Preparation method of inhibitor for drilling fluid
By preparing polyetheramine inhibitors with high positive electrostatic properties and polyhydroxy groups, the problem of insufficient heat resistance performance of existing shale inhibitors at high temperatures is solved, and effective hydration inhibition and environmentally friendly to mud shale are achieved. The drilling fluid performance significantly improves the stability and recovery rate of drilling fluid.
Patent Information
- Application Number
- CN202411303435.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-19
- Publication Date
- 2024-12-20
- Estimated Expiration
- 2044-09-19
AI Technical Summary
The existing shale inhibitors have insufficient heat resistance at high temperatures, which cannot effectively inhibit the hydration and expansion of mud shale, and have poor environmental protection effects, making it difficult to meet the demand for drilling in deep wells and complex areas.
Polyethers are prepared by reacting sorbitol, diethylene glycol and β-cyclodextrin with propylene oxide, and reacting with compounds such as pyridine, p-toluenesulfonyl chloride and N,N-dimethylethylenediamine to form high positive electrical properties Heat-resistant and stable inhibitors for drilling fluids were prepared by reacting with polyhydroxy polyetheramine inhibitors.
This inhibitor has excellent hydration inhibition ability, which reduces the linear expansion rate of shale, improves the rolling recovery rate, and significantly reduces the hydration degree of mud shale through the interaction between surface cations and clay surface, and improves the hydration degree of mud shale. The stability and environmental friendliness of drilling fluid.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of inhibitor preparation, and specifically relates to a method for preparing an inhibitor for drilling fluid. Background Art
[0002] With the development of oil and gas exploration, deep wells, ultra-deep wells, offshore wells and wells in complex areas have emerged. When encountering mud shale formations during drilling, the hydration expansion and dispersion of mud shale will lead to a series of problems such as wellbore instability, drill bit mud packing and wellbore purification, which increases the difficulty of drilling and puts higher requirements on the drilling fluid system, especially shale inhibitors. Commonly used shale inhibitors mainly include polymers, inorganic salts, asphalts and humic acids. These shale inhibitors have some shortcomings. For example, asphalt is not conducive to environmental protection, silicates make the system rheology difficult to control, and glycosides and polyethylene glycols cannot solve the drilling problems of active mud shale.
[0003] The development of amine inhibitors is from the initial common ammonium salts to quaternary ammonium salts with less odor, polyamine acids, polyhydroxyalkyl ammonium salts, diamines, polyethoxy diamines, and new primary diamines. The inhibitory performance and environmental acceptance of amine shale inhibitors are constantly improving. According to the different chemical structures, polyamine shale inhibitors can be divided into several categories, such as chain polyamines, branched polyamines, aromatic amines, and polyquaternary amines. From the perspective of inhibition mechanism, polyamine shale inhibitors are mainly due to the unique adsorption effect of amine groups. The positively charged ammonium ions are adsorbed on the clay surface, and the binding of clay sheets is strengthened through hydrogen bonding, thereby preventing the entry of water molecules and inhibiting clay hydration. However, the adsorption of polyamine inhibitors on the surface of clay particles is physical adsorption. At high temperatures, the molecular thermal motion is intensified, and the inhibitors will fail due to desorption, which is manifested as insufficient temperature resistance. Therefore, it is necessary to explore a new type of inhibitor for drilling fluids. Summary of the invention
[0004] The purpose of the present invention is to provide a method for preparing a drilling fluid inhibitor. The drilling fluid inhibitor prepared by the method has excellent hydration inhibition ability, reduces the linear expansion of shale and improves the rolling recovery rate of shale.
[0005] The method for preparing the inhibitor for drilling fluid of the present invention comprises the following steps:
[0006] (1) Add sorbitol, diethylene glycol, β-cyclodextrin and sodium hydroxide to a reactor, replace with nitrogen 3-4 times, evacuate to -0.1 MPa, raise the temperature to 102-105° C., introduce propylene oxide, maintain the reaction temperature at 110-113° C. and keep the pressure in the reactor ≤0.5 MPa after the reaction is stable, and mature the reaction for 3-3.2 hours after the feeding is completed, and remove the unreacted propylene oxide in vacuum to prepare a polyether;
[0007] (2) adding the polyether prepared in step (1) and pyridine into a reaction vessel, stirring and dissolving them, dropping a pyridine solution of p-toluenesulfonyl chloride, reacting at 63-65° C. for 2 h, cooling to room temperature, and continuing the reaction for 23-25 h to prepare an esterified polyether, and dropping the esterified polyether into a toluene solution of N,N-dimethylethylenediamine under nitrogen reflux, and performing aminolysis at 108-110° C. for 30-35 min to prepare a polyetheramine;
[0008] (3) Add 3-chloro-2-hydroxypropyltrimethylammonium chloride to the polyetheramine prepared in step (2) at room temperature, stir evenly, then heat to 66-68° C. and continue the reaction for 2.5-2.7 hours to prepare an inhibitor for drilling fluid.
[0009] Wherein: in step (1), the molar ratio of sorbitol, diethylene glycol and β-cyclodextrin is 0.9-1.1: 0.5-0.7: 0.1-0.12.
[0010] The mass of propylene oxide in step (1) is 7-9 times the sum of the masses of sorbitol, diethylene glycol and β-cyclodextrin.
[0011] In step (1), the mass of sodium hydroxide accounts for 0.8-1% of the total mass of sorbitol, diethylene glycol and β-cyclodextrin.
[0012] The mass volume ratio of polyether to pyridine in step (2) is 3:4.5-4.7, expressed in g / mL.
[0013] In step (2), the mass volume ratio of p-toluenesulfonyl chloride to pyridine in the pyridine solution of p-toluenesulfonyl chloride is 1:2.4-2.5, expressed in g / mL.
[0014] In step (2), the molar ratio of polyether to p-toluenesulfonyl chloride is 1:2.3-2.4.
[0015] In step (2), the mass ratio of the esterified polyether to N,N-dimethylethylenediamine is 10:0.8-1.
[0016] In step (2), the mass volume ratio of N,N-dimethylethylenediamine to toluene in the toluene solution of N,N-dimethylethylenediamine is 1:2-3, and the unit is g / mL.
[0017] In step (3), the molar ratio of the polyetheramine to 3-chloro-2-hydroxypropyltrimethylammonium chloride is 2.2-2.4:1.
[0018] Compared with the prior art, the present invention has the following beneficial effects:
[0019] (1) The method for preparing a drilling fluid inhibitor of the present invention comprises the following steps: firstly, sorbitol, diethylene glycol and β-cyclodextrin are used as initiators to react with propylene oxide to prepare a polyether, wherein the sorbitol has a high heat-resistant decomposition temperature, and a high proportion of sorbitol in the initiator will improve the heat stability of the prepared polyether; and a small amount of β-cyclodextrin is compounded to improve the chemical stability of the polyether, thereby making the prepared polyether have excellent heat stability and chemical stability, thereby fundamentally ensuring the heat resistance of the prepared polyamine inhibitor; and then, the prepared polyether is reacted with N,N-dimethylethylenediamine to prepare a polyetheramine, and then, the polyetheramine is reacted with 3-chloro-2-hydroxypropyltrimethylammonium chloride to prepare a drilling fluid inhibitor. The drilling fluid inhibitor prepared in this way has the characteristics of high positive charge, multiple hydroxyl groups and heat resistance and stability, thereby improving the interaction between the inhibitor and the shale layer, so that the inhibitor has a stronger shale layer penetration ability.
[0020] (2) The drilling fluid inhibitor prepared by the preparation method of the present invention is a diquaternary ammonium salt inhibitor, which has excellent hydration inhibition ability, reduces the linear expansion rate of shale and improves the rolling recovery rate of shale.
[0021] (3) The drilling fluid inhibitor prepared by the preparation method of the present invention can neutralize the negative charge on the surface of clay through the cationic groups on the surface, thereby inhibiting the hydration of shale. At the same time, it can be inserted into the interlayers of shale instead of just adsorbing on the surface, so that the water molecules between the layers are squeezed out, thereby reducing the hydration degree of shale and fundamentally inhibiting the hydration expansion of shale. DETAILED DESCRIPTION
[0022] The present invention is further described below with reference to the embodiments.
[0023] Example 1
[0024] The method for preparing the inhibitor for drilling fluid described in Example 1 comprises the following steps:
[0025] (1) Sorbitol, diethylene glycol, β-cyclodextrin and sodium hydroxide were added to a reactor, and nitrogen was passed through the reactor for 4 times, and the reactor was evacuated to -0.1 MPa. The temperature was raised to 104° C., and propylene oxide was introduced. After the reaction was stable, the reaction temperature was maintained at 112° C. and the pressure in the reactor was maintained at ≤0.5 MPa. After the feeding was completed, the reactor was aged for 3.1 hours, and the unreacted propylene oxide was removed under vacuum to prepare a polyether.
[0026] (2) adding the polyether prepared in step (1) and pyridine into a reaction container, stirring and dissolving them, dropping a pyridine solution of p-toluenesulfonyl chloride, reacting at 64° C. for 2 h, cooling to room temperature, and continuing the reaction for 24 h to prepare an esterified polyether, and dropping the esterified polyether into a toluene solution of N,N-dimethylethylenediamine under nitrogen reflux, and performing aminolysis at 109° C. for 33 min to prepare a polyetheramine;
[0027] (3) Add 3-chloro-2-hydroxypropyltrimethylammonium chloride to the polyetheramine prepared in step (2) at room temperature, stir evenly, then heat to 67° C. and continue the reaction for 2.6 hours to prepare an inhibitor for drilling fluid.
[0028] Wherein: in step (1), the molar ratio of sorbitol, diethylene glycol and β-cyclodextrin is 1.0:0.6:0.11.
[0029] The mass of propylene oxide in step (1) is 8 times the sum of the masses of sorbitol, diethylene glycol and β-cyclodextrin.
[0030] The mass of sodium hydroxide in step (1) accounts for 0.9% of the total mass of sorbitol, diethylene glycol and β-cyclodextrin.
[0031] The mass volume ratio of polyether to pyridine in step (2) is 3:4.6, expressed in g / mL.
[0032] In step (2), the mass volume ratio of p-toluenesulfonyl chloride to pyridine in the pyridine solution of p-toluenesulfonyl chloride is 1:2.45, expressed in g / mL.
[0033] In step (2), the molar ratio of polyether to p-toluenesulfonyl chloride is 1:2.35.
[0034] In step (2), the mass ratio of the esterified polyether to N,N-dimethylethylenediamine is 10:0.9.
[0035] In step (2), the mass volume ratio of N,N-dimethylethylenediamine to toluene in the toluene solution of N,N-dimethylethylenediamine is 1:2.5, expressed in g / mL.
[0036] In step (3), the molar ratio of the polyetheramine to 3-chloro-2-hydroxypropyltrimethylammonium chloride is 2.3:1.
[0037] Example 2
[0038] The method for preparing the inhibitor for drilling fluid described in Example 2 comprises the following steps:
[0039] (1) Sorbitol, diethylene glycol, β-cyclodextrin and sodium hydroxide were added to a reactor, and nitrogen was passed through the reactor for replacement three times. The reactor was evacuated to -0.1 MPa, the temperature was raised to 102° C., propylene oxide was introduced, and after the reaction was stable, the reaction temperature was maintained at 110° C. and the pressure in the reactor was maintained at ≤0.5 MPa. After the feeding was completed, the reactor was aged for 3 hours, and the unreacted propylene oxide was removed under vacuum to prepare a polyether;
[0040] (2) adding the polyether prepared in step (1) and pyridine into a reaction container, stirring and dissolving them, dropping a pyridine solution of p-toluenesulfonyl chloride, reacting at 63° C. for 2 h, cooling to room temperature, and continuing the reaction for 25 h to prepare an esterified polyether, and dropping the esterified polyether into a toluene solution of N,N-dimethylethylenediamine under nitrogen reflux, and performing aminolysis at 108° C. for 35 min to prepare a polyetheramine;
[0041] (3) Add 3-chloro-2-hydroxypropyltrimethylammonium chloride to the polyetheramine prepared in step (2) at room temperature, stir evenly, then heat to 66° C. and continue the reaction for 2.5 hours to prepare an inhibitor for drilling fluid.
[0042] Wherein: in step (1), the molar ratio of sorbitol, diethylene glycol and β-cyclodextrin is 0.9:0.5:0.12.
[0043] The mass of propylene oxide in step (1) is 7 times the sum of the masses of sorbitol, diethylene glycol and β-cyclodextrin.
[0044] The mass of sodium hydroxide in step (1) accounts for 0.8% of the total mass of sorbitol, diethylene glycol and β-cyclodextrin.
[0045] The mass volume ratio of polyether to pyridine in step (2) is 3:4.5, expressed in g / mL.
[0046] In step (2), the mass volume ratio of p-toluenesulfonyl chloride to pyridine in the pyridine solution of p-toluenesulfonyl chloride is 1:2.4, expressed in g / mL.
[0047] In step (2), the molar ratio of polyether to p-toluenesulfonyl chloride is 1:2.3.
[0048] In step (2), the mass ratio of the esterified polyether to N,N-dimethylethylenediamine is 10:1.
[0049] In step (2), the mass volume ratio of N,N-dimethylethylenediamine to toluene in the toluene solution of N,N-dimethylethylenediamine is 1:2, and the unit is g / mL.
[0050] In step (3), the molar ratio of the polyetheramine to 3-chloro-2-hydroxypropyltrimethylammonium chloride is 2.2:1.
[0051] Example 3
[0052] The method for preparing the inhibitor for drilling fluid described in Example 3 is composed of the following steps:
[0053] (1) Sorbitol, diethylene glycol, β-cyclodextrin and sodium hydroxide were added to a reactor, and nitrogen was passed through the reactor for 4 times, and the reactor was evacuated to -0.1 MPa. The temperature was raised to 105° C., and propylene oxide was introduced. After the reaction was stable, the reaction temperature was maintained at 113° C. and the pressure in the reactor was maintained at ≤0.5 MPa. After the feeding was completed, the reactor was aged for 3.2 hours, and the unreacted propylene oxide was removed under vacuum to prepare a polyether.
[0054] (2) adding the polyether prepared in step (1) and pyridine into a reaction container, stirring and dissolving them, dropping a pyridine solution of p-toluenesulfonyl chloride, reacting at 65° C. for 2 h, cooling to room temperature, and continuing the reaction for 23 h to prepare an esterified polyether, and dropping the esterified polyether into a toluene solution of N,N-dimethylethylenediamine under nitrogen reflux, and performing aminolysis at 110° C. for 30 min to prepare a polyetheramine;
[0055] (3) Add 3-chloro-2-hydroxypropyltrimethylammonium chloride to the polyetheramine prepared in step (2) at room temperature, stir evenly, then heat to 68° C. and continue the reaction for 2.7 h to prepare an inhibitor for drilling fluid.
[0056] Wherein: in step (1), the molar ratio of sorbitol, diethylene glycol and β-cyclodextrin is 1.1:0.7:0.1.
[0057] The mass of propylene oxide in step (1) is 9 times the sum of the masses of sorbitol, diethylene glycol and β-cyclodextrin.
[0058] The mass of sodium hydroxide in step (1) accounts for 1% of the total mass of sorbitol, diethylene glycol and β-cyclodextrin.
[0059] The mass volume ratio of polyether to pyridine in step (2) is 3:4.7, expressed in g / mL.
[0060] In step (2), the mass volume ratio of p-toluenesulfonyl chloride to pyridine in the pyridine solution of p-toluenesulfonyl chloride is 1:2.5, expressed in g / mL.
[0061] In step (2), the molar ratio of polyether to p-toluenesulfonyl chloride is 1:2.4.
[0062] In step (2), the mass ratio of the esterified polyether to N,N-dimethylethylenediamine is 10:0.8.
[0063] In step (2), the mass volume ratio of N,N-dimethylethylenediamine to toluene in the toluene solution of N,N-dimethylethylenediamine is 1:3, expressed in g / mL.
[0064] In step (3), the molar ratio of the polyetheramine to 3-chloro-2-hydroxypropyltrimethylammonium chloride is 2.4:1.
[0065] Comparative Example 1
[0066] The only difference between the method for preparing the drilling fluid inhibitor described in Comparative Example 1 and Example 1 is that sorbitol is no longer added when preparing the polyether in step (1).
[0067] Comparative Example 2
[0068] The only difference between the method for preparing the drilling fluid inhibitor described in Comparative Example 2 and Example 1 is that step (3) is omitted.
[0069] In order to further illustrate the effect of the drilling fluid inhibitor of the present invention, the drilling fluid inhibitor prepared in Examples 1-3 and Comparative Examples 1-2 was tested in terms of linear expansion rate and rolling recovery rate. The drilling fluid inhibitor prepared in Examples 1-3 and Comparative Examples 1-2 was mixed with deionized water at a mass ratio of 1.5% for the experiment. Deionized water was used as a reference. The test standard was the petroleum and natural gas industry standard SY / T 5613-2016 Drilling Fluid Test "Test Method for Physical and Chemical Properties of Shale". The high temperature conditions for the rolling recovery rate test were aging temperature 180°C and aging time 16h. The test results are shown in Table 1 below:
[0070] Table 1 Test results of drilling fluid inhibitor performance
[0071]
[0072] It can be seen from Table 1 that the linear expansion rate of the drilling fluid inhibitor prepared in Examples 1-3 of the present invention is significantly lower than that of Comparative Examples 1-2, and the rolling recovery rate is significantly higher than that of Comparative Examples 1-2. The lower the linear expansion rate and the higher the rolling recovery rate, the better the inhibition performance of the drilling fluid inhibitor. It can be seen that the drilling fluid inhibitor prepared in this application has excellent hydration inhibition performance.
Claims
1. A method for preparing an inhibitor for drilling fluid, characterized in that: It consists of the following steps: (1) Add sorbitol, diethylene glycol, β-cyclodextrin and sodium hydroxide to a reactor, replace with nitrogen 3-4 times, evacuate to -0.1 MPa, raise the temperature to 102-105° C., introduce propylene oxide, maintain the reaction temperature at 110-113° C. and keep the pressure in the reactor ≤0.5 MPa after the reaction is stable, and mature the reaction for 3-3.2 hours after the feeding is completed, and remove the unreacted propylene oxide in vacuum to prepare a polyether; (2) adding the polyether prepared in step (1) and pyridine into a reaction vessel, stirring and dissolving them, dropping a pyridine solution of p-toluenesulfonyl chloride, reacting at 63-65° C. for 2 h, cooling to room temperature, and continuing the reaction for 23-25 h to prepare an esterified polyether, and dropping the esterified polyether into a toluene solution of N,N-dimethylethylenediamine under nitrogen reflux, and performing aminolysis at 108-110° C. for 30-35 min to prepare a polyetheramine; (3) adding 3-chloro-2-hydroxypropyltrimethylammonium chloride to the polyetheramine prepared in step (2) at room temperature, stirring evenly, heating to 66-68° C. and continuing the reaction for 2.5-2.7 hours to prepare an inhibitor for drilling fluid; in: In step (1), the molar ratio of sorbitol, diethylene glycol and β-cyclodextrin is 0.9-1.1: 0.5-0.7: 0.1-0.
12.
2. The method for preparing an inhibitor for drilling fluid according to claim 1, characterized in that: The mass of propylene oxide in step (1) is 7-9 times the sum of the masses of sorbitol, diethylene glycol and β-cyclodextrin.
3. The method for preparing an inhibitor for drilling fluid according to claim 1, characterized in that: In step (1), the mass of sodium hydroxide accounts for 0.8-1% of the total mass of sorbitol, diethylene glycol and β-cyclodextrin.
4. The method for preparing an inhibitor for drilling fluid according to claim 1, characterized in that: The mass volume ratio of polyether to pyridine in step (2) is 3:4.5-4.7, expressed in g / mL.
5. The method for preparing an inhibitor for drilling fluid according to claim 1, characterized in that: In step (2), the mass volume ratio of p-toluenesulfonyl chloride to pyridine in the pyridine solution of p-toluenesulfonyl chloride is 1:2.4-2.5, expressed in g / mL.
6. The method for preparing an inhibitor for drilling fluid according to claim 1, characterized in that: In step (2), the molar ratio of polyether to p-toluenesulfonyl chloride is 1:2.3-2.
4.
7. The method for preparing an inhibitor for drilling fluid according to claim 1, characterized in that: In step (2), the mass ratio of the esterified polyether to N,N-dimethylethylenediamine is 10:0.8-1.
8. The method for preparing an inhibitor for drilling fluid according to claim 1, characterized in that: In step (2), the mass volume ratio of N,N-dimethylethylenediamine to toluene in the toluene solution of N,N-dimethylethylenediamine is 1:2-3, and the unit is g / mL.
9. The method for preparing an inhibitor for drilling fluid according to claim 1, characterized in that: In step (3), the molar ratio of the polyetheramine to 3-chloro-2-hydroxypropyltrimethylammonium chloride is 2.2-2.4:1.