride and ammonium chloride; the W/O inverse emulsion type drag reducer is carboxyl-containing inverse emulsion polymerization type modified polyacrylamide.
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| US4488975A (en) * | 1982-12-13 | 1984-12-18 | Halliburton Company | High temperature stable crosslinked gel fracturing fluid |
| CN105712865B (en) * | 2014-12-02 | 2019-05-07 | 中国石油天然气股份有限公司 | Solid citric acid aluminum crosslinker, preparation method and its application |
| CN108456513B (en) * | 2017-02-20 | 2021-09-10 | 中国石油化工股份有限公司 | Organic aluminum crosslinking agent for fracturing fluid, preparation method and application |
| CN108084986A (en) * | 2017-12-21 | 2018-05-29 | 中国石油集团川庆钻探工程有限公司工程技术研究院 | A kind of recyclable polymer fracturing fluid crosslinking agent and its preparation method and application |
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