Method for preparing filtrate reducer for drilling fluid by utilizing bisphenol S residue extracted from phenol-containing wastewater

Abstract

The invention discloses a method for preparing a low-cost sulfonated phenolic resin filtrate reducer for drilling fluid by utilizing bisphenol S residues extracted from phenol-containing wastewater of industrial production of bisphenol S. Compared with a conventional sulfonated phenolic resin filtrate reducer product, the method has the advantages that the production cost is greatly reduced, the high-temperature stability of the product performance is more excellent, and the product quality is improved. The temperature resistance of the product can reach 200 DEG C, the salt resistance of the product can reach 36% NaCl, and the apparent viscosity increasing effect of the product on the drilling fluid is not obvious when the product is used. According to the method, high-concentration and degradation-resistant sulfonation side reaction product creosote residues in the phenol-containing wastewater are prepared into high-value oil and gas field drilling fluid chemicals, so that clean treatment and resource utilization of the phenol-containing wastewater are realized, and the method has remarkable environmental and economic benefits.

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 low-cost sulfomethylphenolic resin fluid loss reducer for drilling fluid by utilizing bisphenol S residue extracted from phenol-containing wastewater. 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 extracts, 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 generate a large number of bubbles during use, affecting the stability of drilling fluid performance.

[0005] Existing industrial production methods for SMP products mainly include one-step and two-step processes. The one-step process involves a one-pot reaction of phenolic reactants, aldehyde reactants, an alkaline sulfonating agent, a catalyst, and sufficient water, gradually forming a transparent glue solution. The two-step process, on the other hand, first generates a small-molecule linear phenolic resin from phenolic and aldehyde reactants under acidic conditions. An alkaline catalyst, aldehyde reactants, and a sulfonating agent are then added for further polycondensation and sulfonation reactions, causing the solution to transition from transparent to milky white and finally back to transparent. The former process is simple to operate, but molecular weight is difficult to control and product quality is unstable. The latter process has a high controllability coefficient and stable product quality, but the reaction time is longer.

[0006] Currently, bisphenol S is mostly synthesized industrially through the phenol sulfonation process, which generates large amounts of phenolic wastewater. Safely treating phenolic wastewater is complex and expensive, making it a typical difficult-to-treat organic wastewater. The phenolic wastewater generated during the synthesis of bisphenol S primarily consists of bisphenol S isomers (2,4'-bisphenol S and 4,4'-bisphenol S), which have similar physical properties and present significant challenges in their complete purification and separation. Bisphenol S residue, primarily composed of the two isomers of bisphenol S, phenols as a byproduct of the sulfonation reaction, and a small amount of residual phenol, has high utilization value. Current treatment methods, such as incineration, waste the phenolic resources contained. As bisphenol S production scales up, the generation of bisphenol S residue continues to increase. Therefore, improving the comprehensive resource utilization of bisphenol S residue and promoting green and clean production in the bisphenol S production sector is of great significance. Summary of the Invention

[0007] In response to the shortcomings of the existing technology, the present invention provides a method for preparing a low-cost phenolic resin fluid loss reducer using bisphenol S residue extracted from phenol-containing wastewater in the industrial production of bisphenol S. The method has lower production costs than conventional resin products and has better high-temperature performance and stability. The product obtained by the present invention has a temperature resistance of up to 200°C and a salt resistance of up to 36% NaCl. During use, the product has little effect on increasing the apparent viscosity of the drilling fluid.

[0008] In order to achieve the above object, the present invention provides a method for preparing a low-cost phenolic resin fluid loss additive using bisphenol S residue extracted from phenol-containing wastewater in the industrial production of bisphenol S, comprising the following steps:

[0009] (1) Synthesis of mixed phenol sodium salt

[0010] Add dry bisphenol S residue solid powder to the reaction vessel, then slowly add melted phenol under stirring, then slowly pour the uniformly dissolved alkaline solution into the system, and react at 80℃-100℃ for 30min-80min;

[0011] (2) Synthesis of sulfomethylphenolic resin

[0012] Add 37% formaldehyde solution and pre-dissolved sulfonating agent solution into the reaction vessel, stir evenly, add water, and reflux at 90-110°C for 3-5 hours;

[0013] (3) Control of reaction degree

[0014] During the reaction, the viscosity of the system will gradually increase. As the reaction proceeds, water is added to the system every 30-80 minutes to adjust the degree of reaction.

[0015] In the present invention, the bisphenol S residue used in step (1) is a recovered product extracted from phenol-containing wastewater in the industrial production of bisphenol S.

[0016] In a preferred embodiment of the present invention, in step (1), the mass ratio of the bisphenol S residue powder to phenol is 80:(40-240), more preferably 80:80.

[0017] In a preferred embodiment of the present invention, in step (1), the base used as the catalyst is preferably a composite base of sodium hydroxide or potassium hydroxide and anhydrous sodium carbonate, more preferably a composite base of sodium hydroxide and anhydrous sodium carbonate, preferably prepared as a 25% aqueous solution for use.

[0018] In a preferred embodiment of the present invention, in step (1), the material dosage ratio is (total mass of bisphenol S residue and phenol): sodium hydroxide / potassium hydroxide: anhydrous sodium carbonate mass ratio of 80: (2-8): (10-40); preferably, the (total mass of bisphenol S residue and phenol): sodium hydroxide: anhydrous sodium carbonate mass ratio is 80:4:16.

[0019] In a preferred embodiment of the present invention, in step (1), the bisphenol S residue, phenol and alkaline catalyst are reacted at 80°C-100°C for 30min-80min; preferably, the bisphenol S residue, phenol and alkaline catalyst are reacted at 97°C for 60min.

[0020] In the present invention, the sulfonating agent in step (2) is one or more of sodium metabisulfite, anhydrous sodium sulfite and anhydrous sodium bisulfite, preferably prepared as a 40% aqueous solution for use.

[0021] In a preferred embodiment of the present invention, in step (2), the material dosage ratio is 80:(40-70):(80-140) in terms of the mass ratio of (total mass of bisphenol S residue and phenol):sulfonating agent:37% formaldehyde solution; preferably, the mass ratio of (total mass of bisphenol S residue and phenol):sulfonating agent:37% formaldehyde solution is 80:50:100.

[0022] In a preferred embodiment of the present invention, 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.

[0023] In a preferred embodiment of the present invention, in step (3), the mass ratio of the total amount of water added to (the total mass of bisphenol S residue and phenol) is (45-80):80; preferably, the mass ratio of the total amount of water added to (the total mass of bisphenol and phenol) is 60:80.

[0024] Further preferably, in step (3), the time interval for adding water is 30 min-80 min; preferably, the time interval for adding water is 60 min.

[0025] After the reaction is completed, the temperature of the reaction glue solution is lowered to 50° C. using circulating water, and then the reaction glue solution is dried into powder by spray drying.

[0026] The beneficial effects achieved by the present invention include:

[0027] (1) The present invention uses bisphenol S recovery residue to replace the phenol raw material in the traditional production of sulfomethylphenolic resin, thereby achieving resource utilization of industrial solid waste while ensuring the excellent fluid loss reduction performance requirements of the resin product, while also reducing the production cost of the resin product and improving production efficiency;

[0028] (2) The use of phenol in the present invention can increase the reactivity of BPS residue, shorten the production cycle, and improve production efficiency;

[0029] (3) The structure of the product obtained by the present invention is different from that of traditional products. A bisphenol structure is introduced into the molecular chain of the traditional phenol-formaldehyde resin. The rigidity of the bisphenol structure is utilized to improve the high temperature resistance of the sulfomethylphenol-formaldehyde resin. Compared with traditional products, the fluid loss reduction performance is better.

[0030] (4) In the synthesis process of the present invention, phenol monomers with different chemical reaction activities are used as raw materials. If a "one-pot method" is adopted for preparation, it is easy to explode and form a bulk gel resin that is insoluble in water, thereby affecting the product performance. Therefore, the present invention adopts an alkaline step-by-step synthesis process, firstly subjecting the phenol monomers to a sufficient alkalization reaction under alkaline conditions to obtain the corresponding mixed phenol sodium salt, thereby improving the controllability of subsequent co-condensation and co-sulfonation reactions and enhancing the stability of product performance;

[0031] (5) 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;

[0032] (6) The sulfomethylphenolic resin product of the present invention can be used in a 200°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;

[0033] (7) The product of the present invention greatly improves the utilization value of bisphenol S residue and is expected to achieve clean production in the field of bisphenol S. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The present invention shows the process of preparing a low-cost phenolic resin fluid loss reducer by using bisphenol S residue extracted from phenol-containing wastewater in the industrial production of bisphenol S. DETAILED DESCRIPTION

[0035] 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.

[0036] Example

[0037] The bisphenol S residue used in the examples is extracted from phenolic wastewater in the industrial production of bisphenol S and is a recycled product of bisphenol S produced by Jiangsu Jiangyin Changsheng Chemical Co., Ltd. Its main components are 4,4'-bisphenol S, 2,4'-bisphenol S, sulfonation side reaction products, miscellaneous phenols, and residual unconverted phenol.

[0038] 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.

[0039] The sulfomethylphenolic resin product (SMP-II) used in the comparative example is an industrial-grade reagent purchased from Shandong Weifang Sanlibenuo Chemical Industry Co., Ltd. and Sichuan Zhengrong Industrial Co., Ltd.

[0040] The sulfonated methylphenolic resin supporting detection reagents sulfonated lignite (SMC) and sulfonated tannin (SMK) used in the experimental test are industrial-grade reagents purchased from Chengdu Chuanfeng Chemical Engineering Co., Ltd.

[0041] Example 1 Preparation of low-cost phenolic resin fluid loss additive using bisphenol S residue

[0042] (1) Pour 40 g of dried bisphenol S residue powder into a three-necked flask, and slowly add 40 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 97°C for 50 min;

[0043] (2) 40 g of sodium metabisulfite was uniformly dissolved in 80 g of water to prepare a sulfonating agent solution, and 88 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 4 h;

[0044] (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, and 140 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.

[0045] Example 2 Preparation of low-cost phenolic resin fluid loss additive using bisphenol S residue

[0046] (1) Pour 50 g of dried bisphenol S residue 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 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 98°C for 40 min;

[0047] (2) 47 g of sodium metabisulfite was uniformly dissolved in 80 g of water to prepare a sulfonating agent solution, and 80 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 98°C for 4 h;

[0048] (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.

[0049] Example 3 Preparation of low-cost phenolic resin fluid loss additive using bisphenol S residue

[0050] (1) Pour 20 g of dried bisphenol S residue powder into a three-necked flask, and slowly add 60 g of molten phenol into the flask under stirring; dissolve 2.5 g of sodium hydroxide and 24 g of anhydrous sodium carbonate in 60 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 60 min;

[0051] (2) 60 g of sodium metabisulfite was uniformly dissolved in 100 g of water to prepare a sulfonating agent solution, and 140 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 100 ° 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, 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.

[0053] Example 4 Preparation of low-cost phenolic resin fluid loss additive using bisphenol S residue

[0054] (1) Pour 40 g of dried bisphenol S residue powder into a three-necked flask, and slowly add 40 g of molten phenol into the flask under stirring; dissolve 4.5 g of sodium hydroxide and 20 g of anhydrous sodium carbonate in 60 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 60 min;

[0055] (2) 54 g of sodium metabisulfite was uniformly dissolved in 90 g of water to prepare a sulfonating agent solution, and 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. 10 g of water was added and the mixture was refluxed at 100 ° 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, 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.

[0057] Example 5 Preparation of low-cost phenolic resin fluid loss additive using bisphenol S residue

[0058] (1) Pour 40 g of dried bisphenol S residue powder into a three-necked flask, and slowly add 40 g of molten phenol into the flask under stirring; dissolve 4 g of sodium hydroxide and 18 g of anhydrous sodium carbonate in 60 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 50 min;

[0059] (2) 50 g of sodium metabisulfite was uniformly dissolved in 90 g of water to prepare a sulfonating agent solution, and 100 g of formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence, and the mixture was stirred continuously. 10 g of water was added and the mixture was refluxed at 98°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 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 6 Preparation of low-cost phenolic resin fluid loss additive using bisphenol S residue

[0062] (1) Pour 40 g of dried bisphenol S residue powder into a three-necked flask, and slowly add 40 g of molten phenol into the flask under stirring; dissolve 4.5 g of potassium hydroxide and 14 g of anhydrous sodium carbonate in 60 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 40 min;

[0063] (2) 45 g of sodium metabisulfite was uniformly dissolved in 90 g of water to prepare a sulfonating agent solution, and 90 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 98°C for 6 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, 120 min, 180 min, 240 min, and 300 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 7 Preparation of low-cost phenolic resin fluid loss additive using bisphenol S residue

[0066] (1) Pour 35 g of dried bisphenol S residue powder into a three-necked flask, and slowly add 40 g of molten phenol into the flask under stirring; dissolve 3.5 g of sodium hydroxide and 14 g of anhydrous sodium carbonate in 60 g of water to prepare an alkaline catalyst solution, add the solution to the three-necked flask after uniform dissolution, and reflux at 104° C. for 50 min;

[0067] (2) 44 g of anhydrous sodium bisulfite was uniformly dissolved in 90 g of water to prepare a sulfonating agent solution, and 85 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 104°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 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 8 Preparation of low-cost phenolic resin fluid loss additive using bisphenol S residue

[0070] (1) Pour 45 g of dried bisphenol S residue powder into a three-necked flask, and slowly add 40 g of molten phenol into the flask under stirring; dissolve 5 g of sodium hydroxide and 12 g of anhydrous sodium carbonate in 60 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) 55 g of anhydrous sodium bisulfite was uniformly dissolved in 90 g of water to prepare a sulfonating agent solution, and 90 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 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, 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.

[0073] Comparative Example 1

[0074] (1) Slowly add 40 g of bisphenol S residue powder and 40 g of molten phenol into a three-necked flask under stirring; dissolve 4 g of sodium hydroxide and 16 g of anhydrous sodium carbonate in 60 g of water to prepare an alkaline catalyst solution, and add the solution to the three-necked flask after the solution is uniformly dissolved;

[0075] (2) 45 g of sodium metabisulfite was uniformly dissolved in 90 g of water to prepare a sulfonating agent solution, and 90 g of formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence, and stirring was continued. 40 g of water was added and the mixture was refluxed at 98°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 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] Comparative Example 2

[0078] (1) Slowly add 30 g of bisphenol S residue powder, 50 g of molten phenol, 30 g of formaldehyde solution, and 30 g of water into a three-necked flask under stirring, stir and dissolve evenly, and then reflux at 100° C. for 20 min;

[0079] (2) Dissolve 3.5 g of sodium hydroxide and 14 g of anhydrous sodium carbonate in 60 g of water to prepare an alkaline catalyst solution; stir 50 g of sodium metabisulfite, 70 g of formaldehyde solution, and 20 g of water to prepare a sulfonating agent solution; and slowly add the prepared alkaline catalyst solution and sulfonating agent solution to a three-necked flask in sequence, continue stirring, add 20 g of water, and reflux at 100°C for 4 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, 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.

[0081] Comparative Example 3

[0082] (1) 80 g of bisphenol S residue powder was slowly added to a three-necked flask under stirring, and 5 g of sodium hydroxide and 20 g of anhydrous sodium carbonate were dissolved in 60 g of water to prepare an alkaline catalyst solution. After the solution was uniformly dissolved, the solution was added to the three-necked flask and refluxed at 100° C. for 60 min.

[0083] (2) 40 g of sodium metabisulfite was uniformly dissolved in 90 g of water to prepare a sulfonating agent solution, and 80 g of formaldehyde solution and the prepared sulfonating agent solution were slowly added to a three-necked flask in sequence, and stirring was continued. 40 g of water was added and the mixture was refluxed at 100 ° C for 4 h;

[0084] (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.

[0085] Comparative Example 4

[0086] The sample of comparative example 4 selected the SMP-Ⅱ product of Shandong Weifang Sanlibennuo Chemical Co., Ltd.

[0087] Comparative Example 5

[0088] The sample of comparative example 5 uses the SMP-Ⅱ product of Sichuan Zhengrong Industrial Co., Ltd.

[0089] Test example

[0090] 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 sulfomethylphenolic resin products of Examples 1-8 were tested, and the specific technical indicators are shown in Table 1.

[0091] Table 1 Technical indicators

[0092]

[0093] 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 drilling fluid properties of the products of Examples 1-8 and Comparative Examples 1-5 were tested. The specific results are shown in Table 2 below.

[0094] Table 2 Performance evaluation results of Examples 1 to 8

[0095]

[0096]

[0097] It can be seen from the data in Table 2 that the products of Examples 1-8 prepared by the present invention all have low high-temperature and high-pressure fluid loss and have no obvious viscosity-increasing effect on the drilling fluid.

[0098] Table 3 Performance evaluation results of comparative examples 1 to 7

[0099]

[0100] As can be seen from Tables 2 and 3, the products of Examples 1-8 have a fluid loss comparable to that of conventional phenolic resin SMP-II products made from phenol and formaldehyde in industry, and have no significant viscosity-increasing effect on drilling fluid mud, indicating that they have a good fluid loss reduction effect. The high-temperature and high-pressure fluid loss is much lower than 35 mL, meeting the standard requirements of "SY / T 5094-2017 Sulfomethylphenolic Resin SMP for Fluid Loss Reducers for Drilling Fluids".

[0101] Because industrial waste is used as production raw materials, the production cost of the product of the invention is greatly reduced based on the traditional sulfomethyl phenolic resin production process.

[0102] Table 4 below shows the performance evaluation results of Example 3, Example 7 and Comparative Example 4, Comparative Example 5 after aging at 200°C for 16 hours.

[0103] Table 4

[0104]

[0105] As shown in Table 4, the temperature resistance of the product of the present invention is better than that of the traditional SMP-II product, and it can withstand high temperatures of 200°C, which can meet the requirements of deep well drilling.

[0106] The present invention has been described in detail above with reference to specific embodiments and exemplary examples. 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 fluid loss reducer for drilling fluid using bisphenol S residue extracted from phenol-containing wastewater, comprising the following steps: (1) Synthesis of mixed phenol sodium salt Add dry bisphenol S residue solid powder to the reaction vessel, then slowly add melted phenol under stirring, then slowly pour the uniformly dissolved alkaline solution into the system, and react at 80℃-100℃ for 30min-80min; (2) Synthesis of sulfomethylphenolic resin Add 37% formaldehyde solution and pre-dissolved sulfonating agent solution into the reaction vessel, stir evenly, add water, and reflux at 90-110°C for 3-5 hours; (3) Control of reaction degree During the reaction, the viscosity of the system will gradually increase. As the reaction proceeds, water is added to the system every 30-80 minutes to adjust the degree of reaction.

2. The method according to claim 1, wherein In step (1), the mass ratio of the bisphenol S residue powder to phenol is 80:(40-240), preferably 80:

80.

3. The method according to claim 1, wherein In step (1), the alkali used as the catalyst is a composite alkali of sodium hydroxide or potassium hydroxide and anhydrous sodium carbonate, more preferably a composite alkali of sodium hydroxide and anhydrous sodium carbonate, preferably prepared into a 25% aqueous solution for use.

4. The method according to claim 1, wherein In step (1), the material dosage ratio is (total mass of bisphenol S residue and phenol): sodium hydroxide / potassium hydroxide: anhydrous sodium carbonate mass ratio of 80: (2-8): (10-40); preferably 80:4:

16.

5. The method according to claim 1, wherein In step (1), bisphenol S residue, phenol and alkaline catalyst are reacted at 80° C.-100° C. for 30 min-80 min; preferably at 97° C. for 60 min.

6. 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, and is preferably prepared as a 40% aqueous solution for use.

7. The method according to claim 1, wherein In step (2), the material dosage ratio is 80: (40-70): (80-140) based on the mass ratio of (total mass of bisphenol S residue and phenol): sulfonating agent: 37% formaldehyde solution; preferably 80:50:

100.

8. The method according to claim 1, wherein 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, refluxed at 97° C.-105° C. for 4 hours.

9. The method according to claim 1, wherein In step (3), the mass ratio of the total amount of water added to the total mass of bisphenol S residue and phenol is (45-80):80; preferably 60:80; The time interval for adding water is 30min-80min, preferably 60min.

10. A phenolic resin fluid loss additive prepared according to the method according to any one of claims 1 to 9.

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