Preparation method of high-temperature-resistant and salt-resistant sulfomethyl phenolic resin filtrate reducer for drilling fluid

Abstract

The invention provides a preparation method of a high-temperature-resistant salt-resistant sulfomethyl phenolic resin filtrate reducer, which comprises the following steps: (1) synthesis of mixed sodium phenolate: adding bisphenol A reactant powder into a reaction container, then slowly adding molten phenol under a stirring condition, then slowly pouring a uniformly dissolved alkali solution into the system, and carrying out heat preservation for 2-4 hours; reacting to obtain mixed phenol sodium salt; and (2) synthesis of sulfomethylated phenolic resin: adding a 37% formaldehyde solution and a sulfonating agent solution which is uniformly dissolved in advance into the reaction kettle, uniformly stirring, replenishing water, carrying out reflux reaction, and replenishing water in batches during the period. The sulfomethylated phenolic resin prepared by the method can resist the temperature of 180 DEG C and the salt of 30% NaCl, the use amount of the sulfomethylated phenolic resin is only 50% of that of similar products, and the product has no obvious effect of increasing the apparent viscosity of the drilling fluid during use.

Description

Technical Field

[0001] The invention belongs to the technical field of drilling fluid treatment agents in the petroleum and natural gas industry, and particularly relates to a method for preparing a high-temperature and salt-resistant sulfonylmethylphenolic resin fluid loss reducer for drilling fluid. Background Art

[0002] With the continuous development of shallow and simple formations, oil exploration and development are expanding into deeper and more complex formations. The drilling environment is becoming increasingly complex, often accompanied by high temperatures, high pressures, and highly mineralized formations. Filter loss reducers for drilling fluids effectively control fluid loss, ensuring safe and efficient drilling. They are the most widely used and most expensive drilling fluid treatment agent in the oil drilling process. Complex and harsh formation environments require filter loss reducers with superior resistance to high temperatures, salt, and calcium and magnesium ion contamination.

[0003] Since the 1970s, sulfomethyl phenolic resin (SMP) fluid loss additives have been widely used in deep and complex well exploration and operations due to their excellent resistance to high temperatures and salts. Numerous modified derivatives have been developed. These products offer stable temperature and salt tolerance and excellent fluid loss reduction. A high-temperature, deep-well drilling fluid system ("tri-sulfonated" drilling fluid) composed of sulfonated lignite (SMC) and sulfonated tannin (SMT) effectively reduces high-temperature, high-pressure fluid loss. SMP products have become one of the most widely used key treatment agents in high-temperature, deep-well water-based drilling fluids both domestically and internationally.

[0004] SMP products must meet three conditions to be effective in field applications: first, they must be used in deep-well drilling fluids; second, they must be used in saline drilling fluids, particularly when the salt content is high; and third, they must be used simultaneously with cross-linking treatment agents such as sulfonated lignite or sulfonated tannin extract (SMK), making them ineffective when used independently. Furthermore, the dosage of sulfomethylphenolic resin is high, typically 4%-6%, resulting in waste of drilling fluid material and increased drilling costs. Furthermore, SMP products can generate a large number of bubbles during use, affecting the stability of drilling fluid performance.

[0005] Chinese patent application CN111253541A, "A Foam-Free Modified Sulfomethyl Phenolic Resin for Drilling Fluid and Preparation Method," discloses a method for preparing a foam-free modified sulfomethyl phenolic resin for drilling fluid. The resin comprises, by weight, 110-130 parts of phenolic formaldehyde, 50-70 parts of formaldehyde, 80-110 parts of sodium metabisulfite, 45-70 parts of anhydrous sodium sulfite, 60-90 parts of nonylphenol polyoxyethylene ether and / or octylphenol polyoxyethylene ether, and 30-60 parts of water. The modified sulfomethyl phenolic resin containing polyether functional groups is obtained by polycondensing the alcoholic hydroxyl groups at the long-chain ends of the nonylphenol / octylphenol polyoxyethylene ether with hydrogen atoms located opposite to the phenolic hydroxyl groups on the sulfomethyl phenolic resin. This modified sulfomethyl phenolic resin exhibits salt resistance and fluid loss reduction properties, as well as a certain defoaming function. It has no effect on other drilling fluid properties and is easy to use with a small dosage.

[0006] Chinese patent application CN114736342A, "A method for preparing a high-temperature-resistant and high-efficiency sulfomethylphenol-formaldehyde resin," discloses a method for preparing a high-temperature-resistant and high-efficiency sulfomethylphenol-formaldehyde resin. The method comprises reacting phenol, p-hydroxyphenoxyacetic acid, and an alkaline sulfonic acid agent, followed by dropwise addition of formaldehyde. The reaction is heated to a system viscosity of 60-80 mPa·s, followed by dilution with water, followed by addition of sodium p-hydroxybenzenesulfonate, and then an oxidant. Finally, a cross-linking agent is added to react, thereby obtaining a high-temperature-resistant and salt-resistant sulfomethylphenol-formaldehyde resin. The added oxidant can further oxidize the non-temperature-resistant groups such as ether bonds produced by the side reaction to form temperature-resistant groups such as carboxyl groups. An appropriate amount of cross-linking agent increases the degree of cross-linking of the resin material, allowing the prepared product to be used alone. At the same time, the sulfomethylphenol-formaldehyde resin obtained by this method introduces carboxyl and benzenesulfonic acid groups into its structure, which can better adsorb on the clay surface, forming a spatial grid structure, giving the product good fluid loss reduction performance. However, its preparation process is relatively complex and the production cycle is long.

[0007] Chinese patent application CN114085343A, "A Modified Sulfomethyl Phenolic Resin Fluid Loss Control Agent for Drilling Fluids and Its Preparation Method," discloses a method for preparing a modified sulfomethyl phenolic resin for drilling fluids. The modified sulfomethyl phenolic resin fluid loss control agent is obtained by sulfonating and polycondensing raw materials such as hydroxyphenylacetate, phenol, formaldehyde, and sulfite. The high sulfonic acid content in the sulfomethyl phenolic resin structure improves the product's solubility, but its adsorption to solids is weak. The introduction of sodium hydroxyphenylacetate increases the carboxyl content in the product's molecular structure, improving its adsorption to solids. Therefore, the appropriate amount of sodium hydroxyphenylacetate incorporated into the sulfomethyl phenolic resin structure can increase the product's adsorption to solids such as clay, improving its fluid loss control performance. When added at a dosage of 4%, the product maintained good fluid loss control performance after aging at temperatures between 90°C and 180°C, indicating its applicability as a fluid loss control agent in deep, medium-deep, and shallow wells. However, its high-temperature and high-pressure fluid loss performance was not tested.

[0008] Chinese patent application CN106608958A, "A Method for Producing Carboxymethylsulfonylphenol-Formaldehyde Resin and Application of Carboxymethylsulfonylphenol-Formaldehyde Resin," discloses a method for producing a carboxymethylsulfonylphenol-Formaldehyde resin. The resin is synthesized using partially carboxymethylated phenol and phenol, and then subjected to cationization and sulfonation reactions to obtain a modified carboxymethylsulfonylphenol-Formaldehyde resin. A substitution reaction adds carboxymethyl groups to the benzene ring, thereby improving the product's resistance to calcium and magnesium ions. Subsequent cationic modification of the carboxymethylsulfonylphenol-Formaldehyde resin significantly enhances its adsorption capacity on clay surfaces. This product can maintain the drilling fluid's temperature and salt resistance while reducing the amount of treatment agent used, but the preparation process involves numerous steps and is somewhat complex.

[0009] Chinese patent application CN106188446A "A modified sulfomethyl phenolic resin and a drilling mud treating agent containing the same" provides a modified sulfomethyl phenolic resin, which is prepared by the following steps, calculated by weight: (1) adding phenol, dihydric phenol, formaldehyde and 20% hydrochloric acid solution into a reaction kettle, and reacting at 97°C-105°C for 10-15 minutes; (2) adding 20% ​​sulfonating agent solution, and then adding sulfonating agent solution, and reacting at 97°C-105°C for 10-15 minutes; The invention also provides a drilling mud treating agent, which is composed of the following components in parts by weight: 16-22 parts of modified sulfonyl phenolic resin, 8-12 parts of sodium hydroxypropyl sulfonate, 6-10 parts of oleamide hydroxysulfobetaine, 5-8 parts of trifluoropropyl methylcyclotrisiloxane, 12-18 parts of acrylamide, 0.02-0.1 parts of ammonium persulfate, 1-5 parts of nano titanium dioxide, and 3-6 parts of sodium bicarbonate. The obtained drilling fluid mud treatment agent has a temperature resistance of up to 200°C, and the addition amount is generally 1.0%-3.0%; the dosage is only about 50% of similar products, which reduces production costs and reduces the amount of mud used. However, its preparation process is cumbersome, the production cycle is long, and the production efficiency is low.

[0010] Chinese patent application CN1047886343A, "A Method for Preparing a High-Temperature-Resistant Modified Sulfomethylphenol-Formaldehyde Resin for Drilling Fluid," discloses a method for preparing a high-temperature-resistant modified sulfomethylphenol-formaldehyde resin for drilling fluid. The method comprises the following steps: 1) adding a phenolic reactant, an aldehyde reactant, and an acid catalyst to a reactor, mixing and stirring, and reacting at 50°C-110°C for 10-400 minutes; 2) adding an alkaline catalyst and an aldehyde reactant to the reactor, adding a sulfonating agent in batches while maintaining the temperature between 50°C-110°C, and reacting for 10-600 minutes; 3) after the reaction, cooling the reaction mixture, discharging the mixture, and spray drying the mixture to obtain the product. The modified sulfomethylphenol-formaldehyde resin prepared by this invention has a temperature resistance of up to 200°C. After addition, under aging conditions at 200°C, it can effectively reduce high-temperature and high-pressure fluid loss in drilling fluids, achieving salt tolerance of up to 15% NaCl. However, the preparation process is complex, and the amount of sulfonating agent used is relatively high, increasing drilling costs.

[0011] Therefore, how to provide a sulfomethylphenolic resin high-efficiency fluid loss reducer with simple production process, low usage amount, high temperature and salt resistance, and excellent fluid loss reduction performance is a problem that people in this field urgently need to solve. Summary of the Invention

[0012] In response to the shortcomings of the existing technology, the present invention provides a method for preparing a high-temperature and salt-resistant sulfomethylphenol-formaldehyde resin. The sulfomethylphenol-formaldehyde resin prepared by this method has a temperature resistance of up to 180°C and a salt resistance of up to 30% NaCl. At the same time, the usage amount is only 50% of that of similar products. Moreover, when used, the product has no obvious effect on increasing the apparent viscosity of the drilling fluid.

[0013] In order to achieve the above object, the technical solution adopted by the present invention is a method for preparing a high temperature and salt resistant sulfonylmethyl phenolic resin fluid loss reducer, comprising the following steps:

[0014] (1) Synthesis of mixed phenol sodium salt

[0015] Add bisphenol A reactant powder to a reaction vessel, then slowly add melted phenol under stirring conditions, and then slowly pour a uniformly dissolved alkaline solution into the system to react to obtain a mixed phenol sodium salt;

[0016] (2) Synthesis of sulfomethylphenolic resin

[0017] Then add 37% formaldehyde solution and pre-dissolved sulfonating agent solution into the reactor, stir evenly, add water, and reflux to react, during which water is added in batches.

[0018] In a preferred embodiment, the method comprises the following steps:

[0019] (1) Synthesis of mixed phenol sodium salt

[0020] Add bisphenol A reactant powder to a reaction vessel, then slowly add melted phenol under stirring conditions, then slowly pour a uniformly dissolved alkaline solution into the system, and react at 80°C-100°C for 30min-60min to obtain a mixed phenol sodium salt;

[0021] (2) Synthesis of sulfomethylphenolic resin

[0022] Then add 37% formaldehyde solution and pre-dissolved sulfonating agent solution into the reactor, stir evenly, add water, and reflux at 90°C-110°C for 3-5 hours. During the reaction, add water to the system every 30min-80min to adjust the viscosity of the system and the degree of reaction.

[0023] According to the technical solution of the present invention, in step (1), the mass ratio of the melted phenol to the bisphenol A reactant powder is 240:(80-240); preferably, the mass ratio of the melted phenol to the bisphenol A reactant powder is 240:160.

[0024] Preferably, in step (1), the base used as a catalyst is preferably a composite base of sodium hydroxide or potassium hydroxide and anhydrous sodium carbonate, which is prepared into an aqueous solution for use.

[0025] In step (1), the mass ratio of (bisphenol A + phenol): sodium hydroxide / potassium hydroxide: anhydrous sodium carbonate is 400:(8-40):(80-130). Preferably, the mass ratio of (bisphenol A + phenol): sodium hydroxide / potassium hydroxide: anhydrous sodium carbonate is 400:32:120, and the composite alkali catalyst is prepared into a 25% aqueous solution for use.

[0026] In step (1), the bisphenol A, phenol and alkaline catalyst are reacted at 80° C.-100° C. for 30 min-60 min. Preferably, the bisphenol A, phenol and alkaline catalyst are reacted at 95° C. for 40 min.

[0027] According to the technical solution of the present invention, preferably, in step (2), the sulfonating agent is one or more of sodium metabisulfite, anhydrous sodium sulfite and anhydrous sodium bisulfite, which are prepared into an aqueous solution for use, preferably a 40% aqueous solution for use.

[0028] In step (2), the mass ratio of (bisphenol A + phenol): sulfonating agent: 37% formaldehyde solution is 400: (240-400): (530-720), preferably, the mass ratio of (bisphenol A + phenol): sulfonating agent: 37% formaldehyde solution is 400: 360: 640.

[0029] In step (2), the mass ratio of the amount of water added: (bisphenol A + phenol) is (120-160):400.

[0030] In step (2), the mixed phenol sodium salt, sulfonating agent, and 37% formaldehyde solution are refluxed at 90° C.-110° C. for 3-5 hours; preferably, the mixed phenol sodium salt, sulfonating agent, and 37% formaldehyde solution are refluxed at 97° C.-105° C. for 4 hours.

[0031] According to a preferred embodiment of the technical solution of the present invention, in step (2), the mass ratio of the total amount of added water to (bisphenol A + phenol) is (320-640):400; preferably, the mass ratio of the total amount of added water to (bisphenol A + phenol) is 480:400.

[0032] In step (2), water is added in batches, and the time interval for adding water is 30min-80min; preferably, the time interval for adding water is 60min.

[0033] Preferably, the preparation method of the high temperature and salt resistant sulfonylmethyl phenolic resin fluid loss reducer provided by the present invention further comprises the following steps:

[0034] (3) After the reaction is completed, the temperature of the reaction gel is lowered to 50°C using circulating water, and then the reaction gel is dried into powder by spray drying.

[0035] The present invention also provides a high-temperature and salt-resistant sulfonylmethylphenolic resin fluid loss reducer prepared according to the method.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] (1) The present invention introduces a bisphenol A structure into the molecular chain of a conventional phenol-formaldehyde polycondensation resin (linear phenolic resin), utilizing the rigidity of the bisphenol A structure to improve the high-temperature resistance of the sulfomethylphenolic resin. Furthermore, the present invention still has an excellent fluid loss reduction effect even when the usage amount is only 50% of that of similar products.

[0038] (2) The process of the present invention is reasonable and the product performance is excellent: in the synthesis process, phenol and bisphenol A with different chemical reaction activities are used as raw materials. If the "one-pot method" is adopted for preparation, they are prone to explosion and polymerization, generating a bulk gel resin that is difficult to dissolve in water, thereby affecting the product performance. Therefore, the present invention first fully alkalinizes the two under alkaline conditions to obtain the corresponding mixed phenol sodium salt, thereby solving the problem of different chemical reaction activities of the two, improving the controllability of subsequent co-condensation and co-sulfonation reactions, and enhancing the stability of product performance;

[0039] (3) The preparation method of the present invention is simple and easy to operate, has a short production cycle, has fewer product side reactions, and the synthesis process does not require high equipment;

[0040] (4) The sulfomethylphenolic resin product of the present invention can reduce the usage amount during operation, generally 2%-3% is sufficient, which can significantly reduce drilling costs and reduce the amount of mud used;

[0041] (5) The sulfomethylphenolic resin product of the present invention can be used under high temperature and high salt conditions, for example, in a 180°C, 30% NaCl environment, without significantly increasing the viscosity of the mud, and can effectively reduce the API fluid loss and high temperature and high pressure fluid loss of the drilling fluid. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 The present invention shows a process flow chart for preparing a high-temperature and salt-resistant sulfonylmethylphenolic resin fluid loss reducer. DETAILED DESCRIPTION

[0043] The present invention will be described in detail below through specific embodiments, and the features and advantages of the present invention will become clearer and more distinct with these descriptions.

[0044] Example

[0045] The bisphenol A powder raw material used in the examples is an industrial-grade reagent purchased from Shandong Pulis Chemical Co., Ltd.

[0046] The phenol, sodium hydroxide, potassium hydroxide, anhydrous sodium carbonate, 37% formaldehyde solution, sodium metabisulfite, anhydrous sodium sulfite and anhydrous sodium bisulfite used in the examples were all chemically pure reagents purchased from Beijing Yili Fine Chemicals Co., Ltd.

[0047] The sulfomethylphenolic resin products (SMP-I and SMP-II) used in the comparative examples were industrial-grade reagents purchased from Shandong Weifang Sanlibenuo Chemical Industry Co., Ltd. and Sichuan Zhengrong Industrial Co., Ltd., respectively.

[0048] The sulfonated tannin extract (SMK) used as a supporting detection reagent for sulfomethylphenolic resin in the experimental test was an industrial-grade reagent purchased from Chengdu Chuanfeng Chemical Engineering Co., Ltd.

[0049] Example 1 Preparation of high temperature and salt resistant sulfonyl methyl phenolic resin fluid loss reducer

[0050] (1) Pour 20 g of bisphenol A powder into a three-necked flask, and slowly add 30 g of molten phenol into the flask under stirring; dissolve 4 g of sodium hydroxide and 14 g of anhydrous sodium carbonate in 50 g of water to prepare an alkaline catalyst solution, add the solution to the three-necked flask after uniform dissolution, and reflux at 95°C for 30 min;

[0051] (2) 44 g of sodium metabisulfite was uniformly dissolved in 80 g of water to prepare a sulfonating agent solution. 80 g of 37% formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence, stirred evenly, and 20 g of water was added. The mixture was refluxed at 95°C for 4 h.

[0052] (3) Observe the change in the viscosity of the system in the three-necked flask, and add 20 mL of water to the system at 60 min, 100 min, 140 min, and 180 min to adjust the reaction degree. After the reaction is completed, reduce the temperature of the reaction gel to 50 °C, and then dry the reaction gel into powder by spray drying.

[0053] Example 2 Preparation of high temperature and salt resistant sulfonylmethyl phenolic resin fluid loss reducer

[0054] (1) Pour 25 g of bisphenol A powder into a three-necked flask, and slowly add 30 g of molten phenol into the flask under stirring; dissolve 4.5 g of potassium hydroxide and 16 g of anhydrous sodium carbonate in 50 g of water to prepare an alkaline catalyst solution, add the solution to the three-necked flask after uniform dissolution, and reflux at 97°C for 40 min;

[0055] (2) 48 g of sodium metabisulfite was uniformly dissolved in 80 g of water to prepare a sulfonating agent solution. 90 g of 37% formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence. The mixture was stirred continuously, and 20 g of water was added. The mixture was refluxed at 97°C for 4 h.

[0056] (3) Observe the change in the viscosity of the system in the three-necked flask and add 20 mL of water to the system at 60 min, 120 min, and 180 min of reaction to adjust the reaction degree. After the reaction is completed, reduce the temperature of the reaction gel to 50 °C and then dry the reaction gel into powder by spray drying.

[0057] Example 3 Preparation of high temperature and salt resistant sulfonylmethyl phenolic resin fluid loss reducer

[0058] (1) Pour 15 g of bisphenol A powder into a three-necked flask, and slowly add 30 g of molten phenol into the flask under stirring; dissolve 3.5 g of sodium hydroxide and 12 g of anhydrous sodium carbonate in 50 g of water to prepare an alkaline catalyst solution, add the solution to the three-necked flask after uniform dissolution, and reflux at 100° C. for 40 min;

[0059] (2) 46 g of anhydrous sodium bisulfite was uniformly dissolved in 80 g of water to prepare a sulfonating agent solution. 75 g of 37% formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence. The mixture was stirred continuously, and 20 g of water was added. The mixture was refluxed at 100° C. for 4 h.

[0060] (3) Observe the change in the viscosity of the system in the three-necked flask and add 20 mL of water to the system at 60 min, 120 min, and 180 min of reaction to adjust the reaction degree. After the reaction is completed, reduce the temperature of the reaction gel to 50 °C and then dry the reaction gel into powder by spray drying.

[0061] Example 4 Preparation of High-Temperature-Resistant and Salt-Resistant Sulfomethylphenolic Resin Fluid Loss Reducer

[0062] (1) Pour 22 g of bisphenol A powder into a three-necked flask, and slowly add 30 g of molten phenol into the flask under stirring; dissolve 5 g of sodium hydroxide and 10 g of anhydrous sodium carbonate in 50 g of water to prepare an alkaline catalyst solution, add the solution to the three-necked flask after uniform dissolution, and reflux at 100° C. for 50 min;

[0063] (2) 60 g of anhydrous sodium sulfite was uniformly dissolved in 80 g of water to prepare a sulfonating agent solution, and 90 g of 37% formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence, and stirring was continued. 20 g of water was added and the mixture was refluxed at 100°C for 4 h;

[0064] (3) Observe the change in the viscosity of the system in the three-necked flask, and add 15 mL of water to the system at 60 min, 100 min, 140 min, and 180 min to adjust the reaction degree. After the reaction is completed, reduce the temperature of the reaction gel to 50 °C, and then dry the reaction gel into powder by spray drying.

[0065] Example 5 Preparation of high temperature and salt resistant sulfonylmethyl phenolic resin fluid loss reducer

[0066] (1) Pour 25 g of bisphenol A powder into a three-necked flask, and slowly add 30 g of molten phenol into the flask under stirring; dissolve 4 g of sodium hydroxide and 14 g of anhydrous sodium carbonate in 50 g of water to prepare an alkaline catalyst solution, add the solution to the three-necked flask after uniform dissolution, and reflux at 98°C for 60 min;

[0067] (2) 25 g of anhydrous sodium bisulfite and 20 g of sodium metabisulfite were uniformly dissolved in 80 g of water to prepare a sulfonating agent solution. 85 g of 37% formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence. The mixture was stirred continuously, and 20 g of water was added. The mixture was refluxed at 98°C for 4 h.

[0068] (3) Observe the change in the viscosity of the system in the three-necked flask and add 20 mL of water to the system at 60 min, 120 min, and 180 min of reaction to adjust the reaction degree. After the reaction is completed, reduce the temperature of the reaction gel to 50 °C and then dry the reaction gel into powder by spray drying.

[0069] Example 6 Preparation of high temperature and salt resistant sulfonated methylphenolic resin fluid loss reducer

[0070] (1) Pour 25 g of bisphenol A powder into a three-necked flask, and slowly add 32 g of molten phenol into the flask under stirring; dissolve 4.5 g of potassium hydroxide and 12 g of anhydrous sodium carbonate in 50 g of water to prepare an alkaline catalyst solution, add the solution to the three-necked flask after uniform dissolution, and reflux at 100° C. for 40 min;

[0071] (2) 22 g of anhydrous sodium bisulfite and 27 g of anhydrous sodium sulfite were uniformly dissolved in 80 g of water to prepare a sulfonating agent solution. 85 g of 37% formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence. The mixture was stirred continuously, and 20 g of water was added. The mixture was refluxed at 100° C. for 4 h.

[0072] (3) Observe the change in the viscosity of the system in the three-necked flask and add 20 mL of water to the system at 60 min, 100 min, 140 min, and 180 min of reaction to adjust the reaction degree. After the reaction is completed, reduce the temperature of the reaction gel to 50 °C and then dry the reaction gel into powder by spray drying.

[0073] Example 7 Preparation of High-Temperature-Resistant and Salt-Resistant Sulfomethylphenolic Resin Fluid Loss Reducer

[0074] (1) Pour 25 g of bisphenol A powder into a three-necked flask, and slowly add 30 g of molten phenol into the flask under stirring; dissolve 3 g of sodium hydroxide and 14 g of anhydrous sodium carbonate in 50 g of water to prepare an alkaline catalyst solution, add the solution to the three-necked flask after uniform dissolution, and reflux at 105° C. for 60 min;

[0075] (2) 22 g of sodium metabisulfite and 30 g of anhydrous sodium sulfite were uniformly dissolved in 80 g of water to prepare a sulfonating agent solution. 80 g of 37% formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence. The mixture was stirred continuously, and 20 g of water was added. The mixture was refluxed at 105° C. for 4 h.

[0076] (3) Observe the change in the viscosity of the system in the three-necked flask and add 20 mL of water to the system at 60 min, 120 min, and 180 min of reaction to adjust the reaction degree. After the reaction is completed, reduce the temperature of the reaction gel to 50 °C and then dry the reaction gel into powder by spray drying.

[0077] Example 8 Preparation of High-Temperature-Resistant and Salt-Resistant Sulfonylmethyl Phenolic Resin Fluid Loss Reducer

[0078] (1) Pour 25 g of bisphenol A powder into a three-necked flask, and slowly add 35 g of molten phenol into the flask under stirring; dissolve 5 g of sodium hydroxide and 16 g of anhydrous sodium carbonate in 50 g of water to prepare an alkaline catalyst solution, add the solution to the three-necked flask after uniform dissolution, and reflux at 97°C for 50 min;

[0079] (2) 15 g of sodium metabisulfite, 20 g of anhydrous sodium sulfite, and 17 g of anhydrous sodium bisulfite were uniformly dissolved in 80 g of water to prepare a sulfonating agent solution. 100 g of formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence, and stirring was continued. 20 g of water was added, and the mixture was refluxed at 97°C for 5 h.

[0080] (3) Observe the change in the viscosity of the system in the three-necked flask and add 20 mL of water to the system at 60 min, 120 min, 180 min, and 240 min of reaction to adjust the reaction degree. After the reaction is completed, reduce the temperature of the reaction gel to 50 °C and then dry the reaction gel into powder by spray drying.

[0081] Test example

[0082] For the modified sulfomethylphenolic resin product prepared in the example, the drilling fluid performance was tested according to the petroleum and natural gas industry standard of the People's Republic of China "SY / T 5094-2017 Sulfomethylphenolic Resin SMP for Drilling Fluid Loss Reducer", and the specific technical indicators are shown in Table 1 below.

[0083] Table 1 Technical indicators

[0084]

[0085] According to the Petroleum and Natural Gas Industry Standard of the People's Republic of China "SY / T 5094-2017 Sulfomethylphenolic Resin SMP for Drilling Fluid Loss Reducer", the high temperature and salt resistant sulfomethylphenolic resin fluid loss reducer obtained in Examples 1-8 was tested for drilling fluid performance. The specific results are shown in Table 2.

[0086] Table 2 Performance evaluation results

[0087]

[0088] As can be seen from Table 2, the products obtained in Examples 1-8 all have relatively low high-temperature and high-pressure fluid loss and have no significant viscosity-increasing effect on the drilling fluid.

[0089] Comparative Example

[0090] Comparative Example 1

[0091] (1) Slowly add 40 g of molten phenol to a three-necked flask under stirring; dissolve 1 g of sodium hydroxide and 14 g of anhydrous sodium carbonate in 50 g of water to prepare an alkaline catalyst solution, add the solution to the three-necked flask after uniform dissolution, and reflux at 97°C for 40 min;

[0092] (2) 30 g of sodium metabisulfite was uniformly dissolved in 60 g of water to prepare a sulfonating agent solution. 80 g of 37% formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence. The mixture was stirred continuously and 15 g of water was added. The mixture was refluxed at 97°C for 4 h.

[0093] (3) Observe the change in the viscosity of the system in the three-necked flask and add 20 mL of water to the system at 60 min, 120 min, and 180 min to adjust the reaction degree. After the reaction is completed, reduce the temperature of the reaction gel to 50 °C and then dry the reaction gel into powder by spray drying.

[0094] Comparative Example 2

[0095] (1) Under stirring conditions, 20 g of bisphenol A and 30 g of molten phenol were slowly added to a three-necked flask; 4 g of sodium hydroxide and 18 g of anhydrous sodium carbonate were dissolved in 50 g of water to prepare an alkaline catalyst solution, which was added to the three-necked flask after being uniformly dissolved;

[0096] (2) 42 g of sodium metabisulfite was uniformly dissolved in 80 g of water to prepare a sulfonating agent solution. 80 g of 37% formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence. The mixture was stirred continuously and 20 g of water was added. The mixture was refluxed at 97°C for 4 h.

[0097] (3) Observe the change in the viscosity of the system in the three-necked flask, and add 20 mL of water to the system at 60 min, 120 min, and 180 min of reaction to adjust the reaction degree. After the reaction is completed, reduce the temperature of the reaction gel to 50 °C and then dry the reaction gel into powder by spray drying.

[0098] Comparative Example 3

[0099] (1) Pour 24 g of bisphenol A powder into a three-necked flask, and slowly add 30 g of molten phenol into the three-necked flask under stirring; dissolve 4 g of sodium hydroxide and 14 g of anhydrous sodium carbonate in 50 g of water to prepare an alkaline catalyst solution, and add the solution to the three-necked flask after the solution is uniformly dissolved;

[0100] (2) 45 g of sodium metabisulfite was uniformly dissolved in 80 g of water to prepare a sulfonating agent solution. 80 g of 37% formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence. The mixture was stirred continuously and 20 g of water was added. The mixture was refluxed at 100° C. for 5 h.

[0101] (3) Observe the change in the viscosity of the system in the three-necked flask, and add 20 mL of water to the system at 60 min, 120 min, 180 min, and 240 min of reaction to adjust the reaction degree. After the reaction is completed, reduce the temperature of the reaction gel to 50 °C and then dry the reaction gel into powder by spray drying.

[0102] Comparative Example 4

[0103] The sample of comparative example 4 selected the SMP-Ⅰ product of Shandong Weifang Sanlibennuo Chemical Co., Ltd.

[0104] Comparative Example 5

[0105] The sample of comparative example 5 selected the SMP-Ⅱ product of Shandong Weifang Sanlibennuo Chemical Co., Ltd.

[0106] Comparative Example 6

[0107] The sample of comparative example 6 selected the SMP-Ⅱ product of Sichuan Zhengrong Industrial Co., Ltd.

[0108] Comparative Example 7

[0109] The sample of comparative example 7 selected the SMP-III product used in the field operation of Xinjiang Tarim Oilfield.

[0110] According to the Petroleum and Natural Gas Industry Standard of the People's Republic of China "SY / T5094-2017 Sulfomethylphenolic Resin SMP for Drilling Fluid Loss Reducer", the high temperature and salt resistant sulfomethylphenolic resin fluid loss reducer obtained in Comparative Examples 1-7 was tested for drilling fluid performance. The results are shown in Table 3 below.

[0111] Table 3 Performance evaluation results

[0112]

[0113]

[0114] As shown in Table 3, the traditional sulfomethylphenolic resin SMP-I and SMP-II products, which are industrially made of phenol and formaldehyde as raw materials, have a high-temperature and high-pressure fluid loss of more than 100 mL when the addition amount is 2.5%, far exceeding the index requirements. This shows that under this condition, SMP-I and SMP-II products basically have no fluid loss reduction performance.

[0115] As can be seen from Tables 2 and 3, the high-temperature and salt-resistant sulfonylmethyl phenolic resin products synthesized in Examples 1-8 have a medium-pressure filtration loss at room temperature of less than 6 mL, a high-temperature and high-pressure filtration loss of no more than 28 mL, and have no obvious viscosity-increasing effect on drilling mud, indicating that they have a good filtration loss reduction effect, and their filtration loss reduction performance is basically equivalent to that of the SMP-III product (Comparative Example 7) used in oil fields; the products synthesized in Comparative Examples 1-3 have a medium-pressure filtration loss at room temperature and a high-temperature and high-pressure filtration loss, which are significantly higher than those of the example products, and have extremely high development potential and broad market prospects.

[0116] The present invention has been described in detail above with reference to specific embodiments, exemplary examples, and accompanying drawings. However, these descriptions should not be construed as limiting the present invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications, or improvements may be made to the technical solutions and implementations of the present invention without departing from the spirit and scope of the present invention, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A method for preparing a high temperature and salt resistant sulfonylmethyl phenolic resin fluid loss reducer, comprising the following steps: (1) Synthesis of mixed phenol sodium salt Add bisphenol A reactant powder to a reaction vessel, then slowly add melted phenol under stirring conditions, and then slowly pour a uniformly dissolved alkaline solution into the system to react to obtain a mixed phenol sodium salt; (2) Synthesis of sulfomethylphenolic resin Then add 37% formaldehyde solution and pre-dissolved sulfonating agent solution into the reactor, stir evenly, add water, and reflux to react, during which water is added in batches.

2. The method according to claim 1, further comprising the steps of: (3) After the reaction is completed, the temperature of the reaction gel is lowered to 50°C using circulating water, and then the reaction gel is dried into powder by spray drying.

3. The method according to claim 1, wherein In step (1), the reaction is carried out at 80°C-100°C and the reaction time is 30min-60min.

4. The method according to claim 1, wherein In step (1), the base is used as a catalyst, which is a composite base of sodium hydroxide or potassium hydroxide and anhydrous sodium carbonate, and is prepared into an aqueous solution for use, preferably a 40% aqueous solution for use, and the amount ratio of each material is (bisphenol A + phenol): sodium hydroxide / potassium hydroxide: anhydrous sodium carbonate, calculated by mass ratio of 400: (8-40): (80-130), preferably 400:32:120; The mass ratio of phenol to bisphenol A is 240:(80-240), preferably 240:

160.

5. The method according to claim 1, wherein In step (2), the sulfonating agent is one or more of sodium metabisulfite, anhydrous sodium sulfite and anhydrous sodium bisulfite.

6. The method of claim 1, wherein: In step (2), the alkaline solution is a 40% aqueous solution.

7. The method of claim 1, wherein: In step (2), the mass ratio of (bisphenol A+phenol):sulfonating agent:37% formaldehyde solution is: 400:(240-400):(530-720), preferably 400:360:

640.

8. The method of claim 1, wherein: In step (2), the sodium phenolate, the sulfonating agent and the 37% formaldehyde solution are mixed and refluxed at 90° C.-110° C. for 3-5 hours; preferably, refluxed at 97° C.-105° C. for 4 hours.

9. The method of claim 1, wherein: In step (2), the mass ratio of the total amount of water added in batches to (bisphenol A+phenol) is (320-640):400, preferably 480:400, and the time interval for adding water in batches is 30min-80min, preferably the time interval for adding water is 60min.

10. A high temperature and salt resistant sulfonylmethyl phenolic resin fluid loss reducer, prepared according to the method according to any one of claims 1 to 9.

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