A gel breaker and a method for preparing the same

Abstract

The present application belongs to the technical field of oil and gas field waste mud treatment, and particularly relates to a gel breaker and a preparation method thereof. The gel breaker is used for oil and gas field drilling waste mud treatment, and is made of the following raw materials in mass percentage: 30%-45% of a gel breaking main agent, 15%-25% of a gel breaking auxiliary agent, 2%-3% of a catalyst, 5%-8% of a stabilizer, 3%-5% of an oxidizing agent, 1%-1.5% of an adsorbent, 0.5%-1% of a pH regulator, and the balance of water; the catalyst is obtained by loading metal palladium onto a titanium dioxide carrier. The gel breaker provided by the present application has the advantages of fast gel breaking speed, low cost and wide temperature range, and the preparation method is simple and suitable for large-scale production and application.

Description

Technical Field

[0001] This invention belongs to the field of oil and gas field waste mud treatment technology, specifically relating to a desiccant and its preparation method. Background Technology

[0002] Drilling waste mud is one of the most common pollutants in oil and gas extraction. To achieve safe and rapid drilling, the types and quantities of chemicals added to drilling fluids are increasing, and their composition is becoming increasingly complex. Furthermore, as drilling processes place higher demands on mud, mud systems are becoming more complex, and formulations are becoming more diversified. All of this leads to drilling waste mud not only having increasingly complex compositions but also posing a greater threat to the ecological environment. After drilling operations are completed, almost all waste is discharged and accumulated in waste mud storage pits, eventually forming a multiphase suspended drilling waste mud composed of clay, weighting materials, various chemical treatment agents, wastewater, sludge, and drill cuttings. Direct discharge without treatment will pollute the surrounding soil and water sources. Through the bioaccumulation by crops and plants, it will ultimately endanger human health.

[0003] Currently, oil and gas fields generally use a combination of physical and chemical methods to treat drilling waste mud. The core of this method is to dilute, flocculate, and separate the drilling waste mud into three parts: cuttings, mud cake, and water. The treatment process involves: first, washing and diluting the solids in the mud with water; then, using a composite high-efficiency breaker and flocculant to coagulate the waste mud, disrupting its colloidal stability and allowing the aqueous solution to be released from the mud; finally, using vacuum adsorption to precipitate the aqueous solution from the solids. However, while many types of breaker are used in this process, the treatment effect is generally limited (the time required for the mud viscosity to decrease to 2 mPa·s after breaker dissolution is 1.5-2 hours), and the breaker speed is slow, making it difficult to meet the need for on-site mud treatment while it is being generated, and easily leading to mud accumulation. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a breaker and its preparation method for use in the treatment of waste drilling mud in gas fields. This improves the breaker speed and helps alleviate the problem of mud accumulation.

[0005] The present invention is specifically implemented through the following technical solution.

[0006] The first objective of this invention is to provide a breaker for treating waste drilling mud in oil and gas fields, made from the following raw materials in weight percentages:

[0007] The composition consists of 30%-45% main degreasing agent, 15%-25% degreasing aid, 2%-3% catalyst, 5%-8% stabilizer, 3%-5% oxidant, 1%-1.5% adsorbent, 0.5%-1% pH adjuster, and the remainder is water.

[0008] The catalyst is obtained by loading metallic palladium onto a titanium dioxide support.

[0009] In a preferred embodiment of the present invention, the catalyst is prepared by the following steps:

[0010] At room temperature, a mixed solution of glacial acetic acid and tetrabutyl titanate was prepared using anhydrous ethanol as a solvent; palladium and silicon dioxide were added to the mixed solution, and after stirring until homogeneous, water was added and stirring was continued to obtain a gel; the gel was dried and ground, and then sintered at 500-550℃ for 3-3.5h to obtain the catalyst.

[0011] In a preferred embodiment of the present invention, the volume ratio of glacial acetic acid, tetrabutyl titanate, and anhydrous ethanol in the mixed solution is 0.9-1:4-6:26.

[0012] The ratio of palladium to anhydrous ethanol is 1-3g:26mL, and the mass ratio of palladium to silica powder is 1:1.

[0013] The volume ratio of water to anhydrous ethanol is 3-5:26.

[0014] In a preferred embodiment of the present invention, the debonding agent is prepared by mixing the following raw materials in the following mass percentages: 20% to 30% ammonium persulfate, 10% to 15% sodium perborate, and the balance being potassium peroxymonosulfate.

[0015] In a preferred embodiment of the present invention, the debonding agent is fatty alcohol polyoxyethylene ether, which is prepared by mixing the following raw materials in the indicated mass percentages: penetrant JFC 30%–35%, AEO-5 40%–45%, and leveling agent O 20%–30%.

[0016] In a preferred embodiment of the present invention, the stabilizer is sodium aminotrimethylphosphonate or sodium ethylenediaminetetramethylenephosphonate.

[0017] In a preferred embodiment of the present invention, the oxidant is one of potassium permanganate, sodium hypochlorite, and hydrogen peroxide.

[0018] In a preferred embodiment of the present invention, the adsorbent is one of quicklime, sodium bentonite, and biomass, and the biomass is one of walnut shells, sawdust, and corn stalks.

[0019] In a preferred embodiment of the present invention, the pH adjuster is citric acid or sorbic acid.

[0020] The present invention also provides a method for preparing the above-mentioned breaker, comprising the following steps:

[0021] Weigh the following raw materials by weight percentage: 30%-45% degreasing agent, 15%-25% degreasing aid, 2%-3% catalyst, 5%-8% stabilizer, 3%-5% oxidant, 1%-1.5% adsorbent, 0.5%-1% pH adjuster, and the remainder is water;

[0022] Mix the de-gluing agent with water to prepare mixture 1. Then add the de-gluing aid and catalyst and mix to prepare mixture 2. Add the stabilizer and adsorbent to mixture 2 in sequence, stir evenly, and let stand for 1-2 hours to prepare mixture 3. Add the pH adjuster, oxidant, and the remaining water weighed out to mixture 3 in sequence, mix and stir evenly to obtain the de-gluing agent. The mass fraction of water in mixture 1 is 12% to 44%.

[0023] Compared with the prior art, the present invention has the following advantages:

[0024] To address the problem of slow debriding speed in existing debriding agents, this invention provides a novel debriding agent formulation. The formulation comprises 30%-45% debriding main agent, 15%-25% debriding aid, 2%-3% catalyst, 5%-8% stabilizer, 3%-5% oxidant, 1%-1.5% adsorbent, 0.5%-1% pH adjuster, and the balance being water. In this formulation, the addition of a catalyst with palladium as the active component accelerates the debriding of the mud system. This is because the catalyst of this invention primarily uses palladium as the active component, which is loaded onto titanium dioxide generated during the reaction. Palladium mainly reduces the surface activation energy of the mud colloids, assisting the main agent and aid in accelerating the debriding speed. Titanium dioxide primarily serves as a load for palladium in this catalyst. Titanium dioxide possesses unique properties, exhibiting a strong interaction with the loaded palladium metal, altering the catalyst's adsorption and catalytic performance. This results in an catalyst with advantages such as strong resistance to poisoning, good low-temperature activity, adjustable surface acidity, and high-temperature reducibility. The addition of palladium catalyst lowers the activation energy of the mud colloidal interface, which further reduces the energy required for depolymerization, thereby accelerating the reaction rate and speeding up the depolymerization process.

[0025] In this invention's formulation, the presence of a stabilizer inhibits the reactions between the components of the breaker, allowing the breaker to be stored for extended periods and adaptable to operating environments ranging from 10 to 60°C. It exhibits strong adaptability to waste mud treatment from different mud systems. This is because the stabilizer selected in this invention is a nitrogen-containing organic polyphosphonic acid, a cathodic corrosion inhibitor with a corrosion inhibition rate 3-5 times higher. It is water-miscible, non-toxic, non-polluting, and possesses good chemical stability and temperature resistance, maintaining good scale inhibition even at 200°C. Because it can dissociate into multiple positive and negative ions in water, it can chelate with multiple metal ions to form stable, large-molecule network complexes with multiple monomeric structures, loosely dispersed in water. This not only inhibits corrosion but also provides strong scale inhibition. Adding it to the breaker utilizes the multiple positive and negative ions it dissociates to inhibit chemical reactions among the components of the breaker.

[0026] In the formulation of this invention, the addition of oxidant enhances the gel breaking process, which can quickly destroy the colloidal structure and accelerate the gel breaking speed and efficiency to a certain extent. Moreover, the oxidant can also oxidize and decompose other organic matter in the slurry after gel breaking. While playing the role of gel breaking, it can also reduce the content of organic matter in the slurry, laying the groundwork for the subsequent flocculation and dewatering treatment of the slurry, and further ensuring the complete gel breaking of the slurry system.

[0027] The components of the breaker in this invention are all composed of commercially available common chemical agents, which are inexpensive. Therefore, the breaker provided by this invention has the advantages of fast breaker speed, low cost and wide temperature range. Moreover, the preparation method is simple, which can alleviate the problem of mud accumulation and is suitable for large-scale production applications. Attached Figure Description

[0028] Figure 1 The images show the appearance of the mud before and after using the breaker in Example 1; where (a) and (b) are the appearance of the mud before breaker at room temperature; and (c) and (d) are the appearance of the mud after breaker at room temperature.

[0029] Figure 2 This is an appearance diagram of the breaker in Example 1 at room temperature.

[0030] Figure 3 This is an appearance diagram of the breaker in Example 2 at room temperature.

[0031] Figure 4 This is an appearance diagram of the breaker in Example 3 at room temperature.

[0032] Figure 5 The image shows the appearance of the breaker in Comparative Example 1 at room temperature.

[0033] Figure 6 The image shows the appearance of Comparative Example 3's breaker at room temperature.

[0034] Figure 7 The image shows the appearance of Comparative Example 4's breaker at room temperature.

[0035] Figure 8 The image shows the appearance of the desiccant in Example 1 at 10°C.

[0036] Figure 9 The appearance of the desiccant in Example 1 at 60°C is shown in the diagram. Detailed Implementation

[0037] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific embodiments and accompanying drawings. However, the embodiments described are not intended to limit the present invention.

[0038] Unless otherwise specified, the experimental and detection methods described in the following embodiments are conventional methods; unless otherwise specified, the reagents and materials are commercially available.

[0039] Drilling waste mud has a complex composition, containing clay, weighting materials, various chemical treatment agents, wastewater, oily waste, and drill cuttings. Current treatment methods first involve washing and diluting the solids in the mud with water. Then, a composite high-efficiency breaker and flocculant are used to coagulate the waste mud, disrupting its colloidal stability and allowing the aqueous solution to be released from the mud. Finally, vacuum adsorption is used to precipitate the aqueous solution from the solids. These methods combine physical and chemical approaches and can remove harmful substances from the mud to some extent. However, the types of breaker used in this process are numerous, and their treatment effects are generally limited. Different types of breaker have different mechanisms of action and treatment effects, making it difficult to meet the requirement of treating mud as it is generated on-site. Therefore, mud accumulation is likely to occur.

[0040] Therefore, this invention provides a novel breaker formulation, comprising 30%-45% breaker main agent, 15%-25% breaker aid, 2%-3% catalyst, 5%-8% stabilizer, 3%-5% oxidant, 1%-1.5% adsorbent, 0.5%-1% pH adjuster, and the balance being water. The time required for the slurry viscosity to decrease to 2 mPa·s after breaker breaking is 58-62 minutes, while currently used breaker agents require 1.5-2 hours. This comparison shows that the breaker of this invention has a faster breaker speed and shortens the breaker time, thus mitigating the risk of slurry accumulation and achieving the goal of processing slurry while it is being generated.

[0041] The reason why the breaker of this invention has a fast breaking speed is that the components of the breaker are rationally designed. The formula of this invention adds a catalyst with palladium as the active component. Under the action of the catalyst, the breaking of the mud system is accelerated. The reason why the catalyst can accelerate the breaking is:

[0042] Different catalysts can only accelerate specific types of chemical reactions. The demulsification process is essentially a chemical demulsification reaction involving a catalyst. While demulsification can be achieved using only normal demulsifiers and main agents without a catalyst, the demulsification rate is very slow, making it difficult to meet the requirements of on-site production and processing. The catalyst of this invention primarily uses palladium as the active component, loaded onto the titanium dioxide generated in the reaction. It exhibits high catalytic activity, strong selectivity, low dosage, and can be repeatedly regenerated and reactivated. The addition of palladium catalyst lowers the activation energy of the mud colloid interface, significantly reducing the energy required for demulsification and thus accelerating the reaction rate. The reactivation process of the palladium catalyst is essentially similar to the calcination process in the manufacturing process. Deactivated palladium metal catalysts generally require palladium recovery. The recovery method involves dissolving the palladium on the spent catalyst into palladium nitrate using nitric acid, followed by various purification and reduction steps, and then reducing it back to metallic palladium with hydrogen for reuse in palladium catalyst manufacturing. Palladium mainly serves to lower the activation energy of the mud colloid surface, assisting the main agent and auxiliary agents in accelerating the demulsification rate. Titanium dioxide mainly serves as a support for palladium metal in this catalyst. Titanium dioxide has unique properties and can interact strongly with the supported palladium metal, which changes the adsorption and catalytic performance of the catalyst, giving it advantages such as strong resistance to poisoning, good low-temperature activity, adjustable surface acidity, and high-temperature reducibility.

[0043] Experimental results show that the activation energy for the gel breaking reaction without a catalyst is approximately 110 kJ / mol, while the activation energy for the gel breaking reaction with a catalyst is approximately 35 kJ / mol, which significantly reduces the activation energy of the reaction process.

[0044] In a preferred embodiment of the present invention, the catalyst is prepared by the following steps:

[0045] At room temperature, a mixed solution of glacial acetic acid and tetrabutyl titanate was prepared using anhydrous ethanol as a solvent; palladium and silicon dioxide were added to the mixed solution, and after stirring until homogeneous, water was added and stirring was continued to obtain a gel; the gel was dried and ground, and then sintered at 500-550℃ for 3-3.5h to obtain the catalyst.

[0046] In a preferred embodiment of the present invention, the volume ratio of glacial acetic acid, tetrabutyl titanate, and anhydrous ethanol in the mixed solution is 0.9-1:4-6:26; the amount ratio of palladium to anhydrous ethanol is 1-1.5g:26mL; the mass ratio of palladium to silica powder is 1:1; and the volume ratio of water to anhydrous ethanol is 3-5:26.

[0047] In a preferred embodiment of the present invention, the catalyst preparation step is as follows:

[0048] Commercially available glacial acetic acid (17.5 mol / L, 0.9-1.0 mL) and anhydrous ethanol (10-12 mL) were mixed and then added dropwise to a mixed solution of anhydrous ethanol (14-16 mL) and tetrabutyl titanate (4-6 mL), and mixed thoroughly. 1-3 g of palladium and 1-3 g of silica powder were weighed and dried at 70-80 °C for 4-4.5 h, then added to the above mixed solution. The mixture was stirred for 30-35 min, and then 3-5 mL of distilled water was added and stirred until gelation occurred. The resulting gel was dried in a constant temperature oven at 70-80 °C, ground, and calcined at 500-550 °C for 3-3.5 h. The resulting white powder is the ternary composite nanocatalyst.

[0049] In this invention's formulation, the presence of a stabilizer inhibits the reaction of the mixed agents, allowing the breaker to be stored for extended periods and adaptable to operating environments ranging from 10-60℃. It exhibits strong adaptability to waste mud treatment generated from different mud systems. This is because the stabilizer selected in this invention is a nitrogen-containing organic polyphosphonic acid, a cathodic corrosion inhibitor with a corrosion inhibition rate 3-5 times higher. It is water-miscible, non-toxic, non-polluting, and possesses good chemical stability and temperature resistance, maintaining good scale inhibition even at 200℃. Because it can dissociate into multiple positive and negative ions in water, it can chelate with multiple metal ions, forming multiple monomeric macromolecular network-stable complexes, loosely dispersed in water. This not only provides corrosion inhibition but also exhibits strong scale inhibition capabilities. Adding it to the breaker utilizes the multiple positive and negative ions it dissociates to inhibit chemical reactions among the components of the breaker.

[0050] In a preferred embodiment of the present invention, the stabilizer is sodium aminotrimethylphosphonate or sodium ethylenediaminetetramethylenephosphonate.

[0051] In the formulation of this invention, the addition of oxidant enhances the gel breaking process, which can quickly destroy the colloidal structure and accelerate the gel breaking speed and efficiency to a certain extent. Moreover, the oxidant can also oxidize and decompose other organic matter in the slurry after gel breaking. While playing the role of gel breaking, it can also reduce the content of organic matter in the slurry, laying the groundwork for the subsequent flocculation and dewatering treatment of the slurry, and further ensuring the complete gel breaking of the slurry system.

[0052] In a preferred embodiment of the present invention, the oxidant is one of potassium permanganate, sodium hypochlorite, and hydrogen peroxide.

[0053] In a preferred embodiment of the present invention, the debonding agent is prepared by mixing the following raw materials in the following mass percentages: 20%-30% ammonium persulfate, 10%-15% sodium perborate, and the balance being potassium peroxymonosulfate.

[0054] In a preferred embodiment of the present invention, the debonding agent is fatty alcohol polyoxyethylene ether, which is prepared by mixing the following raw materials in the indicated mass percentages: penetrant JFC 30%-35%, AEO-5 40%-45%, and the balance being leveling agent O. All of these raw materials are commercially available.

[0055] In a preferred embodiment of the present invention, the adsorbent is one of quicklime, clay, or biomass. The clay is mainly sodium bentonite, and the biomass is mainly one of walnut shells, sawdust, or corn stalks.

[0056] In a preferred embodiment of the present invention, the pH adjuster is citric acid or sorbic acid.

[0057] As can be seen from the above components, the components of the de-gumming agent of the present invention are all composed of commercially available common chemical agents, and the cost is low.

[0058] The present invention relates to a method for preparing a desiccant for treating waste drilling mud in gas fields, comprising the following steps:

[0059] Weigh the following raw materials by weight percentage: 30%-45% degreasing agent, 15%-25% degreasing aid, 2%-3% catalyst, 5%-8% stabilizer, 3%-5% oxidant, 1%-1.5% adsorbent, 0.5%-1% pH adjuster, and the remainder is water;

[0060] Mix the de-gluing agent with water to prepare mixture 1. Then add the de-gluing aid and catalyst and mix to prepare mixture 2. Add the stabilizer and adsorbent to mixture 2 in sequence, stir evenly, and let stand for 1-2 hours to prepare mixture 3. Add the pH adjuster, oxidant, and the remaining water weighed out to mixture 3 in sequence, mix and stir evenly to obtain the de-gluing agent. The mass fraction of water in mixture 1 is 12%-44%.

[0061] As can be seen, the method for preparing the breaker provided by this invention is very simple, requires simple equipment, has simple operating steps, uses commercially available reagents as raw materials, has low cost, and has good breaker effect.

[0062] The invention will now be described in detail through the following embodiments and comparative examples.

[0063] Example 1

[0064] This embodiment provides a desiccant for treating waste drilling mud in gas fields. The raw materials and their mass fractions are as follows: 30% desiccant, 15% desiccant aid, 2% catalyst, 5% stabilizer, 3% oxidant, 1.5% adsorbent, 0.5% pH adjuster, and the remainder is water.

[0065] The main de-gumming agents are ammonium persulfate, sodium perborate, and potassium peroxymonosulfate, with mass percentages of 20%, 15%, and 65%, respectively. The de-gumming aid is fatty alcohol polyoxyethylene ether, which is composed of penetrant JFC, AEO-5, and Pingpingjia O, with mass percentages of 35%, 40%, and 25%, respectively. The stabilizer is sodium aminotrimethylphosphonate. The oxidant is sodium hypochlorite. The adsorbent is corn straw. The pH adjuster is citric acid.

[0066] The preparation method of the breaker in this embodiment includes the following steps:

[0067] Add penetrant JFC, AEO-5 and Pingping O to the prepared reactor in the correct proportions, start stirring, and stir for 30 minutes to form a mixed additive.

[0068] The catalyst was prepared using the sol-gel method: 0.9 mL of glacial acetic acid and 10 mL of anhydrous ethanol were mixed and then added dropwise to a mixed solution of 16 mL of anhydrous ethanol and 6 mL of tetrabutyl titanate, and the mixture was thoroughly mixed. 1 g of palladium and 1 g of silica powder were weighed out and dried at 80 °C for 4 h, then added to the above mixed solution. The mixture was stirred for another 30 min, followed by the addition of 5 mL of distilled water and stirring until gelation occurred. The resulting gel was dried in an oven at 80 °C, ground, and calcined at 500 °C for 3 h. The resulting white powder was the catalyst.

[0069] Water was added to the prepared reactor, and stirring was started. Ammonium persulfate, sodium perborate, and potassium peroxymonosulfate were added sequentially according to the reagent ratio. After stirring for 10 minutes, a mixture was formed with a water mass fraction of 12%. Additives and catalysts were added to the mixture, followed by stabilizers and adsorbents. After stirring evenly, the mixture was allowed to stand for 1 hour. After standing for 1 hour, pH adjuster, oxidant, and water were added sequentially according to the reagent ratio, and the mixture was stirred for 4 hours to obtain a special de-gelling agent for drilling waste mud treatment.

[0070] Example 2

[0071] This embodiment provides a desiccant for treating waste drilling mud in gas fields, comprising the following raw material components: 35% desiccant, 25% desiccant aid, 3% catalyst, 5.5% stabilizer, 3.5% oxidant, 1.5% adsorbent, 0.5% pH adjuster, and the balance being water.

[0072] The main de-gelling agent consists of ammonium persulfate, sodium perborate, and potassium monopersulfate, with mass fractions of 25%, 10%, and 65%, respectively. The de-gelling aid is fatty alcohol polyoxyethylene ether, which is composed of penetrant JFC, AEO-5, and Pingpingjia O, with mass fractions of 35%, 45%, and 20%, respectively. The stabilizer is sodium ethylenediaminetetramethylenephosphonate. The oxidant is potassium permanganate. The adsorbent is quicklime. The pH adjuster is sorbic acid.

[0073] The preparation method of the breaker in this embodiment includes the following steps:

[0074] Add penetrant JFC, AEO-5 and Pingping O to the prepared reactor in the correct proportions, start stirring, and stir for 30 minutes to form a mixed additive.

[0075] The catalyst was prepared using the sol-gel method: 1.0 mL of glacial acetic acid and 12 mL of anhydrous ethanol were mixed and then added dropwise to a mixed solution of 14 mL of anhydrous ethanol and 4 mL of tetrabutyl titanate, and the mixture was thoroughly mixed. 1.5 g of palladium and silica powder were weighed and dried at 70 °C for 4.5 h, then added to the above mixed solution. The mixture was stirred for another 35 min, followed by the addition of 3 mL of distilled water and stirring until gelation. The resulting gel was dried in an oven at 80 °C, ground, and calcined at 550 °C for 3.5 h. The resulting white powder was the catalyst.

[0076] Water was added to the prepared reactor, and stirring was started. Ammonium persulfate, sodium perborate, and potassium peroxymonosulfate were added sequentially according to the reagent ratio. After stirring for 10 minutes, a mixture was formed with a water mass fraction of 12%. Additives and catalysts were added to the mixture, followed by stabilizers and adsorbents. After stirring evenly, the mixture was allowed to stand for 1 hour. After standing for 1 hour, pH adjuster, oxidant, and water were added sequentially according to the reagent ratio, and the mixture was stirred for 4 hours to obtain a special de-gelling agent for drilling waste mud treatment.

[0077] Example 3

[0078] A desiccant for treating waste drilling mud in gas fields comprises the following raw material components: 45% main agent, 25% auxiliary agent, 2.5% catalyst, 8% stabilizer, 5% oxidant, 1% adsorbent, 1% pH adjuster, and the balance being water.

[0079] The main degumming agent is ammonium persulfate, sodium perborate, and potassium peroxymonosulfate, with mass percentages of 22%, 13%, and 65%, respectively. The degumming aid is fatty alcohol polyoxyethylene ether, which is composed of penetrant JFC, AEO-5, and Pingpingjia O, with mass percentages of 33%, 42%, and 25%, respectively. The stabilizer is sodium aminotrimethylphosphonate. The oxidant is hydrogen peroxide. The adsorbent is sodium bentonite. The biomass is mainly walnut shells. The pH adjuster is citric acid.

[0080] The preparation method of the breaker in this embodiment includes the following steps:

[0081] Add penetrant JFC, AEO-5 and Pingping O to the prepared reactor in the correct proportions, start stirring, and stir for 30 minutes to form a mixed additive.

[0082] The catalyst was prepared using the sol-gel method: 0.95 mL of glacial acetic acid and 11 mL of anhydrous ethanol were mixed and then added dropwise to a mixed solution of 15 mL of anhydrous ethanol and 5 mL of tetrabutyl titanate, and thoroughly mixed. 1 g of palladium and silica powder were weighed and dried at 75 °C for 4 h, then added to the above mixed solution. The mixture was stirred for another 33 min, followed by the addition of 4 mL of distilled water and stirring until gelation. The resulting gel was dried in an oven at 80 °C, ground, and calcined at 520 °C for 3 h. The resulting white powder was the ternary composite nanocatalyst.

[0083] Water was added to the prepared reactor, and stirring was started. Ammonium persulfate, sodium perborate, and potassium peroxymonosulfate were added sequentially according to the reagent ratio. After stirring for 10 minutes, a mixture was formed with a water mass fraction of 12%. Additives and catalysts were added to the mixture, followed by stabilizers and adsorbents. After stirring evenly, the mixture was allowed to stand for 2 hours. After standing for 2 hours, pH adjuster, oxidant, and water were added sequentially according to the reagent ratio, and the mixture was stirred for 4 hours to obtain a special degumming agent for drilling waste mud treatment.

[0084] Comparative Example 1

[0085] Compared with Example 1, this one does not contain a catalyst. Specifically, the raw materials and their mass fractions are as follows: 30% debriding agent, 15% debriding aid, 5% stabilizer, 3% oxidant, 1.5% adsorbent, 0.5% pH adjuster, and the remainder is water.

[0086] The main de-gumming agents are ammonium persulfate, sodium perborate, and potassium peroxymonosulfate, with mass percentages of 20%, 15%, and 65%, respectively. The de-gumming aid is fatty alcohol polyoxyethylene ether, which is composed of penetrant JFC, AEO-5, and Pingpingjia O, with mass percentages of 35%, 40%, and 25%, respectively. The stabilizer is sodium aminotrimethylphosphonate. The oxidant is sodium hypochlorite. The adsorbent is corn straw. The pH adjuster is citric acid.

[0087] The preparation method of the de-colloiding agent in this comparative example includes the following steps:

[0088] Add penetrant JFC, AEO-5 and Pingping O to the prepared reactor in the correct proportions, start stirring, and stir for 30 minutes to form a mixed additive.

[0089] Water was added to the prepared reactor, and stirring was started. Ammonium persulfate, sodium perborate, and potassium peroxymonosulfate were added sequentially according to the reagent ratio. After stirring for 10 minutes, a mixture was formed with a water mass fraction of 12%. Additives were added to the mixture, followed by stabilizer and adsorbent in sequence. After stirring evenly, the mixture was allowed to stand for 1 hour. After standing for 1 hour, pH adjuster, oxidant, and water were added sequentially according to the reagent ratio, and the mixture was stirred for 4 hours to obtain a special de-gelling agent for drilling waste mud treatment.

[0090] The effect of the catalyst on the breaking effect was tested by selecting two groups of 500 mL mud samples and adding the same mass of the breaking agent prepared in Examples 1-3 and Comparative Example 1, respectively. The amount added was 0.2% of the system mass. The time required for the mud viscosity to decrease to 2 mPa·s after breaking at room temperature was tested, and the activation energy of the breaking process was tested. The results are shown in Table 1.

[0091] The method for detecting the breaking time is as follows: Before adding the breaking agent, the original slurry viscosity is measured using an NDJ-9S rotational viscometer. Then, the breaking agent is added to 1L of slurry, and after stirring for 10s, a timer is started. After that, a sample is taken every 10 minutes to measure the viscosity. In the later part of the experiment, the time interval for measuring the viscosity can be appropriately shortened based on the appearance of the slurry until the measured viscosity drops to 2mPa.s.

[0092] Comparative Example 2

[0093] Compared to Example 1, the catalyst used is palladium.

[0094] Methods for determining activation energy:

[0095] Thermogravimetric Analysis (TG) of Plastic Polymers - Part 2: Determination of Activation Energy (GB / T 33047.2-2021)

[0096] Table 1. Comparison data on the gel breaking effect of Examples 1-3 (containing catalyst) and Comparative Example 1 (without catalyst).

[0097]

[0098]

[0099] As can be seen from Table 1, from an appearance perspective, combined with Figures 2-5 As shown, in Examples 1-3 and Comparative Examples 1-2, the appearance of the demulsifiers was uniform and stable, indicating that the absence of a catalyst in Comparative Example 1 had no effect on the appearance of the demulsifier. Regarding the demulsification effect, the demulsifiers in Examples 1-3 with added catalysts significantly reduced the reaction activation energy and shortened the demulsification time, indicating that the catalyst helps accelerate demulsification. This is because the catalyst used in this invention uses palladium as the active component, which is loaded onto the titanium dioxide generated in the reaction. Palladium mainly reduces the surface activation energy of the mud colloid, assisting the main agent and auxiliary agent in accelerating the demulsification speed. Although a catalyst was used in Comparative Example 2, it was palladium and not loaded onto the titanium dioxide support. Therefore, although its activation energy was lower than that of Comparative Example 1, it was higher than that of Examples 1-3. This indicates that the support plays a positive role in the demulsification of the catalyst. Titanium dioxide mainly serves as a support for palladium in this catalyst. Titanium dioxide has unique properties and can undergo a strong interaction with the loaded palladium metal, altering the adsorption and catalytic performance of the catalyst and giving it strong resistance to poisoning. In Comparative Example 2, no support was used, which reduced the catalytic activity of the catalyst.

[0100] Figure 1 Images show the appearance of the mud before and after using the breaker in Example 1; where (a) and (b) are images of the mud before breaker; and (c) and (d) are images of the mud after breaker. Figure 1 It is evident that after the gel breaks down, the mud exhibits stratification and its viscosity decreases.

[0101] Comparative Example 3

[0102] Compared to Example 1, this formulation does not contain a stabilizer. Specifically, the raw materials and their mass fractions are as follows: 30% degreasing agent, 15% degreasing aid, 2% catalyst, 3% oxidant, 1.5% adsorbent, 0.5% pH adjuster, and the remainder is water.

[0103] The main de-gum breaking agents are ammonium persulfate, sodium perborate, and potassium peroxymonosulfate, with mass percentages of 20%, 15%, and 65%, respectively. The de-gum breaking aid is fatty alcohol polyoxyethylene ether, which is composed of penetrant JFC, AEO-5, and Pingpingjia O, with mass percentages of 35%, 40%, and 25%, respectively. The oxidant is sodium hypochlorite. The adsorbent is corn straw. The pH adjuster is citric acid.

[0104] The preparation method of the de-colloiding agent in this comparative example includes the following steps:

[0105] Add penetrant JFC, AEO-5 and Pingping O to the prepared reactor in the correct proportions, start stirring, and stir for 30 minutes to form a mixed additive.

[0106] The catalyst was prepared using the sol-gel method: 0.9 mL of glacial acetic acid and 10 mL of anhydrous ethanol were mixed and then added dropwise to a mixed solution of 16 mL of anhydrous ethanol and 6 mL of tetrabutyl titanate, and the mixture was thoroughly mixed. 1 g of palladium and 1 g of silica powder were weighed out and dried at 80 °C for 4 h, then added to the above mixed solution. The mixture was stirred for another 30 min, followed by the addition of 5 mL of distilled water and stirring until gelation occurred. The resulting gel was dried in an oven at 80 °C, ground, and calcined at 500 °C for 3 h. The resulting white powder was the catalyst.

[0107] Water was added to the prepared reactor, and stirring was started. Ammonium persulfate, sodium perborate, and potassium peroxymonosulfate were added sequentially according to the reagent ratio. After stirring for 10 minutes, a mixture was formed with a water mass fraction of 12%. Additives and catalysts were added to the mixture, followed by the adsorbent in sequence. After stirring evenly, the mixture was allowed to stand for 1 hour. After standing for 1 hour, pH adjuster, oxidant, and water were added sequentially according to the reagent ratio, and the mixture was stirred for 4 hours to obtain a special de-gelling agent for drilling waste mud treatment.

[0108] Taking Example 1 and Comparative Example 3 as examples, the effect of stabilizer on the breaking effect was tested. The test method was as follows: two groups of 500mL mud test samples were selected respectively, and the same mass of the breaking agent prepared in Example 1 and Comparative Example 3 was added respectively. The amount added was 0.2% of the system mass. The time required for the mud viscosity to decrease to 2mPa.s after breaking at room temperature was tested. The test method was the same as the method described above. The results are shown in Table 2.

[0109] Table 2 shows the debonding effect of Example 1 (with stabilizer) and Comparative Example 3 (without stabilizer).

[0110]

[0111] As can be seen from Table 2, the activation energy data for Example 1 and Comparative Example 3 are similar, indicating that the absence of a stabilizer has almost no effect on the activation energy of the debonding process. However, the addition of a stabilizer in Example 1 affected the debonding speed. This is because without a stabilizer, the components of the debonding agent reacted with each other, producing a small amount of precipitation, and the debonding agent system was no longer homogeneous (e.g., ...). Figure 6As shown in the figure, this leads to a decrease in the effective component of the breaker, thereby prolonging the breaking time. This indicates that the addition of a stabilizer in the formulation of this invention is necessary. The addition of a stabilizer has a positive impact on the breaking effect, which is achieved by inhibiting the mutual reactions between the components in the formulation, maintaining the stability of the system, and preventing a decrease in the content of the effective component.

[0112] Comparative Example 4

[0113] Compared to Example 1, this formulation does not contain an oxidant. Specifically, the raw materials and their mass fractions are as follows: 30% degreasing agent, 15% degreasing aid, 2% catalyst, 5% stabilizer, 1.5% adsorbent, 0.5% pH adjuster, and the remainder is water.

[0114] The main de-gumming agents are ammonium persulfate, sodium perborate, and potassium monopersulfate, with mass percentages of 20%, 15%, and 65%, respectively. The de-gumming aid is fatty alcohol polyoxyethylene ether, which is composed of penetrant JFC, AEO-5, and Pingpingjia O, with mass percentages of 35%, 40%, and 25%, respectively. The stabilizer is sodium aminotrimethylphosphonate. The adsorbent is corn straw. The pH adjuster is citric acid.

[0115] The preparation method of the de-colloiding agent in this comparative example includes the following steps:

[0116] Add penetrant JFC, AEO-5 and Pingping O to the prepared reactor in the correct proportions, start stirring, and stir for 30 minutes to form a mixed additive.

[0117] The catalyst was prepared using the sol-gel method: 0.9 mL of glacial acetic acid and 10 mL of anhydrous ethanol were mixed and then added dropwise to a mixed solution of 16 mL of anhydrous ethanol and 6 mL of tetrabutyl titanate, and the mixture was thoroughly mixed. 1 g of palladium and 1 g of silica powder were weighed out and dried at 80 °C for 4 h, then added to the above mixed solution. The mixture was stirred for another 30 min, followed by the addition of 5 mL of distilled water and stirring until gelation occurred. The resulting gel was dried in an oven at 80 °C, ground, and calcined at 500 °C for 3 h. The resulting white powder was the catalyst.

[0118] Water was added to the prepared reactor, and stirring was started. Ammonium persulfate, sodium perborate, and potassium peroxymonosulfate were added sequentially according to the reagent ratio. After stirring for 10 minutes, a mixture was formed with a water mass fraction of 12%. Additives and catalysts were added to the mixture, followed by stabilizers and adsorbents. After stirring evenly, the mixture was allowed to stand for 1 hour. After standing for 1 hour, pH adjuster and water were added sequentially according to the reagent ratio, and the mixture was stirred for 4 hours to obtain a special de-gelling agent for drilling waste mud treatment.

[0119] Taking Example 1 and Comparative Example 4 as examples, the effect of oxidant on the breaking effect was tested. The test method was as follows: two groups of 500 mL mud test samples were selected respectively, and the same mass of the breaking agent prepared in Example 1 and Comparative Example 4 was added respectively. The amount added was 0.2% of the system mass. The time required for the mud viscosity to decrease to 2 mPa·s after breaking at room temperature was tested. The test method was the same as the method described above. The results are shown in Table 3.

[0120] Table 3 shows the gel breaking effect of Example 1 (containing oxidant) and Comparative Example 4 (without oxidant).

[0121]

[0122] As can be seen from Table 3, from an appearance perspective, such as Figure 7 As shown, the breaker in Example 1 and Comparative Example 4 is uniform and stable, indicating that the oxidant has no effect on the appearance of the breaker. However, the absence of an oxidant increases the activation energy of the breaker process and prolongs the breaker time, indicating that the oxidant plays a role in enhancing the breaker process and can accelerate the breaker speed to some extent.

[0123] Based on the data in Tables 1-3, it can be seen that the breaker prepared in this invention reduces the mud viscosity to 2 mPa·s in 58-62 minutes at room temperature after breaking down the slurry. In contrast, commonly used breakers for oilfield waste mud treatment include: composite iron salt waste mud breaker (model: BHPJ-10X, Tianjin Dagang Oilfield Binhai Group Bohong Petrochemical Co., Ltd.), water-soluble polymeric inorganic salt breaker (Yan'an Shengyuan Chemical Co., Ltd.), 0038 type mud drilling mud breaker (Jinan Ruijintai Chemical Co., Ltd.), and YD-203 type mud breaker (Jinan Ruijintai Chemical Co., Ltd.). These breakers require 1.5-2 hours to achieve the same breaking effect. Therefore, compared with currently used breakers, this invention has a shorter breaking time and faster breaking speed, which can alleviate the risk of mud accumulation and facilitate on-site mud treatment while it is being generated.

[0124] The breaker of this invention can also be applied to environments with a wide temperature range. Two groups of 500mL mud samples were selected, and the same mass of the breaker prepared in Example 1 was added at different temperatures. The amount added was 0.2% of the system mass. The time required for the mud viscosity to decrease to 2mPa.s after breaker was detected at different temperatures. The detection method was the same as the method described above. The results are shown in Table 4.

[0125] Table 4. Debonding effect of the debonding agent in Example 1 at different temperatures.

[0126]

[0127] Figure 8 and Figure 9 The images show the appearance of the breaker in Example 1 at 10℃ and 60℃, respectively, indicating that the system is uniform and stable. Table 4 shows that the breaker of this invention exhibits a faster breaking speed at both 10℃ and 60℃, with a breaking time shorter than the 1.5-2 hours of currently used breaker. This demonstrates that the breaker of this invention has a wide temperature range, allowing for breaking treatment at different temperatures, making it suitable for a wide range of environments and facilitating the simultaneous generation and treatment of mud at different temperatures.

[0128] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from the spirit and scope of the invention. Therefore, it is intended to include any modifications and variations of this invention that fall within the scope of the claims and their equivalents.

Claims

1. A breaker, characterized in that, For the treatment of waste drilling mud in oil and gas fields, the breaker is made from the following raw materials in the following weight percentages: The composition is as follows: 30%-45% main degreasing agent, 15%-25% degreasing aid, 2%-3% catalyst, 5%-8% stabilizer, 3%-5% oxidant, 1%-1.5% adsorbent, 0.5%-1% pH adjuster, and the remainder is water. The debonding agent is made by mixing the following raw materials in the following mass percentages: 20%-30% ammonium persulfate, 10%-15% sodium perborate, and the balance being potassium peroxymonosulfate; The debonding agent is fatty alcohol polyoxyethylene ether; The catalyst is prepared by the following steps: At room temperature, a mixed solution of glacial acetic acid and tetrabutyl titanate was prepared using ethanol as a solvent; palladium and silicon dioxide were added to the mixed solution, and after stirring until homogeneous, water was added and stirring was continued to obtain a gel; the gel was dried and ground, and then sintered at 500-550℃ for 3-3.5h to obtain the catalyst; The stabilizer is sodium aminotrimethylphosphonate or sodium ethylenediaminetetramethylenephosphonate. The oxidant is one of potassium permanganate, sodium hypochlorite, and hydrogen peroxide; The adsorbent is one of quicklime, sodium bentonite and biomass, and the biomass is one of walnut shell, sawdust and corn stalks. The pH adjuster is citric acid or sorbic acid.

2. The breaker according to claim 1, characterized in that, The ethanol is anhydrous ethanol, and the volume ratio of glacial acetic acid, tetrabutyl titanate and anhydrous ethanol is 0.9-1:4-6:26; The ratio of palladium to anhydrous ethanol is 1-3 g: 26 mL, and the mass ratio of palladium to silicon dioxide is 1:

1. In the catalyst preparation step, the volume ratio of water to anhydrous ethanol is 3-5:

26.

3. A method for preparing a breaker, characterized in that, The preparation of the breaker according to claim 1 includes the following steps: Weigh the following raw materials by mass percentage: 30%-45% breaking agent, 15%-25% breaking aid, 2%-3% catalyst, 5%-8% stabilizer, 3%-5% oxidant, 1%-1.5% adsorbent, 0.5%-1% pH adjuster, and the remainder is water; Mix the de-gluing agent with water to prepare mixture 1, wherein the mass fraction of water in mixture 1 is 12%-44%; add the de-gluing aid and catalyst to mixture 1 to prepare mixture 2; add the stabilizer and adsorbent to mixture 2 in sequence, stir evenly and let stand for 1-2 hours to prepare mixture 3; add the pH adjuster, oxidant and the remaining water to mixture 3 in sequence, mix and stir evenly to obtain the de-gluing agent.

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