Preparation method of high-temperature-resistant and anti-shearing organic boron-zirconium cross-linking agent

Abstract

The invention relates to the technical field of oil field fracturing fluid, in particular to a preparation method of a high-temperature-resistant and anti-shearing organic boron-zirconium cross-linking agent. According to the technical scheme, the method comprises the following steps: 1) weighing deionized water and an alcohol stabilizer, adding the weighed deionized water and alcohol stabilizer into a reaction container, adding inorganic zirconium salt into the reaction container, and stirring until the inorganic zirconium salt is completely dissolved; 2) adding an organic ligand, stirring to dissolve the organic ligand, and continuously stirring for 0.5 hour; (3) adding a complexing agent, heating to 50-70 DEG C, stirring and keeping the temperature for 11-15 hours to obtain an organic zirconium cross-linking agent; and 4) adding the organic zirconium cross-linking agent obtained in the step 3) and a boron compound into a reaction container according to a ratio, and stirring at room temperature until the organic zirconium cross-linking agent and the boron compound are completely dissolved so as to obtain the organic boron zirconium cross-linking agent, and the preparation method has the beneficial effects that the prepared cross-linking agent has excellent temperature resistance and shear resistance, and is simple and convenient to operate, mild in condition, wide in raw material source and low in price.

Description

Technical Field

[0001] The invention relates to the technical field of oilfield fracturing fluid, and in particular to a method for preparing a high temperature resistant and shear resistant organic boron zirconium cross-linking agent. Background Art

[0002] The commonly used crosslinkers in oilfield fracturing fluids are generally organic boron crosslinkers and organic zirconium crosslinkers. However, organic boron crosslinkers have good shear resistance but are not resistant to high temperatures; organic zirconium crosslinkers have excellent temperature resistance but are not resistant to shear. In addition, triethanolamine borate (TEAB) is an organic compound with the molecular formula C6H12BNO3. Triethanolamine borate is widely used in machinery, metallurgy, petrochemical and other industries, and has good anti-rust properties in cutting fluids, rolling oils, emulsified oils, and rust inhibitors. However, it is not used to prepare crosslinkers.

[0003] The Chinese patent application number is CN201410807656.4, and the patent name is "An organic boron zirconium crosslinking agent". Its formula is (by weight): 1 part of inorganic zirconium salt; 2-4 parts of water; 3-6 parts of isopropanol; 0.4-1 part of inorganic boron compound; 4-20 parts of methanol; 2-4 parts of polyol; 1-2 parts of sodium α-hydroxycarboxylate; 1-2 parts of triethanolamine; 0.5-1 part of tetrahydroxypropyl ethylenediamine. The organic boron zirconium crosslinking agent provided by the present invention uses cheap inorganic zirconium salt as raw material, which greatly saves costs and is conducive to the marketization of organic boron zirconium crosslinking agents and their wide application in high temperature resistant fracturing fluid systems. Among them, the above-mentioned inorganic boron compound is one or a combination of two of boric acid or borax.

[0004] The Chinese patent application number is CN201410807511.4, and the patent name is "An organic boron zirconium crosslinking agent and its preparation method". Inorganic zirconium salt and isopropanol are added to water, stirred evenly, and then ammonia is introduced at 55-60°C and refluxed for 0.5-1 hour; then polyol, sodium α-hydroxycarboxylate and alkanolamine are added, and the reaction is continued for 2-4 hours, and then a boron solution prepared by an inorganic boron compound and methanol is added, and the reaction is continued for 2-4 hours to obtain the organic boron zirconium crosslinking agent. The preparation method provided by the present invention has mild and easy-to-control preparation conditions, and the preparation process is simple and easy to operate. The organic boron zirconium crosslinking agent prepared by this method is applied to the high-temperature fracturing fluid system, and the formed gel has good heat resistance and shear resistance at high temperatures above 135°C. The above-mentioned inorganic boron compound is one or a combination of two of boric acid or borax.

[0005] The Chinese patent application number is CN201610680231.0, and the patent name is "An ultra-high temperature fracturing fluid organic boron zirconium crosslinking agent and its preparation method", which is made of the following components: 2-5 parts of inorganic zirconium salt; 10-16 parts of glycerol; 10-18 parts of boron compound; 9-17 parts of ligand; 0.2-1 part of complexing agent; 44-70 parts of water. The organic boron zirconium crosslinking agent provided by the present invention is applied to the high temperature fracturing fluid system, and the formed gel has good temperature resistance and shear resistance at an ultra-high temperature of 180°C. Among them, the boron compound is at least one of borax and boric acid. Summary of the invention

[0006] The purpose of the present invention is to provide a method for preparing a high temperature resistant and shear resistant organic boron zirconium crosslinking agent in view of the above-mentioned defects in the prior art. The boron compound of the present invention adopts triethanolamine borate and is compounded with an organic zirconium crosslinking agent. The obtained organic boron zirconium crosslinking agent has both good temperature resistance and excellent shear resistance.

[0007] The present invention provides a method for preparing a high temperature resistant and shear resistant organic boron zirconium crosslinking agent, and the technical scheme thereof comprises the following steps, measured by weight: 1) Weigh 30-31 parts of deionized water and 18-20 parts of alcohol stabilizer into a reaction container, weigh 8-9 parts of inorganic zirconium salt into the reaction container, and stir to dissolve them completely; 2) Add 2-3 parts of organic ligand and stir to dissolve, and continue stirring for 0.5 hours; 3) adding 38-42 parts of a complexing agent, heating to 50-70° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 11-15 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and the boron compound in step 3) into a reaction container at a mass ratio of 9:1 to 6:1, and stirring at room temperature until completely dissolved to obtain an organic boron zirconium crosslinking agent; The alcohol stabilizer is ethanol or isopropanol or a mixture of the two; The inorganic zirconium salt is zirconium tetrachloride or zirconium oxychloride or a mixture of the two; The organic ligand is DL-alanine or citric acid or a mixture of the two; The boron compound is triethanolamine borate; The complexing agent is triethanolamine.

[0008] The present invention provides a method for preparing a high temperature resistant and shear resistant organic boron zirconium crosslinking agent, comprising the following steps, measured by weight: 1) Weigh 30 parts of deionized water and 18 parts of isopropanol into a reaction container, weigh 9 parts of zirconium oxychloride into the reaction container, and stir to dissolve them completely; 2) Add 3 parts of citric acid and stir to dissolve; continue stirring for 30 minutes; 3) adding 40 parts of triethanolamine, heating to 58° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 12 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and triethanolamine borate into a reaction container at a mass ratio of 9:1, and stirring at room temperature until completely dissolved, thereby obtaining a high temperature resistant and shear resistant organic boron zirconium crosslinking agent.

[0009] The present invention provides a method for preparing a high temperature resistant and shear resistant organic boron zirconium crosslinking agent, comprising the following steps, measured by weight: 1) Weigh 31 parts of deionized water and 20 parts of isopropanol into a reaction container, weigh 8 parts of zirconium tetrachloride into the reaction container, and stir to dissolve them completely; 2) Add 2 parts of DL-alanine and stir to dissolve; continue stirring for 0.5 hours; 3) adding 39 parts of triethanolamine, heating to 60° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 11 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and triethanolamine borate into a reaction container at a mass ratio of 6:1, and stirring at room temperature until completely dissolved, thereby obtaining a high temperature resistant and shear resistant organic boron zirconium crosslinking agent.

[0010] The present invention provides a method for preparing a high temperature resistant and shear resistant organic boron zirconium crosslinking agent, comprising the following steps, measured by weight: 1) Weigh 30 parts of deionized water and 18 parts of isopropanol into a reaction container, weigh 8 parts of zirconium oxychloride into the reaction container, and stir to dissolve them completely; 2) Add 2 parts of DL-alanine and stir to dissolve, and continue stirring for 0.5 hours; 3) adding 42 parts of triethanolamine, raising the temperature to 60° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 11 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and triethanolamine borate into a reaction container at a mass ratio of 7:1, and stirring at room temperature until completely dissolved, thereby obtaining a high temperature resistant and shear resistant organic boron zirconium crosslinking agent.

[0011] The present invention provides a method for preparing a high temperature resistant and shear resistant organic boron zirconium crosslinking agent, comprising the following steps, measured by weight: 1) Weigh 30 parts of deionized water and 18 parts of a mixture of ethanol and isopropanol into a reaction vessel, weigh 8 parts of a mixture of zirconium tetrachloride and zirconium oxychloride into a reaction vessel, turn on stirring to completely dissolve the zirconium tetrachloride and zirconium oxychloride in a mass ratio of 1:2, and ethanol and isopropanol in a mass ratio of 4:1; 2) adding 2 parts of a mixture of DL-alanine and citric acid and stirring to dissolve, and continuing stirring for 0.5 hours, DL-alanine and citric acid are mixed in a mass ratio of 1:3; 3) adding 38 parts of triethanolamine, raising the temperature to 60° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 11 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and triethanolamine borate into a reaction container at a mass ratio of 8:1, and stirring at room temperature until completely dissolved, thereby obtaining a high temperature resistant and shear resistant organic boron zirconium crosslinking agent.

[0012] Compared with the prior art, the beneficial effects of the present invention are as follows: The invention adopts a method of compounding a self-made organic zirconium crosslinking agent and triethanolamine borate. Compared with a preparation method of an organic boron zirconium crosslinking agent prepared by using organic zirconium and organic boron, the invention requires fewer raw materials and is simpler and easier to operate. The organic boron zirconium crosslinking agent prepared by the invention has good crosslinking performance. The formed gel has a fracturing fluid viscosity of 300-400 mPa·s after 2 hours and four variable shear processes at 155°C. The fracturing fluid prepared by the crosslinking agent prepared by the invention can recover to more than 200 mPa·s after the viscosity decreases after high-speed shearing, which fully demonstrates that the crosslinking agent prepared by the invention has excellent heat and shear resistance, greatly broadens the application range of the fracturing fluid prepared by the crosslinking agent, and the crosslinking agent prepared by the invention has the characteristics of controllable delayed crosslinking time, high temperature resistance, good shear resistance and adjustable zirconium-boron ratio. In addition, the invention is not only simple to operate and mild in conditions, but also has a wide source of raw materials and a low price, and has good industrial application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] FIG1 is a schematic diagram of viscosity change curves of Example 1 and Example 2 of the present invention; FIG. 2 is a schematic diagram of the viscosity change curve of the fracturing fluid with the same formulation prepared using the cross-linking agent prepared in Example 3 and the organic zirconium cross-linking agent. DETAILED DESCRIPTION

[0014] The preferred embodiments of the present invention are described below in conjunction with the accompanying drawings. It should be understood that the preferred embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0015] Example 1, a method for preparing a high temperature resistant and shear resistant organic boron zirconium crosslinking agent mentioned in the present invention, comprising the following steps, calculated by weight: 1) Weigh 30 parts of deionized water and 18 parts of isopropanol into a reaction container, weigh 9 parts of zirconium oxychloride into the reaction container, and stir to dissolve them completely; 2) Add 3 parts of citric acid and stir to dissolve; continue stirring for 30 minutes; 3) adding 40 parts of triethanolamine, heating to 58° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 12 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and triethanolamine borate into a reaction container at a mass ratio of 9:1, and stirring at room temperature until completely dissolved, thereby obtaining a high temperature resistant and shear resistant organic boron zirconium crosslinking agent.

[0016] Example 2, a method for preparing a high temperature resistant and shear resistant organic boron zirconium crosslinking agent mentioned in the present invention, comprising the following steps, calculated by weight: 1) Weigh 31 parts of deionized water and 20 parts of isopropanol into a reaction container, weigh 8 parts of zirconium tetrachloride into the reaction container, and stir to dissolve them completely; 2) Add 2 parts of DL-alanine and stir to dissolve; continue stirring for 0.5 hours; 3) adding 39 parts of triethanolamine, heating to 60° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 11 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and triethanolamine borate into a reaction container at a mass ratio of 6:1, and stirring at room temperature until completely dissolved, thereby obtaining a high temperature resistant and shear resistant organic boron zirconium crosslinking agent.

[0017] Embodiment 3, a method for preparing a high temperature resistant and shear resistant organic boron zirconium crosslinking agent mentioned in the present invention comprises the following steps, calculated by weight: 1) Weigh 30 parts of deionized water and 18 parts of isopropanol into a reaction container, weigh 8 parts of zirconium oxychloride into the reaction container, and stir to dissolve them completely; 2) Add 2 parts of DL-alanine and stir to dissolve, and continue stirring for 0.5 hours; 3) adding 42 parts of triethanolamine, raising the temperature to 60° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 11 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and triethanolamine borate into a reaction container at a mass ratio of 7:1, and stirring at room temperature until completely dissolved, thereby obtaining a high temperature resistant and shear resistant organic boron zirconium crosslinking agent.

[0018] Example 4, a method for preparing a high temperature resistant and shear resistant organic boron zirconium crosslinking agent mentioned in the present invention, comprising the following steps, calculated by weight: 1) Weigh 30 parts of deionized water and 18 parts of a mixture of ethanol and isopropanol into a reaction vessel, weigh 8 parts of a mixture of zirconium tetrachloride and zirconium oxychloride into a reaction vessel, turn on stirring to completely dissolve the zirconium tetrachloride and zirconium oxychloride in a mass ratio of 1:2, and ethanol and isopropanol in a mass ratio of 4:1; 2) adding 2 parts of a mixture of DL-alanine and citric acid and stirring to dissolve, and continuing stirring for 0.5 hours, DL-alanine and citric acid are mixed in a mass ratio of 1:3; 3) adding 38 parts of triethanolamine, raising the temperature to 60° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 11 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and triethanolamine borate into a reaction container at a mass ratio of 8:1, and stirring at room temperature until completely dissolved, thereby obtaining a high temperature resistant and shear resistant organic boron zirconium crosslinking agent.

[0019] Specific experimental data refer to Figure 1 and Figure 2 , 1 is a viscosity change curve of the gel prepared with the organic boron zirconium crosslinking agent prepared in Example 1 and Example 2 of the present invention at 155° C., after 2 hours, and four variable shear processes. It can be seen that the organic boron zirconium crosslinking agent prepared by the method of the present invention has good crosslinking performance and heat and shear resistance.

[0020] FIG2 is a fracturing fluid with the same formula prepared by the cross-linking agent prepared in Example 3 and the organic zirconium cross-linking agent, respectively. The viscosity change curves of the two fracturing fluids after high-speed shearing for 120 seconds, and then at 155°C for 2 hours, and four variable shearing processes. As can be seen from FIG2, the fracturing fluid prepared by the organic zirconium in the prior art has a rapid decrease in viscosity after high-speed shearing, and the viscosity has not recovered; while the fracturing fluid prepared by the cross-linking agent prepared in Example 3 can still recover to more than 200 mPa·s after the viscosity decreases after high-speed shearing, which fully demonstrates that the cross-linking agent prepared in the present invention has excellent heat and shear resistance.

[0021] The above are only some preferred embodiments of the present invention. Any person skilled in the art may modify the above technical solutions or modify them into equivalent technical solutions. Therefore, the corresponding simple modifications or equivalent transformations made according to the technical solutions of the present invention shall fall within the scope of protection claimed by the present invention.

Claims

1. A method for preparing a high temperature resistant and shear resistant organic boron zirconium crosslinking agent, characterized in that The method comprises the following steps, measured by weight: 1) Weigh 30-31 parts of deionized water and 18-20 parts of alcohol stabilizer into a reaction container, weigh 8-9 parts of inorganic zirconium salt into the reaction container, and stir to dissolve them completely; 2) Add 2-3 parts of organic ligand and stir to dissolve, and continue stirring for 0.5 hours; 3) adding 38-42 parts of a complexing agent, heating to 50-70° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 11-15 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and the boron compound in step 3) into a reaction container at a mass ratio of 9:1 to 6:1, and stirring at room temperature until completely dissolved to obtain an organic boron zirconium crosslinking agent; The alcohol stabilizer is ethanol or isopropanol or a mixture of the two; The inorganic zirconium salt is zirconium tetrachloride or zirconium oxychloride or a mixture of the two; The organic ligand is DL-alanine or citric acid or a mixture of the two; The boron compound is triethanolamine borate; The complexing agent is triethanolamine.

2. The method for preparing the high temperature resistant and shear resistant organic boron zirconium crosslinking agent according to claim 1, characterized in that The method comprises the following steps, measured by weight: 1) Weigh 30 parts of deionized water and 18 parts of isopropanol into a reaction container, weigh 9 parts of zirconium oxychloride into the reaction container, and stir to dissolve them completely; 2) Add 3 parts of citric acid and stir to dissolve; continue stirring for 30 minutes; 3) adding 40 parts of triethanolamine, heating to 58° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 12 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and triethanolamine borate into a reaction container at a mass ratio of 9:1, and stirring at room temperature until completely dissolved, thereby obtaining a high temperature resistant and shear resistant organic boron zirconium crosslinking agent.

3. The method for preparing the high temperature resistant and shear resistant organic boron zirconium crosslinking agent according to claim 1, characterized in that The method comprises the following steps, measured by weight: 1) Weigh 31 parts of deionized water and 20 parts of isopropanol into a reaction container, weigh 8 parts of zirconium tetrachloride into the reaction container, and stir to dissolve them completely; 2) Add 2 parts of DL-alanine and stir to dissolve; continue stirring for 0.5 hours; 3) adding 39 parts of triethanolamine, heating to 60° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 11 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and triethanolamine borate into a reaction container at a mass ratio of 6:1, and stirring at room temperature until completely dissolved, thereby obtaining a high temperature resistant and shear resistant organic boron zirconium crosslinking agent.

4. The method for preparing the high temperature resistant and shear resistant organic boron zirconium crosslinking agent according to claim 1, characterized in that The method comprises the following steps, measured by weight: 1) Weigh 30 parts of deionized water and 18 parts of isopropanol into a reaction container, weigh 8 parts of zirconium oxychloride into the reaction container, and stir to dissolve them completely; 2) Add 2 parts of DL-alanine and stir to dissolve, and continue stirring for 0.5 hours; 3) adding 42 parts of triethanolamine, raising the temperature to 60° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 11 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and triethanolamine borate into a reaction container at a mass ratio of 7:1, and stirring at room temperature until completely dissolved, thereby obtaining a high temperature resistant and shear resistant organic boron zirconium crosslinking agent.

5. The method for preparing the high temperature resistant and shear resistant organic boron zirconium crosslinking agent according to claim 1, characterized in that The method comprises the following steps, measured by weight: 1) Weigh 30 parts of deionized water and 18 parts of a mixture of ethanol and isopropanol into a reaction vessel, weigh 8 parts of a mixture of zirconium tetrachloride and zirconium oxychloride into a reaction vessel, turn on stirring to completely dissolve the zirconium tetrachloride and zirconium oxychloride in a mass ratio of 1:2, and ethanol and isopropanol in a mass ratio of 4:1; 2) adding 2 parts of a mixture of DL-alanine and citric acid and stirring to dissolve, and continuing stirring for 0.5 hours, DL-alanine and citric acid are mixed in a mass ratio of 1:3; 3) adding 38 parts of triethanolamine, raising the temperature to 60° C., stirring and maintaining the temperature, stirring and maintaining the temperature for 11 hours to obtain an organic zirconium crosslinking agent; 4) adding the organic zirconium crosslinking agent and triethanolamine borate into a reaction container at a mass ratio of 8:1, and stirring at room temperature until completely dissolved, thereby obtaining a high temperature resistant and shear resistant organic boron zirconium crosslinking agent.

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