Compounds, processes for their preparation and use

Abstract

The application relates to the technical field of oil production engineering, and discloses a compound, a preparation method and application of the compound, the compound has the structure shown in formula (1), wherein n1, n2 and n3 are each independently a natural number of 0-4; when the compound is used as a clay anti-swelling agent, the compound has the advantages of moderate molecules, many adsorption points, strong combination with a stratum, high water washing resistance, good anti-swelling performance, good effect of preventing clay particle migration and high temperature resistance.

Description

Technical Field

[0001] This invention relates to the field of oilfield engineering technology, specifically to a compound, its preparation method, and its application. Background Technology

[0002] Clay is a common mineral found in geological formations. Because clay swells when exposed to water, during reservoir development processes such as water injection, acidizing, or fracturing in oilfields, the porosity in clay-rich reservoirs decreases due to clay expansion, leading to significant pore blockage and water-sensitive damage. To mitigate this reservoir damage, clay anti-swelling agents are widely used. These agents effectively adsorb onto the clay surface, preventing the hydration, expansion, and dispersion of water-sensitive minerals within the reservoir, thus preventing damage to the oil and gas layer and impacting oilfield development.

[0003] Currently used anti-swelling agents mainly include inorganic salts, cationic polymers, and quaternary ammonium salts. Inorganic salts, as the earliest clay anti-swelling agents, primarily utilize inorganic salt ions such as K+. + Inorganic salt-based clay anti-swelling agents are embedded in the clay crystal structure to neutralize the electronegativity of the clay. However, they have weak bonding with the formation and poor ability to prevent clay migration. Cationic polymers contain multiple positive charges in their molecules, allowing for multi-point adsorption on the surface of clay minerals, resulting in good anti-swelling effects and erosion resistance. However, their large molecular weight easily clogs formation pores and throats, impairing formation permeability and making them unsuitable for dense formations. Furthermore, cationic polymers have poor temperature resistance and are prone to decomposition at high temperatures, causing their anti-swelling effect to disappear. Although quaternary ammonium salts have small molecular weights and do not clog the formation themselves, their anti-swelling effect is not as good as that of cationic polymers because they can only produce single-point adsorption on the clay surface.

[0004] Existing anti-swelling agents have limited adsorption sites, resulting in poor anti-swelling effects. Their excessively large molecular weight prevents their application in low-permeability formations. Furthermore, their poor molecular stability leads to chain breakage at high temperatures, resulting in low temperature resistance. Therefore, there is a need to develop a clay anti-swelling agent with excellent anti-swelling properties, water resistance, and temperature resistance. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems of poor anti-swelling effect, poor washability and low temperature resistance of existing anti-swelling agents, and to provide a compound, its preparation method and application.

[0006] To achieve the above objectives, a first aspect of the present invention provides a compound, wherein the compound has the structure shown in formula (1).

[0007]

[0008] Among them, n1, n2, and n3 are each independent natural numbers from 0 to 4.

[0009] A second aspect of the present invention provides a method for preparing a compound, comprising: reacting triethanolamine and ethyleneamine in the presence of a catalyst and hydrogen to obtain the compound.

[0010] A third aspect of the present invention provides a compound obtained by the preparation method described above.

[0011] A fourth aspect of the present invention provides the application of the compound in a clay anti-swelling agent.

[0012] Through the above technical solution, the present invention provides a compound, its preparation method and application. When the compound is used as a clay anti-swelling agent, it has moderate molecular size, many adsorption sites, and has the advantages of strong binding force with the stratum, high water washability, good anti-swelling performance, good effect in preventing clay particle migration and high temperature resistance. Detailed Implementation

[0013] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0014] In a first aspect, the present invention provides a compound, wherein the compound has the structure shown in formula (1).

[0015]

[0016] Among them, n1, n2, and n3 are each independent natural numbers from 0 to 4.

[0017] In this invention, the compound's molecular structure contains multiple amine groups, and the number of amine groups is large. In aqueous solution, it ionizes to form amine cations with high charge density, which can significantly reduce the electronegativity of clay and inhibit clay hydration and dispersion. The multi-point adsorption formed by the amine groups allows it to firmly adsorb onto the clay surface, improving its erosion resistance. More preferably, n1, n2, and n3 are the same. Specifically, when n1 = n2 = n3 = 0, the ethyleneamine is selected from ethylenediamine; when n1 = n2 = n3 = 1, the ethyleneamine is selected from diethylenetriamine; when n1 = n2 = n3 = 2, the ethyleneamine is selected from triethylenetetramine; the ethyleneamine is selected from diethylenetriamine; when n1 = n2 = n3 = 3, the ethyleneamine is selected from tetraethylenepentamine; the ethyleneamine is selected from diethylenetriamine; when n1 = n2 = n3 = 4, the ethyleneamine is selected from pentaethylenehexamine. Preferably, n1, n2, and n3 are each independently preferred to be an integer from 1 to 3. When the compound is used as a clay anti-swelling agent, it has moderate molecular size, many adsorption sites, and has the advantages of strong bonding with the stratum, high water washability, good anti-swelling performance, good effect in preventing clay particle migration, and high temperature resistance.

[0018] The composition and structure of the compound can be determined by NMR, IR, GPC, elemental analysis, or by preparation and feeding.

[0019] A second aspect of the present invention provides a method for preparing a compound, comprising: reacting triethanolamine and ethyleneamine in the presence of a catalyst and hydrogen to obtain the compound.

[0020] In this invention, the compound is prepared by amination reaction using triethanolamine, ethyleneamine and hydrogen as raw materials in the presence of a supported solid catalyst.

[0021] The compound is prepared by a one-step reaction, which involves fewer reaction steps, a simple process, and is easy to industrialize; no organic solvents are used, resulting in less waste and is environmentally friendly.

[0022] In this invention, during the reaction process, under the action of a catalyst and in a hydrogen atmosphere, triethanolamine first undergoes dehydrogenation to convert the hydroxyl group into an aldehyde group. The aldehyde group then reacts with the amino group in ethyleneamine to produce an imine. The resulting imine is further hydrogenated to form an amine, thus yielding the compound. The degree of reaction can be determined by titration to analyze the amine value of the compound, and its structure can be analyzed by infrared spectroscopy.

[0023] In some specific embodiments of the present invention, the ethyleneamine is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, preferably one or more of diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

[0024] In some specific embodiments of the present invention, the molar ratio of triethanolamine to ethyleneamine is 1:3-6, and the amount of catalyst is 1-5 wt% of the total amount of triethanolamine and ethyleneamine.

[0025] In some specific embodiments of the present invention, the reaction temperature is 160-220°C, the hydrogen partial pressure is 1-2.5 MPa, and the reaction time is 4-8 h. By limiting the reaction temperature, time, and hydrogen partial pressure to the above ranges, the reaction between triethanolamine and ethyleneamine can be made more complete, side reactions can be controlled to prevent them, and a better catalytic effect can be achieved.

[0026] In some specific embodiments of the present invention, the catalyst comprises a main active component, an auxiliary agent, and a support, wherein the support is selected from silica and / or alumina, the main active component is Ni and Cu, and the auxiliary agent is Cr and Mo. The main active component and the auxiliary agent are loaded on the support.

[0027] In some specific embodiments of the present invention, based on the total weight of the catalyst, the catalyst contains 20-40 wt% Ni, 4-8 wt% Cu, 1-3 wt% Cr, 0.5-1.5 wt% Mo, and 47.5-74.5% support. The defined catalyst components within the above range exhibit better catalytic performance, enabling more complete reaction of triethanolamine and ethyleneamine, controlling the absence of side reactions, and achieving better catalytic effects.

[0028] A third aspect of the present invention provides a compound obtained by the preparation method described above.

[0029] In this invention, the composition and structure of the compound can be determined by nuclear magnetic resonance, infrared spectroscopy, elemental analysis, or by preparation and feeding.

[0030] A fourth aspect of the present invention provides the application of the compound in a clay anti-swelling agent.

[0031] In some specific embodiments of the present invention, the clay anti-swelling agent at a dosage of 0.5 wt% has a room temperature anti-swelling rate of ≥90%, a water washability of ≥95%, and a temperature resistance of ≥350℃.

[0032] In this invention, the clay anti-swelling agent has a moderate molecular weight, which will not cause blockage in low-permeability formations, resulting in good oil recovery.

[0033] The present invention will be described in detail below through embodiments.

[0034] Referring to the "Sy / T5971-2016 Performance Evaluation Method of Clay Anti-swelling Agent for Water Injection", the anti-swelling rate and water wash resistance of the clay anti-swelling agent were tested.

[0035] High-temperature swelling resistance test method: Add 3.00g of sodium bentonite to 60mL of 1% clay swelling resistant agent solution, shake thoroughly to mix, and then put into an aging kettle; then place it in a high-temperature aging furnace and age at a constant temperature for 24h at the set temperature; after cooling to room temperature, transfer all the clay swelling resistant agent solution in the aging kettle into a 100mL beaker, shake thoroughly, quickly take out 10mL and add it to a centrifuge tube, put it into a centrifuge with automatic balancing function, centrifuge at 1500r / min for 15min, and read the swelling volume V1 of the bentonite. The high-temperature swelling resistance calculation formula is shown in Equation 3.

[0036]

[0037] Where: F—high temperature anti-swelling rate, %;

[0038] V0—Volume of sodium bentonite in kerosene, mL;

[0039] V1—Volume of sodium bentonite in clay anti-swelling agent, mL;

[0040] V2—Volume of sodium bentonite in pure water, mL.

[0041] The purity of the compound was tested using the triethanolamine conversion rate test method.

[0042] Weigh 1g of the separated product into an Erlenmeyer flask, then add 50mL of a pyridine solution containing phthalic anhydride, wherein the mass ratio of phthalic anhydride to pyridine is 20:120. React at 115℃ under reflux for 1h. After cooling, titrate the excess phthalic anhydride with 0.5mol / L sodium hydroxide solution. At the same time, perform a blank experiment with 50mL of a pyridine solution containing phthalic anhydride. The formula for calculating the hydroxyl content of the product is shown in Equation 1, and the formula for calculating the triethanolamine conversion rate is shown in Equation 2.

[0043] S=C*(V0-V1) / m Equation 1;

[0044] S: Hydroxyl content, mmol / g

[0045] C: Sodium hydroxide concentration, mol / L;

[0046] V0: Volume of sodium hydroxide consumed by the blank sample, in mL;

[0047] V1: Volume of sodium hydroxide consumed by the sample (mL);

[0048] m: Sample mass;

[0049] Triethanolamine conversion rate X% = (20.13 - S) * 100 / 20.13 (Equation 2)

[0050] 20.13: Hydroxyl content in triethanolamine, mmol / g.

[0051] Unless otherwise specified, the following examples and comparative examples were conducted under standard conditions or conditions recommended by the manufacturer. Reagents and instruments used, unless otherwise specified, are all commercially available products. The composition and structure of the compounds described in the following examples can be determined through preparative feeding.

[0052] Example 1

[0053] Weigh 37.25g of triethanolamine, 77.25g of diethylenetriamine, and 4.58g of supported solid catalyst (20% Ni, 8% Cu, 3% Cr, 1% Mo, with silica as the support) and add them to the reactor. Introduce 8-10MPa nitrogen gas into the magnetic high-pressure reactor, check for leaks with foam water, let stand for 30 minutes (if the pressure does not drop), then purge three times with 0.5MPa nitrogen gas, followed by two times with 0.5MPa hydrogen gas. Introduce 1MPa hydrogen gas and slowly heat to 180℃ while stirring at 800rpm. React for 6 hours. After the reaction, cool with cooling water until the temperature drops to 60℃, then slowly vent the gas. The gas is absorbed by water and discharged. Separate the catalyst and reaction product by hot filtration, and remove unreacted raw materials by vacuum distillation to obtain compound S1 with a purity of 100%. Compound S1 has the structure shown in formula (1), and n1=n2=n3=1.

[0054] Example 2

[0055] Weigh 37.25g of triethanolamine, 164.25g of triethylenetetramine, and 3.67g of supported solid catalyst (30% Ni, 6% Cu, 2% Cr, 0.5% Mo, with alumina as the support) and add them to a reactor. The reactor is then filled with nitrogen gas at 8-10 MPa. A foam water test is performed to check for leaks. After standing for 30 minutes, if the pressure does not drop, the reactor is purged three times with 0.5 MPa nitrogen gas, followed by two times with 0.5 MPa hydrogen gas. Hydrogen gas at 1.5 MPa is then introduced, and the mixture is slowly heated to 200℃ with stirring at 600 rpm for 8 hours. After the reaction, cooling water is introduced to lower the temperature to 60℃. The gas is then slowly vented, absorbed by water, and discharged. The catalyst and reaction products are separated by hot filtration, and unreacted raw materials are removed by vacuum distillation to obtain compound S2 with a purity of 100%. Compound S2 has the structure shown in formula (1), and n1 = n2 = n3 = 2.

[0056] Example 3

[0057] 37.25g of triethanolamine, 189g of tetraethylenepentamine, and 11.31g of supported solid catalyst (25% Ni, 7% Cu, 1% Cr, 1.5% Mo, with alumina as the support) were weighed and added to a reactor. The reactor was then charged with nitrogen at 8-10 MPa. A foaming water test was performed to check for leaks. After standing for 30 minutes, if the pressure did not drop, the reactor was purged three times with 0.5 MPa nitrogen, followed by two times with 0.5 MPa hydrogen. Hydrogen gas at 2.5 MPa was then introduced, and the mixture was slowly heated to 210℃ with stirring at 700 rpm for 7 hours. After the reaction, cooling water was introduced to lower the temperature. Once the temperature dropped to 60℃, the gas was slowly vented, absorbed by water, and discharged. The catalyst and reaction product were separated by hot filtration, and unreacted raw materials were removed by vacuum distillation to obtain compound S3 with a purity of 100%. Compound S3 has the structure shown in formula (1), and n1 = n2 = n3 = 3.

[0058] Example 4

[0059] Weigh 37.25g of triethanolamine, 290g of pentaethylenehexamine, and 6.55g of supported solid catalyst (35% Ni, 5% Cu, 2% Cr, 1% Mo, with silica as the support) and add them to the reactor. Introduce 8-10MPa nitrogen gas into the magnetically pressurized reactor and check for leaks with foam water. Let it stand for 30 minutes. If the pressure does not drop, replace it three times with 0.5MPa nitrogen gas, then twice with 0.5MPa hydrogen gas. Introduce 2MPa hydrogen gas and slowly heat to 220℃ while stirring at 800rpm. React for 5 hours. After the reaction, cool with cooling water until the temperature drops to 60℃. Slowly exhaust the gas, allowing it to be absorbed by water and discharged. Separate the catalyst and reaction products while hot by filtration. Remove unreacted raw materials by vacuum distillation to obtain compound S4, with a purity of 100%. Compound S4 has the structure shown in formula (1), where n1 = n2 = n3 = 4.

[0060] Example 5

[0061] Weigh 37.25g of triethanolamine, 75g of ethylenediamine, and 1.13g of supported solid catalyst (40% Ni, 4% Cu, 1% Cr, 1.5% Mo, with alumina as the support) and add them to the reactor. Introduce 8-10MPa nitrogen gas into the magnetically pressurized reactor and check for leaks with foam water. Let it stand for 30 minutes. If the pressure does not drop, replace it three times with 0.5MPa nitrogen gas, then twice with 0.5MPa hydrogen gas. Introduce 2MPa hydrogen gas and slowly heat to 220℃ while stirring at 500rpm. React for 4 hours. After the reaction, cool with cooling water until the temperature drops to 60℃. Slowly vent the gas, allowing it to be absorbed by water and discharged. Separate the catalyst and reaction products by hot filtration. Remove unreacted raw materials by vacuum distillation to obtain compound S5, with a purity of 100%. Compound S5 has the structure shown in formula (1), and n1=n2=n3=0.

[0062] Example 6

[0063] Weigh 37.25g of triethanolamine, 60g of ethylenediamine, and 1.27g of supported solid catalyst (35% Ni, 8% Cu, 2.5% Cr, 0.5% Mo, with alumina as the support) and add them to a reactor. The reactor is then filled with nitrogen gas at 8-10 MPa. A foam water test is performed to check for leaks. After standing for 30 minutes, if the pressure does not drop, the reactor is purged three times with 0.5 MPa nitrogen gas, followed by two times with 0.5 MPa hydrogen gas. Hydrogen gas at 1.5 MPa is then introduced, and the mixture is slowly heated to 190℃ with stirring at 600 rpm for 8 hours. After the reaction, cooling water is introduced to lower the temperature. Once the temperature drops to 60℃, the gas is slowly vented, absorbed by water, and discharged. The catalyst and reaction products are separated by hot filtration, and unreacted raw materials are removed by vacuum distillation to obtain compound S5 with a purity of 92.3%. Compound S5 has the structure shown in formula (1), and n1 = n2 = n3 = 0.

[0064] Example 7

[0065] 37.25g of triethanolamine, 103g of diethylenetriamine, and 2.81g of supported solid catalyst (35% Ni, 8% Cu, 2.5% Cr, 0.5% Mo, with silica as the support) were weighed and added to a reactor. The reactor was charged with nitrogen at 8-10 MPa, and leaks were checked using foam water. After standing for 30 minutes without pressure drop, the pressure was replaced three times with 0.5 MPa nitrogen, followed by two times with 0.5 MPa hydrogen. Hydrogen gas was then introduced at 2 MPa, and the mixture was slowly heated to 210℃ with stirring at 800 rpm for 5 hours. After the reaction, cooling water was introduced to lower the temperature to 60℃. The gas was slowly vented, absorbed by water, and discharged. The catalyst and reaction products were separated by hot filtration, and unreacted raw materials were removed by vacuum distillation to obtain compound S1 with a purity of 92.2%. Compound S1 has the structure shown in formula (1), and n1 = n2 = n3 = 1.

[0066] Example 8

[0067] 37.25 g of triethanolamine, 219 g of triethylenetetramine, and 8.97 g of supported solid catalyst (35% Ni, 8% Cu, 2.5% Cr, 0.5% Mo, with silica as the support) were weighed and added to a reactor. The reactor was charged with nitrogen at 8-10 MPa, and leaks were checked using foam water. After standing for 30 minutes, if the pressure did not drop, the reactor was purged three times with 0.5 MPa nitrogen, followed by two times with 0.5 MPa hydrogen. Hydrogen gas at 1.5 MPa was then introduced, and the mixture was slowly heated to 220 °C with stirring at 800 rpm for 6 hours. After the reaction, cooling water was introduced to lower the temperature. When the temperature dropped to 60 °C, the gas was slowly vented, absorbed by water, and discharged. The catalyst and reaction product were separated by hot filtration, and unreacted raw materials were removed by vacuum distillation to obtain compound S2 with a purity of 91.8%. Compound S2 has the structure shown in formula (1), and n1 = n2 = n3 = 2.

[0068] Example 9

[0069] 37.25 g of triethanolamine, 236.25 g of tetraethylenepentamine, and 10.94 g of supported solid catalyst (35% Ni, 8% Cu, 2.5% Cr, 0.5% Mo, with silica as the support) were weighed and added to a reactor. The reactor was charged with nitrogen at 8-10 MPa, and leaks were checked using foam water. After standing for 30 minutes, if the pressure did not drop, the reactor was purged three times with 0.5 MPa nitrogen, followed by two times with 0.5 MPa hydrogen. Hydrogen gas at 1 MPa was then introduced, and the mixture was slowly heated to 200 °C with stirring at 700 rpm for 8 hours. After the reaction, cooling water was introduced to lower the temperature. When the temperature dropped to 60 °C, the gas was slowly vented, absorbed by water, and discharged. The catalyst and reaction products were separated by hot filtration, and unreacted raw materials were removed by vacuum distillation to obtain compound S3 with a purity of 93.1%. Compound S3 has the structure shown in formula (1), and n1 = n2 = n3 = 3.

[0070] Example 10

[0071] 37.25g of triethanolamine, 174g of pentaethylenehexamine, and 10.56g of supported solid catalyst (35% Ni, 8% Cu, 2.5% Cr, 0.5% Mo, with alumina as the support) were weighed and added to a reactor. The reactor was then charged with nitrogen at 8-10 MPa. A foam water test was performed to check for leaks. After standing for 30 minutes, if the pressure did not drop, the reactor was purged three times with 0.5 MPa nitrogen, followed by two times with 0.5 MPa hydrogen. Hydrogen gas was then introduced at 2 MPa, and the mixture was slowly heated to 180℃ with stirring at 800 rpm for 7 hours. After the reaction, cooling water was introduced to lower the temperature. Once the temperature dropped to 60℃, the gas was slowly vented, absorbed by water, and discharged. The catalyst and reaction products were separated by hot filtration, and unreacted raw materials were removed by vacuum distillation to obtain compound S4 with a purity of 91.2%. Compound S4 has the structure shown in formula (1), and n1 = n2 = n3 = 4.

[0072] Example 11

[0073] 37.25 g of triethanolamine, 103 g of diethylenetriamine, and 2.81 g of supported solid catalyst (15% Ni, 3% Cu, 7.5% Cr, 6.5% Mo, with silica as the support) were weighed and added to a reactor. The reactor was charged with nitrogen at 8-10 MPa, and leaks were checked using foam water. After standing for 30 minutes without pressure drop, the pressure was purged three times with 0.5 MPa nitrogen, followed by two times with 0.5 MPa hydrogen. Hydrogen gas was then introduced at 2 MPa, and the mixture was slowly heated to 210 °C with stirring at 800 rpm for 5 hours. After the reaction, cooling water was introduced to lower the temperature to 60 °C. The gas was slowly vented, absorbed by water, and discharged. The catalyst and reaction product were separated by hot filtration, and unreacted raw materials were removed by vacuum distillation to obtain compound S1 with a purity of 54.2%. Compound S1 has the structure shown in formula (1), and n1 = n2 = n3 = 1.

[0074] Example 12

[0075] 37.25g of triethanolamine, 103g of diethylenetriamine, and 2.81g of supported solid catalyst (35% Ni, 8% Cu, 2.5% Cr, 0.5% Mo, with silica as the support) were weighed and added to a reactor. The reactor was charged with nitrogen at 8-10 MPa, and leaks were checked using foam water. After standing for 30 minutes, if the pressure did not drop, the reactor was purged three times with 0.5 MPa nitrogen, and then twice with 0.5 MPa hydrogen. Hydrogen gas at 0.8 MPa was then introduced, and the mixture was slowly heated to 210℃ with stirring at 800 rpm for 5 hours. After the reaction, cooling water was introduced to lower the temperature. When the temperature dropped to 60℃, the gas was slowly vented, absorbed by water, and discharged. The catalyst and reaction products were separated by hot filtration, and unreacted raw materials were removed by vacuum distillation to obtain compound S1 with a purity of 68.2%. Compound S1 has the structure shown in formula (1), and n1 = n2 = n3 = 1.

[0076] Example 13

[0077] 37.25 g of triethanolamine, 103 g of diethylenetriamine, and 2.81 g of supported solid catalyst (35% Ni, 8% Cu, 2.5% Cr, 0.5% Mo, with silica as the support) were weighed and added to a reactor. The reactor was charged with nitrogen at 8-10 MPa, and leaks were checked using foam water. After standing for 30 minutes without pressure drop, the pressure was replaced three times with 0.5 MPa nitrogen, followed by two times with 0.5 MPa hydrogen. Hydrogen gas was then introduced at 3 MPa, and the mixture was slowly heated to 210 °C with stirring at 800 rpm for 5 hours. After the reaction, cooling water was introduced to lower the temperature to 60 °C. The gas was slowly vented, absorbed by water, and discharged. The catalyst and reaction product were separated by hot filtration, and unreacted raw materials were removed by vacuum distillation to obtain compound S1 with a purity of 66.5%. Compound S1 has the structure shown in formula (1), and n1 = n2 = n3 = 1.

[0078] Comparative Example 1

[0079] Commercially available clay anti-swelling agent FP-HJZ.

[0080] Test Example 1:

[0081] The room temperature anti-swelling rate and washability after three washes were tested using the 100% pure compound obtained in Examples 1-5 as a clay anti-swelling agent and the clay anti-swelling agent of Comparative Example 1. The clay anti-swelling agent was a 0.5 wt% aqueous solution.

[0082] The high-temperature anti-swelling rate of the compound with a purity of 100% obtained in Examples 1-5 as a clay anti-swelling agent and the clay anti-swelling agent of Comparative Example 1 was tested, wherein the clay anti-swelling agent was a 1 wt% aqueous solution.

[0083] The results of room temperature anti-swelling rate, water washability and high temperature anti-swelling rate of Examples 1-5 and Comparative Example 1 are shown in Table 1.

[0084] Table 1

[0085]

[0086] As can be seen from the results in Table 1, the clay anti-swelling agents prepared using the purified compounds of this invention, such as those in Examples 1-5, have multiple and different types of amine groups in their molecular structure. These compounds can effectively adsorb onto the clay surface and effectively encapsulate the clay, resulting in excellent anti-swelling effects and temperature resistance, all of which are better than the conventional clay anti-swelling agent of Comparative Example 1. Comparing Examples 1-5, it is evident that the compounds in Examples 1-3, when used as clay anti-swelling agents, exhibit better room temperature anti-swelling rates, water-wash resistance rates, and high-temperature anti-swelling rates, showing better results than Examples 4 and 5. The ethyleneamine is preferably one or more of diethylenetriamine, triethylenetetraamine, and tetraethylenepentamine, and the resulting compounds, when used as clay anti-swelling agents, exhibit better room temperature anti-swelling rates, water-wash resistance rates, and high-temperature anti-swelling rates.

[0087] Test Example 2:

[0088] The reaction products with a purity of less than 100% obtained in Examples 6-13 were tested as clay swelling inhibitors and the clay swelling inhibitor of Comparative Example 1. The room temperature swelling rate and wash resistance after three washes were compared. The clay swelling inhibitor was a 0.5 wt% aqueous solution. This was to illustrate the influence of different reaction conditions and catalyst components on the reaction.

[0089] The reaction products obtained in Examples 6-13 were used as clay swelling inhibitors and compared with the clay swelling inhibitor in Comparative Example 1 to determine their high-temperature swelling resistance. The clay swelling inhibitor was a 1 wt% aqueous solution. This was to illustrate the influence of different reaction conditions and catalyst components on the reaction.

[0090] The results of room temperature anti-swelling rate, water washability and high temperature anti-swelling rate of Examples 6-13 and Comparative Example 1 are shown in Table 2.

[0091] Table 2

[0092]

[0093] As can be seen from the results in Table 2, the clay anti-swelling agents prepared by the present invention, such as those in Examples 6-13, have multiple amine groups of different types in their molecular structure. These groups can be effectively adsorbed onto the clay surface and effectively encapsulate the clay, giving it good anti-swelling effect and temperature resistance. Their effects are better than those of the conventional clay anti-swelling agent in Comparative Example 1.

[0094] By comparing Example 7 and Example 11, the clay anti-swelling agent of Example 7 has better room temperature anti-swelling rate, water washability, and high temperature anti-swelling rate compared to Example 11. When the catalyst component is within the content range of the components described in this invention, the catalytic effect is better, and the reaction of triethanolamine and ethyleneamine can be more complete, controlling the absence of side reactions and resulting in higher product purity. Therefore, it has better room temperature anti-swelling rate, water washability, and high temperature anti-swelling rate when used as a clay anti-swelling agent.

[0095] By comparing Examples 7 and 12-13, the clay anti-swelling agent in Example 7 exhibits better room temperature anti-swelling rate, water washability, and high temperature anti-swelling rate compared to Examples 12-13. Within the hydrogen partial pressure range described in this invention, the reaction between triethanolamine and ethyleneamine can be more complete, with no side reactions being generated, resulting in better catalytic effect and higher product purity. Therefore, when used as a clay anti-swelling agent, it has better room temperature anti-swelling rate, water washability, and high temperature anti-swelling rate. When the hydrogen partial pressure is outside the range of this application, the test results of the clay anti-swelling agent are poor.

[0096] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a compound, characterized in that, include: The compound was obtained by reacting triethanolamine and ethyleneamine in the presence of a catalyst and hydrogen. The molar ratio of triethanolamine to ethyleneamine is 1:3-6; The catalyst comprises a main active component, an auxiliary agent, and a support, wherein the support is selected from silica and / or alumina, the main active component is Ni and Cu, and the auxiliary agent is Cr and Mo; Based on the total weight of the catalyst, the catalyst contains 20-40 wt% Ni, 4-8 wt% Cu, 1-3 wt% Cr, 0.5-1.5 wt% Mo, and the support content is 47.5-74.5%. The compound has the structure shown in formula (1). （1）， Among them, n1, n2, and n3 are each independent natural numbers from 0 to 4.

2. The preparation method according to claim 1, wherein, The ethyleneamine is selected from one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

3. The preparation method according to claim 1, wherein, The amount of the catalyst is 1-5 wt% of the total amount of triethanolamine and ethyleneamine.

4. The preparation method according to any one of claims 1-3, wherein, The reaction temperature is 160-220℃, the hydrogen partial pressure is 1-2.5MPa, and the reaction time is 4-8h.

5. The application of the compound prepared by the method according to any one of claims 1-4 as a clay swelling inhibitor.

6. The application according to claim 5, wherein, The clay anti-swelling agent, at an addition of 0.5 wt%, has a room temperature anti-swelling rate of ≥90%, a water washability of ≥95%, and a temperature resistance of ≥350℃.

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