CN110093147B - Low-molecular shale anti-swelling agent and preparation method thereof - Google Patents
Low-molecular shale anti-swelling agent and preparation method thereof Download PDFInfo
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- CN110093147B CN110093147B CN201810086200.1A CN201810086200A CN110093147B CN 110093147 B CN110093147 B CN 110093147B CN 201810086200 A CN201810086200 A CN 201810086200A CN 110093147 B CN110093147 B CN 110093147B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
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- C—CHEMISTRY; METALLURGY
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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- C—CHEMISTRY; METALLURGY
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
- C09K8/78—Eroding chemicals, e.g. acids combined with additives added for specific purposes for preventing sealing
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- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
Abstract
The invention belongs to the technical field of petrochemical industry, and particularly relates to a low-molecular-weight shale anti-swelling agent and a preparation method thereof; the molecular structural formula of the low-molecular-weight shale expansion-preventing agent is CH3CH2CH2CONHCH2CH2CH2N(CH3) The preparation method of the swelling inhibitor comprises (1) amidation reaction and (2) tertiary amine oxide preparation, and the swelling inhibitor provided by the invention simultaneously meets the performance requirements of positive charge, low molecular weight, multipoint adsorption and the like, and can be effectively suitable for shale reservoirs.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a low-molecular-weight shale expansion-preventing agent and a preparation method thereof.
Background
Shale is not developed due to microcracks and low matrix permeability, so the shale can be put into production only after being fractured. Shale contains a large amount of clay minerals, and the incompatibility of the fracturing fluid, reservoir fluid and rock can cause the reduction of reservoir permeability and seriously affect the fracturing construction effect.
The commonly used antiswelling agents for fracturing at present mainly comprise three types of inorganic salt potassium chloride, cationic polymer and low molecular quaternary ammonium salt. The potassium chloride has better anti-swelling effect when the pH value is 3-6, the anti-swelling effect can be inhibited under the alkaline condition, and in addition, the potassium chloride is difficult to be continuously added on line. The cationic polymer molecule contains a plurality of positive charges, can be adsorbed on the surface of the clay mineral at multiple points, and has good anti-swelling effect and scouring resistance, but the results of indoor core flow tests show that the organic cationic polymer clay stabilizer with high molecular weight is not suitable for compact strata, and the damage rate of permeability to rocks can exceed 50%. For the low molecular weight quaternary ammonium salt, the molecular weight is small, the formation can not be blocked, but because only single-point adsorption can be generated on the surface of the clay, the anti-swelling effect is not good as that of the cationic polymer. Therefore, the efficient clay anti-swelling agent suitable for shale fracturing needs to meet the performance requirements of positive charge, low molecular weight, multipoint adsorption, good solubility in water and the like. The clay stabilizer meeting the requirements is few in products, or the clay stabilizer meeting the requirements and produced abroad is too expensive, so that the development of the low-cost efficient clay anti-swelling agent for fracturing applicable to the domestic shale reservoir is urgently needed.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and aims to provide a low-molecular-weight shale expansion-preventing agent and a preparation method thereof.
One of the purposes of the invention can be realized by the following technical scheme:
a low-molecular shale anti-swelling agent comprises the main components of which the molecular structural formula is shown as the formula (I):
the second purpose of the invention can be realized by the following technical scheme:
a preparation method of a low-molecular shale expansion-preventing agent comprises the following steps:
(1) Amidation reaction, comprising the following steps:
(1) fixing a four-mouth flask connected with an electric stirring device, a condenser pipe, a thermometer and a constant-pressure dropping funnel in an electric heating jacket;
(2) weighing N-butyric acid, placing the N-butyric acid in a four-neck flask, and placing N, N-dimethyl-1, 3-propane diamine in a constant pressure dropping funnel for later use;
(3) slowly stirring and heating to 55-65 ℃, slowly dropwise adding N, N-dimethyl-1, 3-propanediamine into the reaction system at a high rotating speed, gradually increasing the reaction temperature to the reflux temperature after the dropwise adding is finished, carrying out heat preservation reaction for 2.5-4h, stopping stirring after the reaction is finished, cooling and discharging to obtain an amidated product;
(2) The tertiary amine oxide is prepared by the following steps:
s1, fixing a four-neck flask connected with an electric stirring device, a condenser pipe, a thermometer and a constant-pressure dropping funnel in an electric heating jacket;
s2, weighing the amidation product obtained in the step (1) and disodium ethylene diamine tetraacetate, placing the amidation product and disodium ethylene diamine tetraacetate in a four-neck flask, slowly stirring and heating to 40-60 ℃;
and S3, slowly dropwise adding a certain amount of hydrogen peroxide into the reaction system at the temperature of 40-60 ℃ for 0.8-1.2h, slowly heating to 60-90 ℃ for reaction for 4-8h, stopping stirring after the reaction is finished, cooling and discharging to obtain the catalyst.
The second purpose of the invention can be realized by the following technical scheme:
in the preparation method of the low-molecular-weight shale expansion-preventing agent, the consumption of the N-butyric acid and the N, N-dimethyl-1, 3-propane diamine in the step (2) is respectively 41.8-43.9% and 56.1-58.2% of the total mass of the amidation reaction system in the step (1).
The higher rotating speed in the step (3) is 300-400 r/min.
The dosage of the amidation product and the disodium ethylene diamine tetraacetate in the step S2 is respectively 50.3-58.0 percent and 0.5-1.0 percent of the total mass of the tertiary amine oxide preparation reaction system (2).
The dosage of the hydrogen peroxide solute in the hydrogen peroxide and the deionized water in the step S3 is respectively 12.6-14.8 percent and 28.4-34.4 percent of the total mass of the tertiary amine oxide preparation reaction system (2).
Compared with the prior art, the invention has the beneficial effects that:
the anti-swelling agent provided by the invention simultaneously meets the performance requirements of positive charge, low molecular weight, capability of generating multipoint adsorption and the like, and can be effectively suitable for shale reservoirs.
Detailed Description
For a better understanding of the present invention, specific embodiments thereof are now further described, without limiting the scope of the invention thereto.
Example 1 Low-molecular shale anti-swelling agent and preparation method thereof
The low-molecular shale anti-swelling agent comprises the main components of which the molecular structural formula is shown as the formula (I):
the preparation method comprises the following steps:
(1) Amidation reaction, comprising the following steps:
(1) a four-neck flask connected with an electric stirring device, a condenser pipe, a thermometer and a constant pressure dropping funnel is fixed in an electric heating jacket;
(2) weighing N-butyric acid, placing the N-butyric acid in a four-neck flask, and placing N, N-dimethyl-1, 3-propane diamine in a constant pressure dropping funnel for later use; the dosages of the N-butyric acid and the N, N-dimethyl-1, 3-propane diamine are respectively 43.9 percent and 56.1 percent of the total mass of the amidation reaction system (1);
(3) slowly stirring and heating to 55 ℃, slowly dropwise adding N, N-dimethyl-1, 3-propanediamine into the reaction system at a higher rotating speed of 300r/min, gradually increasing the reaction temperature to the reflux temperature after the dropwise adding is finished, keeping the temperature for reaction for 2.5 hours, stopping stirring after the reaction is finished, cooling and discharging to obtain an amidated product;
(2) The tertiary amine oxide is prepared by the following steps:
s1, fixing a four-neck flask connected with an electric stirring device, a condenser pipe, a thermometer and a constant-pressure dropping funnel in an electric heating jacket;
s2, weighing the amidation product obtained in the step (1) and disodium ethylene diamine tetraacetate, placing the amidation product and disodium ethylene diamine tetraacetate in a four-neck flask, slowly stirring and heating to 60 ℃;
and S3, slowly dropwise adding a certain amount of hydrogen peroxide into the reaction system at the temperature of 60 ℃ for 1.2h, slowly heating to 90 ℃ for reacting for 4h, stopping stirring after the reaction is finished, and cooling and discharging to obtain the hydrogen peroxide.
The dosage of the amidation product and the disodium ethylene diamine tetraacetate in the step S2 are respectively 50.3 percent and 0.5 percent of the total mass of the tertiary amine oxide preparation reaction system (2); the amounts of the hydrogen peroxide solute in the hydrogen peroxide and the deionized water in the step S3 are respectively 14.8% and 34.4% of the total mass of the tertiary amine oxide (2) preparation reaction system. Example 2 Low-molecular shale expansion-preventing agent and preparation method thereof
The low molecular weight shale expansion-proof agent is the same as the example 1;
the preparation method comprises the following steps:
(1) Amidation reaction, comprising the following steps:
(1) fixing a four-mouth flask connected with an electric stirring device, a condenser pipe, a thermometer and a constant-pressure dropping funnel in an electric heating jacket;
(2) weighing N-butyric acid, placing the N-butyric acid in a four-neck flask, and placing N, N-dimethyl-1, 3-propane diamine in a constant pressure dropping funnel for later use; the dosages of the N-butyric acid and the N, N-dimethyl-1, 3-propane diamine are respectively 41.8 percent and 58.2 percent of the total mass of the amidation reaction system (1);
(3) slowly stirring and heating to 65 ℃, slowly dropwise adding N, N-dimethyl-1, 3-propane diamine into a reaction system at a higher rotation speed of 400r/min, gradually increasing the reaction temperature to the reflux temperature after the dropwise adding is finished, keeping the temperature for reaction for 4 hours, stopping stirring after the reaction is finished, cooling and discharging to obtain an amidated product;
(2) The tertiary amine oxide is prepared by the following steps:
s1, fixing a four-neck flask connected with an electric stirring device, a condenser pipe, a thermometer and a constant-pressure dropping funnel in an electric heating jacket;
s2, weighing the amidation product obtained in the step (1) and disodium ethylene diamine tetraacetate, placing the amidation product and disodium ethylene diamine tetraacetate in a four-neck flask, slowly stirring and heating to 40 ℃;
and S3, slowly dropwise adding a certain amount of hydrogen peroxide into the reaction system at 40 ℃ for 0.8h, slowly heating to 60 ℃ for reacting for 8h, stopping stirring after the reaction is finished, and cooling and discharging to obtain the hydrogen peroxide.
The dosage of the amidation product and the disodium ethylene diamine tetraacetate in the step S2 is respectively 58.0 percent and 1.0 percent of the total mass of the tertiary amine oxide preparation reaction system in the step (2); the amounts of the hydrogen peroxide solute in the hydrogen peroxide and the deionized water in the step S3 are respectively 12.6 percent and 28.4 percent of the total mass of the tertiary amine oxide preparation reaction system (2). Example 3 Low molecular shale expansion-preventing agent and preparation method thereof
The low molecular shale expansion-proof agent is the same as the embodiment 1;
the preparation method comprises the following steps:
(1) Amidation reaction, comprising the following steps:
(1) fixing a four-mouth flask connected with an electric stirring device, a condenser pipe, a thermometer and a constant-pressure dropping funnel in an electric heating jacket;
(2) weighing N-butyric acid, placing the N-butyric acid in a four-neck flask, and placing N, N-dimethyl-1, 3-propane diamine in a constant pressure dropping funnel for later use; the dosages of the N-butyric acid and the N, N-dimethyl-1, 3-propane diamine are respectively 41.8 percent and 58.2 percent of the total mass of the amidation reaction system (1);
(3) slowly stirring and heating to 60 ℃, slowly dropwise adding N, N-dimethyl-1, 3-propanediamine into the reaction system at a higher rotation speed of 400r/min, gradually increasing the reaction temperature to the reflux temperature after the dropwise adding is finished, keeping the temperature for reaction for 3 hours, stopping stirring after the reaction is finished, cooling and discharging to obtain an amidated product;
(2) The tertiary amine oxide is prepared by the following steps:
s1, fixing a four-neck flask connected with an electric stirring device, a condenser pipe, a thermometer and a constant-pressure dropping funnel in an electric heating jacket;
s2, weighing the amidation product obtained in the step (1) and disodium ethylene diamine tetraacetate, placing the amidation product and disodium ethylene diamine tetraacetate in a four-neck flask, slowly stirring and heating to 50 ℃;
and S3, slowly dropwise adding a certain amount of hydrogen peroxide into the reaction system at the temperature of 50 ℃ for 1.0h, slowly heating to 75 ℃ for reacting for 6h, stopping stirring after the reaction is finished, and cooling and discharging to obtain the hydrogen peroxide.
The dosage of the amidation product and the disodium ethylene diamine tetraacetate in the step S2 is respectively 55.8 percent and 0.8 percent of the total mass of the tertiary amine oxide preparation reaction system in the step (2); the dosage of the hydrogen peroxide solute in the hydrogen peroxide solution and the deionized water in the step S3 is respectively 13.2 percent and 30.2 percent of the total mass of the tertiary amine oxide preparation reaction system (2). Test example 1 Effect test
The low-molecular-weight shale anti-swelling agent obtained in the embodiment 1 to 3 is taken, and the synthesized stabilizer is evaluated by a centrifugal method in SY-T5971-2016 oil and gas field fracturing acidification and clay stabilizer performance evaluation method for water injection in the petroleum and natural gas industry standard under the condition of room temperature and 25 ℃. The anti-swelling rate is calculated mainly by measuring the swelling volume of the bentonite in kerosene, deionized water and anti-swelling agent solutions with different concentrations, and the experimental results are shown in table 1.
TABLE 1 anti-swelling ratio of each of the anti-swelling agents in examples 1 to 3
As can be seen from Table 1, the low molecular weight shale expansion-preventing agent prepared in the examples 1-3 of the invention has good expansion-preventing effect, wherein the effect of the example 3 is the best, and the expansion-preventing rate is as high as 90.3% when the mass fraction is 2.0%.
Claims (1)
1. The application of the substance as the low-molecular shale expansion-preventing agent is characterized in that: the molecular structural formula of the main components is as follows:
the preparation method comprises the following steps:
(1) Amidation reaction, comprising the following steps:
(1) a four-neck flask connected with an electric stirring device, a condenser pipe, a thermometer and a constant pressure dropping funnel is fixed in an electric heating jacket;
(2) weighing N-butyric acid, placing the N, N-dimethyl-1, 3-propane diamine in a four-neck flask, and placing the N, N-dimethyl-1, 3-propane diamine in a constant pressure dropping funnel for later use;
(3) slowly stirring and heating to 55-65 ℃, slowly dropwise adding N, N-dimethyl-1, 3-propanediamine into the reaction system at the rotating speed of 300-400r/min, gradually increasing the reaction temperature to the reflux temperature after the dropwise adding is finished, carrying out heat preservation reaction for 2.5-4h, stopping stirring after the reaction is finished, cooling and discharging to obtain an amidated product;
(2) The tertiary amine oxide is prepared by the following steps:
s1, fixing a four-neck flask connected with an electric stirring device, a condenser pipe, a thermometer and a constant-pressure dropping funnel in an electric heating jacket;
s2, weighing the amidation product obtained in the step (1) and disodium ethylene diamine tetraacetate, placing the amidation product and disodium ethylene diamine tetraacetate in a four-neck flask, slowly stirring and heating to 40-60 ℃;
s3, slowly dripping a certain amount of hydrogen peroxide into the reaction system at the temperature of 40-60 ℃ for 0.8-1.2h, slowly heating to 60-90 ℃ for reaction for 4-8h, stopping stirring after the reaction is finished, cooling and discharging to obtain the hydrogen peroxide;
the dosages of the N-butyric acid and the N, N-dimethyl-1, 3-propane diamine in the step (2) are respectively 41.8 to 43.9 percent and 56.1 to 58.2 percent of the total mass of the amidation reaction system in the step (1);
the dosage of the amidation product and the disodium ethylene diamine tetraacetate in the step S2 are respectively 50.3-58.0% and 0.5-1.0% of the total mass of the tertiary amine oxide preparation reaction system (2);
the amounts of the hydrogen peroxide solute in the hydrogen peroxide and the deionized water in the step S3 are respectively 12.6-14.8% and 28.4-34.4% of the total mass of the tertiary amine oxide preparation reaction system (2).
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| CN1887861A (en) * | 2005-06-29 | 2007-01-03 | 上海高维化学有限公司 | Prepn of alkyl amidopropyldimethyl amine oxide surfactant |
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