A diquaternary ammonium disulfonate degreasing agent and its synthesis method and application

Abstract

The present invention belongs to the field of sewage treatment technology, and specifically relates to a diquaternary ammonium disulfonate degreasing agent, its synthesis method, and application. The synthesis method is as follows: piperazine, sodium p-hydroxybenzenesulfonate, formaldehyde solution, and water are added to a four-necked flask, stirred, heated, and refluxed to obtain a diquaternary ammonium disulfonate intermediate; the intermediate mixture is vacuum-distilled to dryness to obtain a viscous solid; DMF and an alkyl halide are added, the mixture is kept warm for reaction, and the mixture is evaporated to dryness on a rotary evaporator to obtain a crude diquaternary ammonium disulfonate; ethyl acetate is added to the crude product, heated to dissolve, filtered under reduced pressure, and the filtrate is cooled to precipitate a pale yellow solid; cyclohexane is added, heated to dissolve, filtered under reduced pressure, the filtrate is cooled to precipitate an off-white solid, filtered under reduced pressure, and the solid is dried overnight to obtain the degreasing agent product. The degreasing agent has the characteristics of a simple synthesis process, low dosage, low cost, and a single agent with multiple functions.

Description

Technical Field

[0001] The invention belongs to the technical field of sewage treatment, relates to an oilfield sewage degreasing agent and a preparation method thereof, and particularly relates to a diquaternary ammonium disulfonate degreasing agent and a synthesis method and application thereof. Background Art

[0002] Currently, during oilfield development, reservoir pressure gradually decreases, and crude oil production also decreases. Therefore, technological measures must be implemented to replenish formation energy in a timely manner to maintain a certain reservoir pressure. Reinjecting produced water is currently the predominant method of oilfield development, adopted by most oilfields in my country. Within oilfield water injection systems, a variety of harmful bacteria and microorganisms exist, the most common of which are sulfate-reducing bacteria (SRB), saprophytic bacteria (TGB), and iron bacteria (FB). These bacteria thrive underground or in equipment, easily causing a range of problems, including metal corrosion, formation blockage, and chemical deterioration. Therefore, produced water must be sterilized before reinjection. A variety of chemical agents are used to kill or inhibit microbial growth, and the extent of their microbial killing effects varies depending on the chemical's toxicity, cell permeability, and the type of microorganism. A chemical that is toxic to one microorganism may have no effect on another. Some chemicals are bactericidal at slightly higher concentrations, but can actually stimulate growth at lower concentrations. Therefore, only the proper selection and use of bactericides can effectively inhibit microbial growth.

[0003] At present, the oil field has entered the secondary and tertiary oil recovery stages, during which a large amount of surfactants and polymers are used, resulting in a large amount of suspended oil and emulsified oil in the produced water. The oil droplets in these wastewaters are small in size and exist stably in the water. The wastewater is easily sheared and further emulsified. The above reasons make it difficult to separate oil and water. The treated wastewater is difficult to meet the needs of oil well reinjection. If it is directly reinjected into the bottom layer without treatment, it will cause blockage of the injection well, reduce the pore permeability of the oil layer, hinder water injection and oil production, cause the injection pressure to increase, and directly affect crude oil production.

[0004] Common physical methods, such as flotation, involve introducing air into wastewater, generating tiny bubbles that act as carriers. These bubbles bind to pollutants such as emulsified oil and suspended solids, causing them to rise to the surface. The bubbles then collect the foam or scum that rises to the surface, separating the impurities and purifying the wastewater. While flotation is a relatively low-cost method for oil removal, it presents two challenges: first, the introduction of oxygen during the flotation process can corrode oil well equipment; second, pure flotation treatment is ineffective, often requiring chemical agents for optimal oil removal. Currently, new chemical oil removal methods are attracting increasing attention.

[0005] SYT 5329-2012 "Water Quality Indicators and Analysis Methods for Injection Water in Clastic Reservoirs" strictly regulates the quality of injection water, with sulfate-reducing bacteria, saprophytic bacteria, iron bacteria, and oil content being the main control indicators.

[0006] CN 200810023393.2 discloses a water-insoluble quaternary phosphonium salt bactericide and its preparation method. The bactericide is prepared by surface grafting an amino-quaternary phosphonium salt or a quaternary ammonium-quaternary phosphonium salt functional group having a bactericidal function onto a silica-based inorganic material as a carrier. The water-insoluble quaternary phosphonium salt bactericide provided by the present invention has excellent bactericidal activity and not only possesses the long-lasting effect of quaternary phosphonium salt bactericidal polymers but also possesses an efficient, rapid, and broad-spectrum bactericidal effect. Furthermore, the bactericide is widely available in raw materials, is low in cost, and has a simple synthesis process. The bactericide is insoluble in water and can be reused after activation and regeneration after the bactericidal rate is reduced. It can be widely used in the sterilization and disinfection of fluid media such as various industrial and civil water, as well as in the preparation of antibacterial materials. However, when used as an antibacterial material, it must be carried by a silica-based inorganic material, making it difficult to use on a large scale in field applications.

[0007] Soviet invention patent SU935481 discloses a technology for treating industrial wastewater using aluminum sulfate and a cationic flocculant. The main disadvantages of this invention are that its preparation method is complicated, the price is high, and the effect on oily wastewater is not ideal. Summary of the Invention

[0008] The present invention addresses the shortcomings of the prior art by providing a diquaternary ammonium disulfonate degreasing agent, its synthesis method, and its application. The degreasing agent features a simple synthesis process, low dosage, low cost, and multiple functions in one agent. Furthermore, the degreasing agent exhibits high sterilization efficiency at low concentrations, achieving a sterilization rate of 100% at a concentration of 20 mg / L.

[0009] Therefore, in order to achieve the above-mentioned object, on the one hand, the present invention discloses a method for synthesizing a diquaternary ammonium disulfonate degreasing agent, the synthesis method comprising: firstly, subjecting piperazine, sodium p-hydroxybenzenesulfonate and formaldehyde to a Mannich reaction under heating reflux; secondly, adding a halogenated hydrocarbon in the presence of DMF to cause a quaternization reaction, wherein the halogenated hydrocarbon has a structural formula as shown in formula (1):

[0010] RX (1)

[0011] Where: R is C8-C 18 X is one of chlorine, bromine and iodine.

[0012] On the other hand, the present invention discloses a diquaternary ammonium disulfonate degreasing agent, the molecular structure of which is as follows:

[0013]

[0014] in:

[0015] R is C8-C 18 Alkyl;

[0016] X is one of chlorine, bromine and iodine.

[0017] The third object of the present invention is to disclose the use of the above-mentioned diquaternary ammonium disulfonate degreasing agent in the sterilization and degreasing of oilfield wastewater.

[0018] The diquaternary ammonium disulfonate oil remover of the present invention belongs to a dicationic dianionic amphoteric surfactant, wherein the two cations are quaternary ammonium salts and the two anions are sulfonates. The bacterial surface is negatively charged, and the quaternary ammonium salts and the bacterial cells attract each other to combine, thereby allowing the molecules to penetrate into the cell interior, changing the permeability of the cell wall, making the bacterial protein lose activity and achieving the sterilization purpose, and the diquaternary ammonium salts can double the sterilization effect. The present invention has a stable structure, is less affected by water quality changes, is easily adsorbed on the surface of pipelines and equipment, and has a lasting sterilization effect. Simultaneously, the quaternary ammonium salts and sulfonates in the molecule are both hydrophilic groups, which can be in close contact with water and interact with each other. The long-chain alkyl group is a hydrophobic group with lipophilicity, which can be absorbed by the oil in the sewage and penetrate into the oily dirt. Therefore, the molecules of the present invention can diffuse in the oil-water interface. Since the interfacial activity of the present invention is higher than the oil-water interfacial activity in crude oil, the stability of the original interfacial film is destroyed, and the water coated in the film is released, thereby achieving the oil removal effect.

[0019] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0020] (1) The degreasing agent of the present invention has a wide range of raw material sources, a simple synthesis process, strong adaptability, and a small dosage, and can meet the needs of different sewage sterilization;

[0021] (2) The degreasing agent of the present invention has the advantage of high sterilization efficiency at low concentrations, and the sterilization rate can reach 100% when the concentration is 20 mg / L;

[0022] (3) The degreasing agent of the present invention has the advantage of high efficiency in low-concentration degreasing. When the concentration is 20 mg / L, the degreasing rate can reach more than 90%. DETAILED DESCRIPTION

[0023] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0024] According to a first aspect of the present invention, the present invention discloses a method for synthesizing a diquaternary ammonium disulfonate degreasing agent, the method comprising: firstly, subjecting piperazine, sodium p-hydroxybenzenesulfonate, and formaldehyde to a Mannich reaction under heating and reflux; secondly, adding a halogenated hydrocarbon in the presence of DMF to cause a quaternization reaction, wherein the halogenated hydrocarbon is as shown in structural formula (1):

[0025] RX (1)

[0026] Where: R is C8-C 18 X is one of chlorine, bromine and iodine.

[0027] In the present invention, preferably, R in formula (1) is C8-C 18 A straight chain alkyl group, more preferably C 12 -C 16 of a straight chain alkyl group.

[0028] In the present invention, preferably, X in formula (1) is bromine or iodine.

[0029] In the present invention, based on 1 mol part of piperazine, the amounts of sodium p-hydroxybenzenesulfonate, formaldehyde, and alkyl halide are 2-2.4 mol parts, 2.2-2.6 mol parts, and 2-2.4 mol parts, respectively; preferably, based on 1 mol part of piperazine, the amounts of sodium p-hydroxybenzenesulfonate, formaldehyde, and alkyl halide are 2.1-2.3 mol parts, 2.3-2.5 mol parts, and 2.1-2.3 mol parts, respectively.

[0030] Preferably, the heating reflux time is 24-48 hours; more preferably, the heating reflux time is 30-36 hours.

[0031] In the present invention, the mass ratio of DMF to piperazine is 20-30:1; more preferably, the mass ratio of DMF to piperazine is 20-25:1.

[0032] In the present invention, the quaternization reaction temperature is 110-120°C; more preferably, the quaternization reaction temperature is 110-115°C.

[0033] Preferably, the quaternization reaction time is 24-48 hours; more preferably, the quaternization reaction time is 32-36 hours.

[0034] According to a more specific preferred embodiment, the synthesis method of the disulfonic acid diquaternary ammonium salt deoiling agent comprises the following steps:

[0035] (1) piperazine, sodium p-hydroxybenzenesulfonate, 35-40 wt% formaldehyde solution, and water were added to a four-necked flask, and the mixture was stirred and refluxed for 24-48 hours to obtain a disulfonic acid di-tertiary amine salt intermediate;

[0036] (2) distilling the intermediate mixture to dryness under reduced pressure to obtain a viscous solid, adding DMF and alkyl halide, and reacting at 110-120° C. for 24-48 hours, and evaporating to dryness on a rotary evaporator to obtain a crude diquaternary ammonium salt of disulfonic acid;

[0037] (3) Ethyl acetate was added to the crude product, the temperature was raised to dissolve, and the product was filtered under vacuum. The filtrate was cooled to below 10°C to precipitate a light yellow solid. Cyclohexane was added, the temperature was raised to dissolve, and the product was filtered under vacuum. The filtrate was cooled to below 10°C to precipitate an off-white solid. The product was filtered under vacuum and the solid was dried at 80-90°C overnight to obtain the degreasing agent.

[0038] Preferably, the mass ratio of water to piperazine in step (1) is 20-30:1; more preferably, the mass ratio of water to piperazine is 25-30:1.

[0039] Preferably, the mass ratio of ethyl acetate to piperazine in step (3) is 5-8:1; more preferably, the mass ratio of ethyl acetate to piperazine is 5-6:1.

[0040] Preferably, the mass ratio of cyclohexane to piperazine in step (3) is 4-6:1; more preferably, the mass ratio of cyclohexane to piperazine is 4-5:1.

[0041] The reaction equation for the synthesis of the diquaternary ammonium disulfonate degreasing agent of the present invention is as follows:

[0042]

[0043] In a second aspect, the present invention discloses a diquaternary ammonium disulfonate degreasing agent, the molecular structure of which is as follows:

[0044]

[0045] in:

[0046] R is C8-C 18 Alkyl, preferably C8-C 18 A straight chain alkyl group, more preferably C 12 -C 16 of a straight chain alkyl group.

[0047] The third object of the present invention is to disclose the use of the above-mentioned diquaternary ammonium disulfonate degreasing agent in the sterilization and degreasing of oilfield wastewater. There are no special requirements for the specific application, and the application method conventional in the field can be used, which will not be discussed in detail here.

[0048] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0049] In addition, the various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

[0050] The present invention will be further described below with reference to specific embodiments.

[0051] In the present invention, the devices or equipment used are all conventional devices or equipment known in the art and are commercially available.

[0052] In the following examples and comparative examples, unless otherwise specified, all reagents used were commercially available chemically pure reagents.

[0053] Example 1:

[0054] (1) Add 0.15 mol of piperazine, 0.3 mol of sodium p-hydroxybenzenesulfonate, 0.33 mol of 37 wt% formaldehyde solution, and 258 g of water to a four-necked flask, stir, heat, and reflux for 24 h to obtain a disulfonic acid di-tertiary amine salt intermediate;

[0055] (2) The intermediate mixture was distilled to dryness under reduced pressure to obtain a viscous solid, 258 g of DMF and 0.3 mol of chlorooctane were added, and the mixture was kept at 110-120° C. for 48 h, and then evaporated to dryness on a rotary evaporator to obtain a crude diquaternary ammonium salt of disulfonic acid;

[0056] (3) 65 g of ethyl acetate was added to the crude product, the temperature was raised to dissolve, and the filtrate was filtered under reduced pressure. The filtrate was cooled to below 10° C. to precipitate a light yellow solid, which was filtered under reduced pressure. The light yellow solid was placed in 52 g of cyclohexane, the temperature was raised to dissolve, and the filtrate was filtered under reduced pressure. The filtrate was cooled to below 10° C. to precipitate an off-white solid, which was filtered under reduced pressure. The solid was dried at 80-90° C. overnight to obtain the degreaser product M1.

[0057] The molecular formula of M1 is:

[0058]

[0059] Example 2:

[0060] (1) Add 0.15 mol of piperazine, 0.36 mol of sodium p-hydroxybenzenesulfonate, 0.39 mol of 37 wt% formaldehyde solution, and 387 g of water to a four-necked flask, stir, heat, and reflux for 48 hours to obtain a disulfonic acid di-tertiary amine salt intermediate;

[0061] (2) The intermediate mixture was distilled to dryness under reduced pressure to obtain a viscous solid, 387 g of DMF and 0.33 mol of bromooctadecane were added, and the mixture was kept at 110-120° C. for 24 h, and then evaporated to dryness on a rotary evaporator to obtain a crude diquaternary ammonium salt of disulfonic acid;

[0062] (3) 103 g of ethyl acetate was added to the crude product, the temperature was raised to dissolve, and the filtrate was filtered under reduced pressure. The filtrate was cooled to below 10° C. to precipitate a light yellow solid, which was filtered under reduced pressure. The light yellow solid was placed in 77 g of cyclohexane, the temperature was raised to dissolve, and the filtrate was filtered under reduced pressure. The filtrate was cooled to below 10° C. to precipitate an off-white solid, which was filtered under reduced pressure. The solid was dried at 80-90° C. overnight to obtain the degreaser product M2.

[0063] The molecular formula of M2 is:

[0064]

[0065] Example 3:

[0066] (1) Add 0.15 mol of piperazine, 0.32 mol of sodium p-hydroxybenzenesulfonate, 0.35 mol of 37 wt% formaldehyde solution, and 276 g of water to a four-necked flask, stir, heat, and reflux for 30 h to obtain a disulfonic acid di-tertiary amine salt intermediate;

[0067] (2) The intermediate mixture was distilled to dryness under reduced pressure to obtain a viscous solid, 276 g of DMF and 0.32 mol of iododecane were added, and the mixture was kept at 110-120° C. for 30 h, and then evaporated to dryness on a rotary evaporator to obtain a crude diquaternary ammonium salt of disulfonic acid;

[0068] (3) 77 g of ethyl acetate was added to the crude product, the temperature was raised to dissolve, and the filtrate was filtered under reduced pressure. The filtrate was cooled to below 10° C. to precipitate a light yellow solid, which was filtered under reduced pressure. The light yellow solid was placed in 56 g of cyclohexane, the temperature was raised to dissolve, and the filtrate was filtered under reduced pressure. The filtrate was cooled to below 10° C. to precipitate an off-white solid, which was filtered under reduced pressure. The solid was dried at 80-90° C. overnight to obtain the degreaser product M3.

[0069] The M3 molecular formula is:

[0070]

[0071] Example 4:

[0072] (1) In a four-necked flask, 0.15 mol of piperazine, 0.34 mol of sodium p-hydroxybenzenesulfonate, 0.37 mol of 37 wt% formaldehyde solution, and 354 g of water were added, and the mixture was stirred and refluxed for 40 h to obtain a disulfonic acid di-tertiary amine salt intermediate;

[0073] (2) The intermediate mixture was distilled to dryness under reduced pressure to obtain a viscous solid, 347 g of DMF and 0.33 mol of bromodecane were added, and the mixture was kept at 110-120° C. for 24 h, and then evaporated to dryness on a rotary evaporator to obtain a crude diquaternary ammonium salt of disulfonic acid;

[0074] (3) 96 g of ethyl acetate was added to the crude product, the temperature was raised to dissolve, and the filtrate was filtered under reduced pressure. The filtrate was cooled to below 10° C. to precipitate a light yellow solid, which was filtered under reduced pressure. The light yellow solid was placed in 72 g of cyclohexane, the temperature was raised to dissolve, and the filtrate was filtered under reduced pressure. The filtrate was cooled to below 10° C. to precipitate an off-white solid, which was filtered under reduced pressure. The solid was dried at 80-90° C. overnight to obtain the degreaser product M4.

[0075] The M4 molecular formula is:

[0076]

[0077] Example 5:

[0078] (1) Add 0.15 mol of piperazine, 0.33 mol of sodium p-hydroxybenzenesulfonate, 0.36 mol of 37 wt% formaldehyde solution, and 304 g of water to a four-necked flask, stir, heat, and reflux for 32 h to obtain a disulfonic acid di-tertiary amine salt intermediate;

[0079] (2) The intermediate mixture was distilled to dryness under reduced pressure to obtain a viscous solid, 312 g of DMF and 0.33 mol of bromotetradecane were added, and the mixture was heated at 110-120° C. for 30 h, and then evaporated to dryness on a rotary evaporator to obtain a crude diquaternary ammonium salt of disulfonic acid;

[0080] (3) 82 g of ethyl acetate was added to the crude product, the temperature was raised to dissolve, and the filtrate was filtered under reduced pressure. The filtrate was cooled to below 10° C. to precipitate a light yellow solid, which was filtered under reduced pressure. The light yellow solid was placed in 60 g of cyclohexane, the temperature was raised to dissolve, and the filtrate was filtered under reduced pressure. The filtrate was cooled to below 10° C. to precipitate an off-white solid, which was filtered under reduced pressure. The solid was dried at 80-90° C. overnight to obtain the degreaser product M5.

[0081] The M5 molecular formula is:

[0082]

[0083] Example 6:

[0084] (1) In a four-necked flask, 0.15 mol of piperazine, 0.33 mol of sodium p-hydroxybenzenesulfonate, 0.36 mol of 37 wt% formaldehyde solution, and 318 g of water were added, and the mixture was stirred and refluxed for 36 h to obtain a disulfonic acid di-tertiary amine salt intermediate;

[0085] (2) The intermediate mixture was distilled to dryness under reduced pressure to obtain a viscous solid, 333 g of DMF and 0.33 mol of bromohexadecane were added, and the mixture was kept at 110-120° C. for 30 h, and then evaporated to dryness on a rotary evaporator to obtain a crude diquaternary ammonium salt of disulfonic acid;

[0086] (3) 90 g of ethyl acetate was added to the crude product, the temperature was raised to dissolve, and the filtrate was filtered under reduced pressure. The filtrate was cooled to below 10° C. to precipitate a light yellow solid, which was filtered under reduced pressure. The light yellow solid was placed in 66 g of cyclohexane, the temperature was raised to dissolve, and the filtrate was filtered under reduced pressure. The filtrate was cooled to below 10° C. to precipitate an off-white solid, which was filtered under reduced pressure. The solid was dried at 80-90° C. overnight to obtain the degreaser product M6.

[0087] The molecular formula of M6 is:

[0088]

[0089] Example 7: Evaluation of sterilization rate

[0090] To a series of narrow-necked bottles, 500 ml of water sampled from a joint station at the Dongxin Oilfield Production Plant in Shengli Oilfield was added. The bacterial counts were as follows: 110 SRB cells / ml, 45 TGB cells / ml, and 11 FB cells / ml. Various concentrations of M1-M6 and a fungicide were added, shaken, and placed in a 65°C oven. After 1 hour, samples were taken and the residual bacterial count was determined using the three-tube MPN method. The bactericidal rate was calculated.

[0091] Table 1 SRB sterilization results (sterilization rate, %)

[0092] Concentration, mg / L 10 15 20 30 <![CDATA[M1]]> 94.1 99.3 100 100 <![CDATA[M2]]> 96.4 99.5 100 100 <![CDATA[M3]]> 96.8 99.5 100 100 <![CDATA[M4]]> 96.8 99.5 100 100 <![CDATA[M5]]> 97.3 99.7 100 100 <![CDATA[M6]]> 98.2 100 100 100 Dichlorophen 0 0 59.1 72.7 1227 0 59.1 77.3 85.5

[0093] As can be seen from Table 1: 1-6 At a concentration of 10 mg / L, the sterilization rate against SRB reached over 94%, with a maximum of 98.2% (M6). At a concentration of 20 mg / L or above, the sterilization rate reached 100%. In contrast, the sterilization rates of dichlorophen and 1227 against SRB at a concentration of 10 mg / L were 0% and 0%, respectively, and at a concentration of 20 mg / L, the sterilization rates were 59.1% and 77.3%, respectively. Compared with existing sterilizers, the sterilization effect of the present invention against SRB is superior.

[0094] Table 2 TGB sterilization results (sterilization rate, %)

[0095]

[0096]

[0097] As can be seen from Table 2: 1-6At a concentration of 10 mg / L, the bactericidal rate against TGB reached over 96%, with a maximum of 97.6% (G6). At a concentration of 20 mg / L or above, the bactericidal rate reached 100%. In contrast, the bactericidal rates of dichlorophen and 1227 against TGB at a concentration of 10 mg / L were 0% and 0%, respectively, and at a concentration of 20 mg / L, they were 55.6% and 64.4%, respectively. Compared to existing bactericides, the bactericidal effect of the present invention against TGB was superior.

[0098] Table 3 FB sterilization results (sterilization rate, %)

[0099] Concentration, mg / L 10 15 20 30 <![CDATA[M1]]> 97 100 100 100 <![CDATA[M2]]> 97 100 100 100 <![CDATA[M3]]> 100 100 100 100 <![CDATA[M4]]> 100 100 100 100 <![CDATA[M5]]> 100 100 100 100 <![CDATA[M6]]> 100 100 100 100 Dichlorophen 0 64 97 100 1227 41 90 100 100

[0100] As can be seen from Table 3: 1-6 When the concentration was 10 mg / L, the sterilization rate of FB reached more than 96%, and the highest reached 100% (M 3-6 ); the sterilization rate against FB reached 100% when the concentration was 20 mg / L or above; while the sterilization rates against FB of dichlorophen and 1227 were 0% and 41% at a concentration of 10 mg / L, and 97% and 100% at a concentration of 20 mg / L, respectively. Compared with existing sterilizers, the sterilization effect of the present invention on FB is good.

[0101] Example 8 Evaluation of oil removal effect

[0102] The oily wastewater evaluated indoors was produced water from a block of the Dongxin Oilfield in Shengli Oilfield. The oil content of the wastewater was 456 mg / L. 1000 ml of produced water was added to a series of beakers, along with M1-M6 and deoiling agents at different concentrations. The mixture was stirred at 200 rpm for 60 seconds, allowed to stand for 15 minutes, and the lower layer of water was taken to test the oil content and calculate the oil removal rate.

[0103] Table 4 Degreasing effect (oil removal rate, %)

[0104] Concentration, mg / L 10 20 30 50 <![CDATA[M1]]> 85.4 91.4 94.5 98.1 <![CDATA[M2]]> 88.3 91.5 94.6 98.2 <![CDATA[M3]]> 88.6 91.6 94.6 98.2 <![CDATA[M4]]> 89.1 91.8 94.7 98.2 <![CDATA[M5]]> 89.1 91.8 94.8 98.2 <![CDATA[M6]]> 89.3 92 95 98.3 SGR1711 35.9 74.2 86.1 90.3

[0105] As can be seen from Table 4: 1-6 At a concentration of 10 mg / L, the oil removal rate reached over 85%, with a peak of 89.3% (M6). At concentrations of 20 mg / L and above, the oil removal rate reached over 90%. In contrast, SGR1711 had an oil removal rate of 35.9% at a concentration of 10 mg / L and 74.2% at a concentration of 20 mg / L. Compared to existing fungicides, the fungicide of the present invention exhibited superior bactericidal effects against FB.

[0106] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A method for synthesizing a diquaternary ammonium disulfonate degreasing agent, characterized in that: The synthesis method comprises: firstly, under heating reflux, piperazine, sodium p-hydroxybenzenesulfonate and formaldehyde undergo a Mannich reaction; secondly, in the presence of DMF, a halogenated hydrocarbon is added to undergo a quaternization reaction, wherein the halogenated hydrocarbon has the following structural formula: RX(1) Where: R is C8-C 18 X is one of chlorine, bromine and iodine.

2. The method for synthesizing a diquaternary ammonium disulfonate degreasing agent according to claim 1, wherein: Based on 1 mole of piperazine, the amounts of sodium p-hydroxybenzenesulfonate, formaldehyde and alkyl halide used are 2-2.4 moles, 2.2-2.6 moles and 2-2.4 moles respectively.

3. The method for synthesizing the diquaternary ammonium disulfonate degreasing agent according to claim 1, wherein: Based on 1 mol part of piperazine, the amounts of sodium p-hydroxybenzenesulfonate, formaldehyde and alkyl halide used are 2.1-2.3 mol parts, 2.3-2.5 mol parts and 2.1-2.3 mol parts respectively.

4. The method for synthesizing the diquaternary ammonium disulfonate degreasing agent according to claim 1, wherein: In formula (1), R is C8-C 18 of a straight chain alkyl group.

5. The method for synthesizing the diquaternary ammonium disulfonate degreasing agent according to claim 4, wherein: In formula (1), R is C 12 -C 16 of a straight chain alkyl group.

6. The method for synthesizing the diquaternary ammonium disulfonate degreasing agent according to claim 1, wherein: In formula (1), X is bromine or iodine.

7. The method for synthesizing the diquaternary ammonium disulfonate degreasing agent according to claim 1, wherein: The heating reflux time is 24-48h.

8. The method for synthesizing the diquaternary ammonium disulfonate degreasing agent according to claim 7, wherein: The heating reflux time is 30-36h.

9. The method for synthesizing the diquaternary ammonium disulfonate degreasing agent according to claim 1, wherein: The mass ratio of DMF to piperazine is 20-30:

1.

10. The method for synthesizing the diquaternary ammonium disulfonate degreasing agent according to claim 1, wherein: The quaternization reaction temperature is 110-120°C.

11. The method for synthesizing the diquaternary ammonium disulfonate degreasing agent according to claim 10, wherein: The quaternization reaction temperature is 110-115°C.

12. The method for synthesizing the diquaternary ammonium disulfonate degreasing agent according to claim 1, wherein: The quaternization reaction time is 24-48h.

13. The method for synthesizing the diquaternary ammonium disulfonate degreasing agent according to claim 12, wherein: The quaternization reaction time is 32-36 hours.

14. A diquaternary ammonium disulfonate degreasing agent, characterized in that: The molecular structural formula of the degreasing agent is as follows: in: R is C8-C 18 of alkyl.

15. The diquaternary ammonium disulfonate degreasing agent according to claim 14, characterized in that: The molecular structural formula of the degreasing agent is as follows: in: R is C 12 -C 16 of a straight chain alkyl group.

16. Use of the diquaternary ammonium disulfonate degreasing agent according to any one of claims 14 to 15 in sterilizing and degreasing oil from oilfield wastewater.

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