High-temperature-resistant efficient clay stabilizer and preparation method thereof

Abstract

The invention relates to the technical field of oilfield auxiliaries, and provides a high-temperature-resistant efficient clay stabilizer and a preparation method thereof.The clay stabilizer comprises self-made oligomeric organic ammonium salt containing double benzene rings and a polyether chain segment structure, benzyl quaternary ammonium salt and KCl and has excellent temperature resistance and anti-swelling performance. When the addition amount of the high-temperature-resistant efficient clay stabilizer is only 0.1%, the anti-swelling rate can reach 85% or above, the temperature resistance reaches 300 DEG C, the washing resistance reaches 100%, and the high-temperature-resistant efficient clay stabilizer can be applied to water injection anti-swelling and acid fracturing anti-swelling of oil fields.

Description

Technical Field

[0001] The invention relates to a clay stabilizer with high temperature resistance, belonging to the technical field of oil field additives. Background Art

[0002] Low-permeability reservoirs account for about 70% of my country's oil reservoirs. When exploiting such reservoirs, hydraulic fracturing is often used to increase production capacity. However, during the fracturing process, clay minerals easily swell when exposed to water, causing blockage of formation pores, instability of the well wall, and even collapse, which seriously affects oil and gas production. Clay stabilizer is an oilfield additive that acts on clay minerals. It has a positive charge and can be adsorbed on the surface of negatively charged clay minerals, preventing water molecules from entering the clay flakes, thereby inhibiting the hydration and dispersion of clay minerals.

[0003] The types of clay stabilizers mainly include inorganic salts, cationic surfactants and organic cationic polymers. Inorganic salt clay stabilizers are prone to cation exchange in solution, have poor stability and long-term effectiveness, cannot form multi-point adsorption, have poor erosion resistance, and are prone to harming the formation microbial community, causing soil compaction, which is harmful to the environment. With the continuous deepening of oil field exploitation, the reservoir temperature continues to rise, and cationic surfactant clay stabilizers are prone to decompose at high temperatures and lose the function of stabilizing clay. Organic cationic polymers containing amine groups are particularly effective in preventing the hydration expansion of clay and reducing the dispersion and migration of particles. They have strong temperature resistance and can be applied to medium and high temperature reservoirs, with broad application prospects. Summary of the invention

[0004] In view of the problems that existing clay stabilizers have poor temperature resistance and are prone to damage to the stratum when added in large amounts, the present invention provides a high temperature resistant and efficient clay stabilizer and a preparation method thereof. The clay stabilizer comprises a self-made oligomeric organic ammonium salt with a double benzene ring structure in the main chain, a benzyl quaternary ammonium salt and KCl, and has a temperature resistance of 300°C. When the clay stabilizer is added in an amount of 0.1%, the anti-swelling rate reaches more than 85%.

[0005] The high temperature resistant and efficient clay stabilizer provided by the present invention is characterized in that it comprises an oligomeric organic salt, a benzyl quaternary ammonium salt and an inorganic salt KCl, wherein the structural formula of the oligomeric organic ammonium salt is: Among them, n=8~16.

[0006] Generally, the molar ratio of the oligomeric organic ammonium salt, the benzyl quaternary ammonium salt and KCl in the composition of the high temperature resistant and efficient clay stabilizer is 1:20:12-1:30:18.

[0007] The preparation method of the oligomeric organic ammonium salt comprises the following steps: (1) adding bisphenol A polyoxyethylene ether, solvent, catalyst and activator into a reactor, introducing N2 gas into the reactor for displacement, and exhausting the air in the reactor; (2) introducing ammonia gas into the reaction kettle according to the required hydroxyl-ammonia ratio, and then introducing hydrogen gas, and then heating to the required reaction temperature, and conducting a constant temperature reaction under stirring to obtain an amination reaction product; (3) The reaction product is subjected to reduced pressure distillation and filtration to obtain a viscous liquid, and the viscous liquid is reacted with an acid to obtain an oligomeric organic ammonium salt.

[0008] Furthermore, in the method for preparing the oligomeric organic ammonium salt, the solvent is one or more combinations of cyclohexane, tert-butanol, toluene and tetrahydrofuran.

[0009] In the method for preparing an oligomeric organic ammonium salt, the active metal component in the catalyst is one or a combination of Ni and Co, and the weight of the active component accounts for 40% to 60% of the total weight of the catalyst.

[0010] In the method for preparing an oligomeric organic ammonium salt, the amount of catalyst added accounts for 10wt% to 30wt% of the amount of raw materials added.

[0011] In the method for preparing an oligomeric organic ammonium salt, the catalytic activator is one or more combinations of Na2CO3, NaHCO3, NaOH and NH4Cl.

[0012] The method for preparing an oligomeric organic ammonium salt has a hydroxylamine ratio of 1:2 to 1:7.

[0013] In the method for preparing an oligomeric organic ammonium salt, the hydrogen pressure is controlled at 0-2 MPa.

[0014] The method for preparing the oligomeric organic ammonium salt has a reaction temperature of 160-220°C.

[0015] The method for preparing an oligomeric organic ammonium salt has a reaction time of 3 to 7 hours.

[0016] The method for preparing an oligomeric organic ammonium salt comprises the following steps: the acid used for salt formation is one of hydrochloric acid, formic acid, acetic acid and boric acid.

[0017] The benzyl quaternary ammonium salt is one of benzyltrimethylammonium chloride, benzyltrimethylammonium bromide and benzyltriethylammonium chloride.

[0018] Compared with the prior art, the present invention has the following beneficial effects: (1) it provides a clay stabilizer with a temperature resistance of up to 300°C, and the self-made oligomeric organic ammonium salt contains a double benzene ring structure and a polyether chain segment, which effectively prevents water molecules from entering the clay sheet interlayer while improving the temperature resistance; (2) it provides a clay stabilizer with excellent anti-swelling performance, and when the clay stabilizer is added in an amount of 0.1%, the anti-swelling rate can reach more than 85%; (3) in the preparation method of the oligomeric organic ammonium salt, an activator is introduced to enhance the catalytic effect of the catalyst, thereby effectively improving the reaction conversion rate. DETAILED DESCRIPTION

[0019] The present invention is described in detail below with reference to embodiments and comparative examples. Example 1

[0020] Weigh 50.0 g of bisphenol A polyoxyethylene ether (containing 8 ethylene oxide chains), 100.0 g of tetrahydrofuran, 7.5 g of catalyst (Ni content is 40wt%) and 0.5 g of NaHCO3 in an intermittent high-pressure reactor, and tighten the high-pressure reactor. The air in the reactor was replaced three times with 0.5 MPa nitrogen. Ammonia was charged into the reactor according to the hydroxylamine ratio of 1:5, and then 1.0 MPa of hydrogen was introduced into it. The reactor was slowly heated to 190°C, and the reaction was carried out at a constant temperature for 4 h at a stirring speed of 700 rpm. The obtained product was distilled under reduced pressure at 100°C and filtered, and the obtained filtrate was the reaction product BPN-1. The amine value of the product was determined by hydrochloric acid titration, and the reaction conversion rate and selectivity were calculated. The results are shown in Table 1. A certain amount of formic acid was added to the product to adjust the pH to 7 to obtain an oligomeric organic ammonium salt.

[0021] 1.8 g of homemade oligomeric organic ammonium salt, 9.0 g of benzyltrimethylammonium chloride, 2.4 g of KCl and 31.8 g of H2O were weighed and mixed in a beaker to obtain a clay stabilizer. A 0.1% aqueous solution was prepared and recorded as sample-1. The evaluation results of its anti-swelling performance, temperature resistance and water washability are shown in Table 2. Example 2

[0022] Weigh 50.0 g of bisphenol A polyoxyethylene ether (containing 8 ethylene oxide chains), 100.0 g of tetrahydrofuran, 7.5 g of catalyst (Ni content is 50wt%) and 0.5 g of NaHCO3 in an intermittent autoclave, and tighten the autoclave. The air in the autoclave was replaced three times with 0.5 MPa nitrogen. Ammonia was charged into the autoclave according to the hydroxylamine ratio of 1:5, and then 1.5 MPa of hydrogen was introduced into it. The reactor was slowly heated to 190°C, and the reaction was carried out at a constant temperature for 4 h at a stirring speed of 700 rpm. The obtained product was distilled under reduced pressure at 100°C and filtered, and the obtained filtrate was the reaction product BPN-2. The amine value of the product was determined by hydrochloric acid titration, and the reaction conversion rate and selectivity were calculated. The results are shown in Table 1. A certain amount of formic acid was added to the product to adjust the pH to 7 to obtain an oligomeric organic ammonium salt.

[0023] Weigh 1.8 g of homemade oligomeric organic ammonium salt, 9.0 g of benzyltrimethylammonium chloride, 2.4 g of KCl and 31.8 g of H2O in a beaker and stir them thoroughly to obtain a clay stabilizer. A 0.1% aqueous solution was prepared and recorded as sample-2. The evaluation results of its anti-swelling performance, temperature resistance and water washability are shown in Table 2. Example 3

[0024] Weigh 50.0 g of bisphenol A polyoxyethylene ether (containing 8 ethylene oxide chains), 100.0 g of tetrahydrofuran, 10 g of catalyst (Ni content is 60wt%) and 0.5 g of Na2CO3 in an intermittent high-pressure reactor, and tighten the high-pressure reactor. The air in the reactor was replaced three times with 0.5 MPa nitrogen. Ammonia was charged into the reactor according to the hydroxylamine ratio of 1:5, and then 1.5 MPa of hydrogen was introduced into it. The reactor was slowly heated to 200°C, and the reaction was carried out at a constant temperature for 5 h at a stirring speed of 700 rpm. The obtained product was distilled under reduced pressure at 100°C and filtered, and the obtained filtrate was the reaction product BPN-3. The amine value of the product was determined by hydrochloric acid titration, and the reaction conversion rate and selectivity were calculated. The results are shown in Table 1. A certain amount of formic acid was added to the product to adjust the pH to 7 to obtain an oligomeric organic ammonium salt.

[0025] 1.8 g of homemade oligomeric organic ammonium salt, 9.0 g of benzyltrimethylammonium chloride, 2.4 g of KCl and 31.8 g of H2O were weighed and mixed in a beaker to obtain a clay stabilizer. A 0.1% aqueous solution was prepared and recorded as sample-3. The evaluation results of its anti-swelling performance, temperature resistance and water washability are shown in Table 2. Example 4

[0026] Weigh 50.0 g of bisphenol A polyoxyethylene ether (containing 10 ethylene oxide chains), 100.0 g of tert-butyl alcohol, 10 g of catalyst (Ni content is 50wt%) and 0.5 g of Na2CO3 in an intermittent autoclave, and tighten the autoclave. The air in the autoclave was replaced three times with 0.5 MPa nitrogen. Ammonia was charged into the autoclave according to the hydroxylamine ratio of 1:6, and then 1.5 MPa of hydrogen was introduced into it. The reactor was slowly heated to 200°C, and the reaction was carried out at a constant temperature for 5 h at a stirring speed of 700 rpm. The obtained product was subjected to reduced pressure distillation at 100°C and filtered, and the obtained filtrate was the reaction product BPN-4. The amine value of the product was determined by hydrochloric acid titration, and the reaction conversion rate and selectivity were calculated. The results are shown in Table 1. A certain amount of acetic acid was added to the product to adjust the pH to 7 to obtain an oligomeric organic ammonium salt.

[0027] 1.5 g of homemade oligomeric organic ammonium salt, 9.0 g of benzyltrimethylammonium chloride, 2.4 g of KCl and 32.1 g of H2O were weighed and mixed in a beaker to obtain a clay stabilizer. A 0.1% aqueous solution was prepared and recorded as sample-4. The evaluation results of its anti-swelling performance, temperature resistance and water washing resistance are shown in Table 2. Example 5

[0028] Weigh 50.0 g of bisphenol A polyoxyethylene ether (containing 10 ethylene oxide chains), 100.0 g of tert-butyl alcohol, 7.5 g of catalyst (Co content is 40wt%) and 0.5 g of Na2CO3 in an intermittent autoclave, and tighten the autoclave. The air in the autoclave was replaced three times with 0.5 MPa nitrogen. Ammonia was charged into the autoclave according to the hydroxylamine ratio of 1:6, and then 2.0 MPa of hydrogen was introduced into it. The reactor was slowly heated to 210°C, and the reaction was carried out at a constant temperature for 5 h at a stirring speed of 700 rpm. The obtained product was distilled under reduced pressure at 100°C and filtered, and the obtained filtrate was the reaction product BPN-5. The amine value of the product was determined by hydrochloric acid titration, and the reaction conversion rate and selectivity were calculated. The results are shown in Table 1. A certain amount of acetic acid was added to the product to adjust the pH to 7 to obtain an oligomeric organic ammonium salt.

[0029] 1.5 g of homemade oligomeric organic ammonium salt, 11.0 g of benzyltrimethylammonium bromide, 2.4 g of KCl and 32.1 g of H2O were weighed and mixed in a beaker to obtain a clay stabilizer. A 0.1% aqueous solution was prepared and recorded as sample-5. The evaluation results of its anti-swelling performance, temperature resistance and water washability are shown in Table 2. Example 6

[0030] Weigh bisphenol A polyoxyethylene ether (containing 10 ethylene oxide chains), 100.0 g tert-butyl alcohol, 7.5 g catalyst (Co content 50wt%) and 0.5 g NH4Cl in an intermittent autoclave, and tighten the autoclave. Replace the air in the autoclave with 0.5 MPa nitrogen three times. Fill the autoclave with ammonia at a hydroxylamine ratio of 1:6, and then pass 2.0 MPa hydrogen into it. Slowly heat the autoclave to 220°C, and react at a constant temperature for 5 h at a stirring speed of 700 rpm. The obtained product is vacuum distilled at 100°C and filtered, and the obtained filtrate is the reaction product BPN-6. The amine value of the product is determined by hydrochloric acid titration, and the reaction conversion rate and selectivity are calculated. The results are shown in Table 1. A certain amount of acetic acid is added to the product to adjust the pH to 7 to obtain an oligomeric organic ammonium salt.

[0031] 1.5 g of homemade oligomeric organic ammonium salt, 11.0 g of benzyltrimethylammonium bromide, 2.4 g of KCl and 32.1 g of H2O were weighed and mixed in a beaker to obtain a clay stabilizer. A 0.1% aqueous solution was prepared and recorded as sample-6. The evaluation results of its anti-swelling performance, temperature resistance and water washability are shown in Table 2. Example 7

[0032] Weigh bisphenol A polyoxyethylene ether (containing 12 ethylene oxide chains), 100.0 g toluene, 5.0 g catalyst (Co content 60wt%) and 0.5 g NH4Cl in an intermittent autoclave, and tighten the autoclave. Replace the air in the autoclave with 0.5 MPa nitrogen three times. Fill the autoclave with ammonia at a hydroxylamine ratio of 1:7, and then pass 1.5 MPa hydrogen into it. Slowly heat the autoclave to 220°C, and react at a constant temperature for 6 h at a stirring speed of 700 rpm. The obtained product is vacuum distilled at 100°C and filtered, and the obtained filtrate is the reaction product BPN-7. The amine value of the product is determined by hydrochloric acid titration, and the reaction conversion rate and selectivity are calculated. The results are shown in Table 1. A certain amount of boric acid is added to the product to adjust the pH to 7 to obtain an oligomeric organic ammonium salt.

[0033] 1.3 g of homemade oligomeric organic ammonium salt, 10.0 g of benzyltriethylammonium chloride, 2.4 g of KCl and 31.3 g of H2O were weighed and mixed in a beaker to obtain a clay stabilizer. A 0.1% aqueous solution was prepared and recorded as sample-7. The evaluation results of its anti-swelling performance, temperature resistance and water washability are shown in Table 2. Example 8

[0034] Weigh bisphenol A polyoxyethylene ether (containing 12 ethylene oxide chains), 100.0 g toluene, 7.5 g catalyst (Ni content 50wt%) and 0.5 g NH4Cl in an intermittent autoclave, and tighten the autoclave. Replace the air in the autoclave with 0.5 MPa nitrogen three times. Fill the autoclave with ammonia at a hydroxylamine ratio of 1:7, and then pass 1.5 MPa hydrogen into it. Slowly heat the autoclave to 210°C, and react at a constant temperature for 6 h at a stirring speed of 700 rpm. The obtained product is vacuum distilled at 100°C and filtered, and the obtained filtrate is the reaction product BPN-8. The amine value of the product is determined by hydrochloric acid titration, and the reaction conversion rate and selectivity are calculated. The results are shown in Table 1. A certain amount of boric acid is added to the product to adjust the pH to 7 to obtain an oligomeric organic ammonium salt.

[0035] 1.3 g of homemade oligomeric organic ammonium salt, 10.0 g of benzyltriethylammonium chloride, 2.4 g of KCl and 31.3 g of H2O were weighed and mixed in a beaker to obtain a clay stabilizer. A 0.1% aqueous solution was prepared and recorded as sample-8. The evaluation results of its anti-swelling performance, temperature resistance and water washability are shown in Table 2. Example 9

[0036] Weigh bisphenol A polyoxyethylene ether (containing 12 ethylene oxide chains), 100.0 g toluene, 10.0 g catalyst (Co content 50wt%) and 0.5 g NH4Cl in an intermittent autoclave, and tighten the autoclave. Remove the air in the autoclave by replacing it with 0.5 MPa nitrogen three times. Fill the autoclave with ammonia according to the hydroxylamine ratio of 1:7, and then pass 2.0 MPa hydrogen into it. Slowly heat the reactor to 210℃, and react at a constant temperature for 6 h at a stirring speed of 700 rpm. The obtained product is vacuum distilled at 100℃ and filtered, and the obtained filtrate is the reaction product BPN-9. The amine value of the product is determined by hydrochloric acid titration, and the reaction conversion rate and selectivity are calculated. The results are shown in Table 1. A certain amount of boric acid is added to the product to adjust the pH to 7 to obtain an oligomeric organic ammonium salt.

[0037] 1.3 g of homemade oligomeric organic ammonium salt, 10.0 g of benzyltriethylammonium chloride, 2.4 g of KCl and 31.3 g of H2O were weighed and mixed in a beaker to obtain a clay stabilizer. A 0.1% aqueous solution was prepared and recorded as sample-9. The evaluation results of its anti-swelling performance, temperature resistance and water washability are shown in Table 2.

[0038] Comparative Example 1 In Example 1, the addition of raw materials does not introduce an activating agent, NaHCO3, and the remaining reaction steps are the same as in Example 1. The amine value of the product is determined by hydrochloric acid titration, and the reaction conversion rate and selectivity are calculated. The results are shown in Table 1. A certain amount of formic acid is added to the product to adjust the pH to 7 to obtain an oligomeric organic ammonium salt.

[0039] 1.8 g of homemade oligomeric organic ammonium salt, 9.0 g of benzyltrimethylammonium chloride, 2.4 g of KCl and 31.8 g of H2O were weighed and mixed in a beaker to obtain a clay stabilizer. A 0.1% aqueous solution was prepared as Comparative Example 1. The evaluation results of its anti-swelling performance, temperature resistance and water washability are shown in Table 2.

[0040] The steps of measuring amine value by hydrochloric acid titration method:

[0041] (1) Determination of total amine value: Weigh about 1g of sample into a 250mL conical flask (accurate to 0.1mg), add 50mL of ethanol and heat for 1 minute to prevent NH4 + The solution was cooled to room temperature after removing the interference. Five drops of bromophenol blue indicator were added and titrated to the yellow end point with 0.1 mol / L HCl under stirring. The total amine value A1 was calculated based on the volume V1 of HCl consumed. The calculation formula is shown in Formula 1.

[0042] A1=C1*V1 / M1 (Formula 1) In the formula: A1: total amine value of the product, mmol / g; M1: sample mass, g; V1: volume of hydrochloric acid consumed, mL; C1: concentration of hydrochloric acid used for titration, mol / L.

[0043] (2) Determination of primary, secondary and tertiary amine groups Weigh two samples of about 1.0 g each and place them in a 250 mL conical flask (dissolve them first if they are solids), mark them as S and T, add 50 mL CHCl3 and heat for 1 minute to prevent NH4 + interference, and then cool to room temperature. Add 3mL of salicylaldehyde to the S sample, let it stand for 30 minutes, add 1mL of bromophenol blue indicator, and titrate with 0.1mol / L HCl to the yellow endpoint under stirring. Calculate the sum of the secondary and tertiary amine values ​​based on the volume V2 of HCl consumed, and the calculation formula is shown in Formula 2. Add 3mL of phenyl isothiocyanate to the T sample, let it stand for 30 minutes, add 1mL of bromophenol blue indicator, and titrate with 0.1mol / L HCl to the yellow endpoint under stirring. Calculate the tertiary amine value based on the volume V3 of HCl consumed, and the calculation formula is shown in Formula 3: A2=C1*V2 / M2 (Formula 2) A3=C1*V1 / M3 (Formula 3) In the formula: A2: the sum of secondary and tertiary amines, mmol / g; A3: the tertiary amine value, mmol / g; M2: sample mass, g; M3: sample mass, g.

[0044] The calculation formulas for the secondary amine value and the primary amine value are shown in Formula 4 and Formula 5 respectively: A4=A2-A3 (Formula 4) A5=A1-A2 (Formula 5) Wherein: A4: secondary amine value, mmol / g; A5: tertiary amine value, mmol / g.

[0045] (3) Calculation method of reaction conversion rate and selectivity The reaction conversion rate and selectivity calculation formulas are shown in Equation 6 and Equation 7 respectively:

[0046] Evaluation method of anti-swelling performance:

[0047] The anti-swelling rate test was carried out in accordance with the "SY / T5971-2016 Performance Evaluation Method of Clay Stabilizer for Water Injection", and the steps are as follows: weigh 0.5g of sodium bentonite, add it to a 10mL centrifuge tube, add deionized water to the 10mL mark, shake it thoroughly, let it stand at room temperature for 2h, put it into a centrifuge, centrifuge it at a speed of 1500r / min for 15min, and read the volume V2 of sodium bentonite in water. Use the same steps to replace the clean water with a certain concentration of clay stabilizer aqueous solution, and measure the volume V1 of the soil after centrifugation. Use kerosene instead of water to measure the volume V0 of the soil. The anti-swelling rate calculation formula is as follows:

[0048] Where: or —anti-swelling rate, %; V0—volume of sodium bentonite in kerosene, mL; V1—volume of sodium bentonite in clay stabilizer, mL; V2—volume of sodium bentonite in clean water, mL.

[0049] Evaluation method of anti-swelling performance after 300℃ high temperature aging:

[0050] According to the "QS / H125-2017 Technical Requirements for Clay Stabilizers", high temperature and anti-swelling rate test was carried out. Weigh 3.00g of bentonite powder, accurate to 0.01g and load it into a high temperature and high pressure closed reactor. Add 60mL of 4% clay stabilizer solution, shake well and mix, put it in an oven at 300±2℃ for 24h, and cool to room temperature. Transfer all the clay stabilizer mixture in the high temperature and high pressure closed reactor into a 100mL beaker, shake well, quickly take out 10mL and add it to a glass centrifuge tube, load it into a centrifuge with automatic balancing function, centrifuge it at 1500r / min for 15min, and read the expansion volume V1 of the bentonite. The anti-swelling rate calculation formula is as follows:

[0051] Where: V0 is the expansion volume of bentonite in kerosene; V1 is the expansion volume of bentonite in clay stabilizer aqueous solution; V2 is the expansion volume of bentonite in clean water.

[0052] Evaluation method for water washability:

[0053] Pour out the supernatant in the centrifuge tube after high temperature aging centrifugation, add deionized water to 10 mL, stir thoroughly, let stand for 2 hours, and centrifuge at 1500r / min for 15 minutes. Finally, read the final volume V1 of the bentonite in the centrifuge tube. ′ The calculation formula of water washability is as follows:

[0054] Where: V1 is the expansion volume of bentonite in clay stabilizer aqueous solution, mL; V1′ is the expansion volume of bentonite after washing, mL; V2 is the expansion volume of bentonite in clean water, mL.

[0055] Table 2 Performance evaluation results of samples of examples and comparative examples

[0056] It can be seen from the above embodiments that the preparation method of the clay stabilizer provided by the present invention is simple to operate, and the reaction performance is effectively improved by introducing an activator. The prepared clay stabilizer has excellent temperature resistance and outstanding anti-swelling effect. When the addition amount is only 0.1%, the anti-swelling rate can reach more than 85%, the temperature resistance can reach 300°C, and the water washing resistance rate can reach 100%.

Claims

1. A high temperature resistant and efficient clay stabilizer, characterized in that It contains oligomeric organic ammonium salt, benzyl quaternary ammonium salt and inorganic salt KCl, wherein the structural formula of the oligomeric organic ammonium salt is: Among them, n=8~16.

2. The high temperature resistant and efficient clay stabilizer according to claim 1, characterized in that The molar ratio of the oligomeric organic ammonium salt, the benzyl quaternary ammonium salt and KCl in the composition is 1:20:12~1:30:

18.

3. The high temperature resistant and efficient clay stabilizer according to claim 1 or 2, characterized in that The preparation method of the oligomeric organic ammonium salt comprises the following steps: (1) Add bisphenol A polyoxyethylene ether, solvent, catalyst and activator into a reactor, introduce N2 gas into the reactor for replacement, and exhaust the air in the reactor; (2) introducing ammonia gas into the reactor according to the required hydroxyl-ammonia ratio, and then introducing hydrogen gas, and then heating to the required reaction temperature, and conducting a constant temperature reaction under stirring to obtain an amination reaction product; (3) The reaction product is subjected to reduced pressure distillation and filtration to obtain a viscous liquid, and the viscous liquid is reacted with an acid to obtain an oligomeric organic ammonium salt.

4. The high temperature resistant and efficient clay stabilizer according to claim 3, characterized in that The solvent is one or more combinations of cyclohexane, tert-butyl alcohol, toluene and tetrahydrofuran.

5. The high temperature resistant and efficient clay stabilizer according to claim 3, characterized in that The active metal component in the catalyst is one or a combination of Ni and Co, and the weight of the active component accounts for 40% to 60% of the total weight of the catalyst.

6. The high temperature resistant and efficient clay stabilizer according to claim 3, characterized in that The amount of the catalyst added is 10wt% to 30wt% of the raw material added.

7. The high temperature resistant and efficient clay stabilizer according to claim 3, characterized in that The activating agent is one or more combinations of Na2CO3, NaHCO3, NaOH and NH4Cl.

8. The high temperature resistant and efficient clay stabilizer according to claim 3, characterized in that The hydroxylamine ratio is 1:2 to 1:

7.

9. The high temperature resistant and efficient clay stabilizer according to claim 3, characterized in that The pressure of the hydrogen gas charged is 0-2MPa.

10. The high temperature resistant and efficient clay stabilizer according to claim 3, characterized in that The reaction temperature is 160~220℃, and the reaction time is 3~7h.

11. The high temperature resistant and efficient clay stabilizer according to claim 3, characterized in that The acid used in the reaction is one of hydrochloric acid, formic acid, acetic acid and boric acid.

12. The high temperature resistant and efficient clay stabilizer according to claim 1 or 2, characterized in that Benzyl quaternary ammonium salt is one of benzyltrimethylammonium chloride, benzyltrimethylammonium bromide and benzyltriethylammonium chloride.

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