Oilfield reinjection water polymer bactericide and synthesis method thereof

Abstract

The invention belongs to the technical field of sewage treatment, and relates to an oilfield reinjection water polymer bactericide and a synthesis method thereof. The synthesis method comprises the following steps: carrying out an addition reaction on 2-cyclohexene-1-ketone and secondary phosphine under the protection of nitrogen in the presence of an organic solvent to obtain tertiary phosphine; secondly, in the presence of a solvent, carrying out quaternary phosphonium reaction on tertiary phosphine and halogen propylene in a reflux state to obtain unsaturated quaternary phosphonium salt; finally, under the action of an initiator and a reducing agent, the unsaturated quaternary phosphonium salt and the unsaturated quaternary ammonium salt are subjected to a polymerization reaction. The bactericide is wide in raw material source and simple in synthesis process; broad-spectrum sterilization is realized; the sterilization efficiency is high; the reinjection water purifying agent has the characteristics of flocculation, reduction of suspended matters in reinjection water and further purification of water quality.

Description

Technical Field

[0001] The invention belongs to the technical field of sewage treatment, and relates to a sewage bactericide and a synthesis method thereof, and in particular to an oilfield reinjection water polymer bactericide and a synthesis method thereof. Background Art

[0002] Reinjecting treated oil production wastewater into the oil layer can not only replenish formation energy and maintain stable oil field production, but also reduce the harm caused by wastewater discharge to humans and ecosystems, which is beneficial to protecting the environment. Therefore, it is widely used.

[0003] However, there are many harmful bacteria and microorganisms in the oil field water injection development system, the most common of which are sulfate reducing bacteria (SRB), saprophytic bacteria (TGB) and iron bacteria (FB). The growth, metabolism and reproduction of these bacteria can cause corrosion and damage to drilling equipment, water injection pipelines and other metal materials, blockage of pipelines and water injection wells, reduce the pore permeability of the oil layer, hinder water injection and oil production, and directly affect crude oil production. Therefore, the produced water must be sterilized before reinjection.

[0004] At present, there are only a few types of fungicides used in oilfield produced water. Long-term use will cause bacteria to develop certain drug resistance, resulting in a significant decrease in the effectiveness of the agents. In addition, some chemical agents are toxic to a certain microorganism, but may have no effect on another microorganism. Some agents have a bactericidal effect at a slightly higher concentration, but at a certain low concentration, they have a stimulating effect on growth. Therefore, only by correctly selecting and using fungicides can the reproduction of microorganisms be effectively inhibited.

[0005] CN107593703B discloses a bactericide for oilfield water treatment system and its preparation method and application, the bactericide comprises 5wt.% to 60wt.% of dodecyl dimethyl benzyl ammonium halide, 0.5wt.% to 5wt.% of D-amino acid, 10wt.% to 30wt.% of surfactant, 3wt.% to 10wt.% of buffer and the balance of water. The bactericide of the invention has high bactericidal efficiency, has high bactericidal effect on sulfate reducing bacteria (SRB) and saprophytic bacteria (TGB), has long duration of efficacy, is simple in production process and has low cost.

[0006] CN200810023393.2 discloses a water-insoluble quaternary phosphonium salt type bactericide and a preparation method thereof. The bactericide is prepared by using a silica gel inorganic material as a carrier and grafting an amino-quaternary phosphonium salt or a quaternary ammonium-quaternary phosphonium salt functional group with a bactericidal function on the surface. The water-insoluble quaternary phosphonium salt type bactericide provided by the invention has excellent bactericidal activity, not only has the long-term effect of the quaternary phosphonium salt type bactericidal polymer, but also has an efficient, rapid and broad-spectrum bactericidal effect. Moreover, the raw material source is wide, the cost is low, and the synthesis process is simple. 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 various industrial and civil water and other fluid media and the preparation of antibacterial materials.

[0007] The above patents have the problem of environmental damage or the problem of large dosage of bactericide and unsatisfactory bactericidal effect; or the problem of requiring other inorganic materials as carriers when using, which limits the on-site use. Summary of the invention

[0008] The present invention aims to provide a high molecular fungicide for oilfield reinjection water and a synthesis method in view of the deficiencies of the above-mentioned prior art. The fungicide has the characteristics of wide raw material sources, simple synthesis process, broad-spectrum bactericidal effect, high bactericidal efficiency, flocculation effect, and can reduce suspended matter in reinjection water and further purify water quality. The fungicide of the present invention has the advantages of low concentration and high efficiency. When the concentration is 20 mg / L, the bactericidal rate of SRB, TGB and FB can reach 100%.

[0009] Therefore, in order to achieve the above-mentioned purpose, on the one hand, the present invention discloses a polymer fungicide for oilfield reinjection water, and the molecular structure of the fungicide is as follows:

[0010]

[0011] Where: m = 50-1000, n = 50-1000, R 1 is a C1-C4 alkyl group, R 2 C1-C 18 wherein X is one of chlorine, bromine and iodine, and Y is chlorine or bromine.

[0012] On the other hand, the present invention discloses a method for synthesizing the above-mentioned high molecular fungicide for oilfield reinjection water, which comprises: under nitrogen protection and in the presence of an organic solvent, 2-cyclohexene-1-one and a secondary phosphine undergo an addition reaction to obtain a tertiary phosphine; secondly, in the presence of a solvent and under reflux, the tertiary phosphine and a propylene halide undergo a quaternization reaction to obtain an unsaturated quaternary phosphonium salt; finally, under the action of an initiator and a reducing agent, the unsaturated quaternary phosphonium salt and an unsaturated quaternary ammonium salt undergo a polymerization reaction.

[0013] In a third aspect, the present invention discloses the application of the above-mentioned oilfield reinjection water polymer fungicide in oilfield wastewater treatment.

[0014] The polymer bactericide of the present invention has strong bactericidal property, and the quaternary ammonium cation in the molecule has strong positive charge, can adsorb negatively charged bacteria, change the permeability of cell membrane, destroy membrane structure, affect cell metabolism process, and cause bacterial death. The bactericidal principle of quaternary phosphonium salt is similar to that of quaternary ammonium salt, and the phosphorus atom has a larger radius than the nitrogen atom and less electronegativity, and the quaternary phosphonium atom has stronger positive charge, so the bactericidal ability is stronger than that of quaternary ammonium salt. The bactericide molecule can penetrate into the inside of the bacterial cell, so that the bacterial protein loses activity and reaches the purpose of sterilization. The polymer of 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 exerts a lasting bactericidal effect.

[0015] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0016] (1) The bactericide of the present invention has a wide range of raw materials, a simple synthesis process, strong adaptability, and a small amount of use, and can meet the needs of different sewage sterilization;

[0017] (2) The bactericide of the present invention has a broad spectrum and can kill SRB, TGB and FB in oily wastewater;

[0018] (3) The fungicide of the present invention has the advantages of low concentration and high efficiency. When the concentration is 20 mg / L, the fungicide rate against SRB, TGB and FB can reach 100%.

[0019] (4) The present invention has a flocculation effect, which can reduce suspended matter in the reinjection water and further purify the water quality. DETAILED DESCRIPTION

[0020] The endpoints and any values ​​of the ranges disclosed in this article 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 endpoint values ​​of each range, the endpoint values ​​of each range and the 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 as specifically disclosed in this article.

[0021] According to the first aspect of the present invention, the present invention discloses a polymer fungicide for oilfield reinjection water, the molecular structure of the fungicide is as follows:

[0022]

[0023] Where: m = 50-1000, n = 50-1000, R 1 is a C1-C4 alkyl group, R 2 C1-C18 wherein X is one of chlorine, bromine and iodine, and Y is chlorine or bromine.

[0024] Preferably, m=100-500, n=100-500.

[0025] Preferably, the R 2 C1-C 12 The alkyl group is more preferably C6-C 10 of normal alkyl.

[0026] Preferably, X is chlorine or bromine.

[0027] According to the second aspect of the present invention, the present invention provides a method for synthesizing the above-mentioned high molecular fungicide for oilfield reinjection water, the synthesis method comprising: under nitrogen protection, in the presence of an organic solvent, 2-cyclohexene-1-one and a secondary phosphine undergo an addition reaction to obtain a tertiary phosphine; secondly, in the presence of a solvent, under reflux, the tertiary phosphine and a propylene halide undergo a quaternization reaction to obtain an unsaturated quaternary phosphonium salt; finally, under the action of an initiator and a reducing agent, the unsaturated quaternary phosphonium salt and an unsaturated quaternary ammonium salt undergo a polymerization reaction.

[0028] In the present invention, preferably, based on 1 mol part of 2-cyclohexene-1-one, the amounts of the secondary phosphine, halogenated propene and unsaturated quaternary ammonium salt are 0.9-1.2 mol parts, 0.9-1 mol parts and 0.5-2 mol parts respectively; more preferably, based on 1 mol part of 2-cyclohexene-1-one, the amounts of the secondary phosphine, halogenated propene and unsaturated quaternary ammonium salt are 0.95-1.1 mol parts, 0.95-1 mol parts and 0.5-1.5 mol parts respectively.

[0029] In the present invention, preferably, the organic solvent is ethanol or isopropanol.

[0030] In the present invention, preferably, the addition reaction time is 6-12 hours, and the temperature is 45-50°C; more preferably, the addition reaction time is 6-10 hours, and the temperature is 45-48°C.

[0031] In the present invention, preferably, the solvent is one or more of methanol, ethanol, propanol, butanol, and isopropanol; more preferably, the solvent is ethanol, isopropanol, or a mixture of the two in any ratio.

[0032] In the present invention, preferably, the mass ratio of the solvent to 2-cyclohexene-1-one is 20-30:1.

[0033] In the present invention, preferably, the quaternary phosphonium reaction time is 24-48 hours; more preferably, the quaternary phosphonium reaction time is 32-42 hours.

[0034] In the present invention, preferably, the initiator is one of sodium persulfate, potassium persulfate and ammonium persulfate, and the mass concentration of the initiator solution is 10-20%.

[0035] In the present invention, preferably, the weight ratio of the initiator solution to 2-cyclohexene-1-one is 0.5-1:1.

[0036] In the present invention, preferably, the reducing agent is sodium sulfite or potassium sulfite, and the mass concentration of the reducing agent solution is 5-10%.

[0037] In the present invention, preferably, the weight ratio of the reducing agent solution to 2-cyclohexene-1-one is 0.5-1:1.

[0038] In the present invention, preferably, the polymerization reaction temperature is 50-80°C and the time is 2-5h; more preferably, the polymerization reaction includes two stages carried out sequentially, the reaction temperature of the first stage is 50-55°C and the time is 1-3h, and the reaction temperature of the second stage is 70-80°C and the time is 1-2h.

[0039] According to a more specific preferred embodiment, the synthesis method of the oilfield reinjection water polymer fungicide specifically comprises the following steps:

[0040] (1) Add 2-cyclohexene-1-one to a four-necked flask equipped with a condenser under nitrogen protection, dissolve the secondary phosphine in an organic solvent and slowly add it dropwise to the four-necked flask. After the addition is complete, heat to 45-50° C., stir and keep warm for 6-12 hours, and distill off the organic solvent and raw materials that have not participated in the reaction under reduced pressure;

[0041] (2) Add the solvent and propylene halide to the above four-necked flask, heat and reflux for 24-48 hours, and distill under reduced pressure to obtain a yellow-brown viscous solid;

[0042] (3) then recrystallizing the solid with ethyl acetate to obtain a solid which is an unsaturated quaternary phosphonium salt;

[0043] (4) In another flask, add the above-mentioned unsaturated quaternary phosphonium salt, unsaturated quaternary ammonium salt OP-10, MS-1 and water, and heat to 50-55°C while stirring. After all are dissolved, add initiator and reducing agent dropwise. After the addition is complete, continue stirring for 1-3 hours, heat to 70-80°C, and continue to react for 1-2 hours to obtain a viscous liquid;

[0044] (5) Granulate the viscous liquid to obtain light yellow particles of 1-4 mm, thus obtaining a high molecular weight fungicide.

[0045] Preferably, in step (4), the weight ratio of OP-10, MS-1 and water to 2-cyclohexene-1-one is 0.2-0.4:0.1-0.2:8-12:1.

[0046] The reaction equation for the synthesis of the polymer fungicide of the present invention is as follows:

[0047]

[0048]

[0049] The third object of the present invention is to disclose the application of the above-mentioned oilfield reinjection water polymer bactericide in oilfield wastewater treatment. There is no special requirement for the specific application, and it can be a conventional application in the field, which will not be discussed in detail here.

[0050] More preferably, the application is application in oilfield reinjection water treatment.

[0051] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0052] In addition, 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.

[0053] The present invention will be further described below with reference to specific embodiments.

[0054] In the present invention, the devices or equipment used are all conventional devices or equipment known in the art and are commercially available.

[0055] In the following examples and comparative examples, unless otherwise specified, all reagents used were commercially available chemically pure reagents.

[0056] Embodiment 1:

[0057] (1) Add 0.1 mol of 2-cyclohexene-1-one to a four-necked flask equipped with a condenser under nitrogen protection, slowly dropwise add 60 ml of a 2 mol / L dimethylphosphine ethanol solution, and after the dropwise addition is complete, raise the temperature to 45° C., stir and keep the reaction for 6 h, and distill off the unreacted solvent ethanol and raw materials under reduced pressure;

[0058] (2) Add 288 g of methanol and 0.09 mol of allyl chloride into the above four-necked flask, heat under reflux for 24 h, and distill under reduced pressure to obtain a yellow-brown viscous solid;

[0059] (3) then recrystallizing the solid with ethyl acetate to obtain a solid which is an unsaturated quaternary phosphonium salt;

[0060] (4) In another flask, add the above-mentioned unsaturated quaternary phosphonium salt, 0.05 mol of allyltrimethylammonium chloride, 1.92 g of OP-10, 1.92 g of MS-1 and 77 g of water, and heat to 50° C. while stirring. After all the mixture is dissolved, add dropwise 4.8 g of 20 wt % sodium persulfate solution and 4.8 g of 10 wt % sodium sulfite solution. After the addition is complete, continue stirring for 1 h, heat to 77° C., and continue reacting for 1 h to obtain a viscous liquid;

[0061] (5) Granulate the viscous liquid to obtain light yellow particles of 1-4 mm, thus obtaining polymer fungicide product A.

[0062] Embodiment 2:

[0063] (1) Add 0.1 mol of 2-cyclohexene-1-one to a four-necked flask equipped with a condenser under nitrogen protection, slowly dropwise add 45 ml of a 2 mol / L dibutylphosphine isopropanol solution, and after the dropwise addition is complete, raise the temperature to 50° C., stir and keep the reaction for 12 h, and distill off the unreacted isopropanol solvent and raw materials under reduced pressure;

[0064] (2) Add 192 g of a mixed solvent of methanol, ethanol, propanol, butanol, and isopropanol in a mass ratio of 1:1:1:1:1 and 0.1 mol of iodopropylene into the above four-necked flask, heat under reflux for 48 h, and distill under reduced pressure to obtain a yellow-brown viscous solid;

[0065] (3) then recrystallizing the solid with ethyl acetate to obtain a solid which is an unsaturated quaternary phosphonium salt;

[0066] (4) In another flask, add the above-mentioned unsaturated quaternary phosphonium salt, 0.2 mol hexadecyldimethylallylammonium chloride, 3.84 g OP-10, 1.92 g MS-1 and 115 g water, and heat to 52° C. while stirring. After all the solution is dissolved, add dropwise 9.6 g 10 wt % sodium persulfate solution and 9.5 g 5 wt % sodium sulfite solution. After the addition is complete, continue stirring for 3 h, heat to 72° C., and continue the reaction for 1 h to obtain a viscous liquid;

[0067] (5) Granulate the viscous liquid to obtain light yellow particles of 1-4 mm, thus obtaining polymer fungicide product B.

[0068] Embodiment 3:

[0069] (1) Add 0.1 mol of 2-cyclohexene-1-one to a four-necked flask equipped with a condenser under nitrogen protection, slowly dropwise add 55 ml of a 2 mol / L diethylphosphine ethanol solution, and after the dropwise addition is complete, raise the temperature to 46° C., stir and keep the reaction for 8 h, and distill off the unreacted raw materials under reduced pressure;

[0070] (2) Add 240 g of ethanol and 0.095 mol of allyl bromide into the above four-necked flask, heat under reflux for 30 h, and distill under reduced pressure to obtain a yellow-brown viscous solid;

[0071] (3) then recrystallizing the solid with ethyl acetate to obtain a solid which is an unsaturated quaternary phosphonium salt;

[0072] (4) In another flask, add the above-mentioned unsaturated quaternary phosphonium salt, 0.15 mol dodecyldimethylallylammonium chloride, 2.46 g OP-10, 1.83 g MS-1 and 85 g water, and heat to 55° C. while stirring. After all the solution is dissolved, add dropwise 6.2 g 15 wt % potassium persulfate solution and 6.2 g 8 wt % sodium sulfite solution. After the addition is complete, continue stirring for 1 h, heat to 75° C., and continue the reaction for 1 h to obtain a viscous liquid;

[0073] (5) Granulate the viscous liquid to obtain light yellow particles of 1-4 mm, thus obtaining polymer fungicide product C.

[0074] Embodiment 4:

[0075] (1) Add 0.1 mol of 2-cyclohexene-1-one to a four-necked flask equipped with a condenser under nitrogen protection, slowly dropwise add 50 ml of a 2 mol / L ethanol solution of di-tert-butylphosphine, and after the dropwise addition is complete, raise the temperature to 47° C., stir and keep the reaction for 10 h, and distill off the unreacted raw materials under reduced pressure;

[0076] (2) Add 260 g of isopropanol and 0.098 mol of allyl chloride to the above four-necked flask, heat under reflux for 36 h, and distill under reduced pressure to obtain a yellow-brown viscous solid;

[0077] (3) then recrystallizing the solid with ethyl acetate to obtain a solid which is an unsaturated quaternary phosphonium salt;

[0078] (4) In another flask, add the above-mentioned unsaturated quaternary phosphonium salt, 0.1 mol dodecyldimethylallylammonium chloride, 2.58 g OP-10, 1.47 g MS-1 and 104 g water, and heat to 52° C. while stirring. After all the solution is dissolved, add dropwise 7.3 g 12 wt % potassium persulfate solution and 7.3 g 6 wt % sodium sulfite solution. After the addition is complete, continue stirring for 2 h, heat to 70° C., and continue to react for 2 h to obtain a viscous liquid;

[0079] (5) Granulate the viscous liquid to obtain light yellow particles of 1-4 mm, thus obtaining polymer fungicide product D.

[0080] Embodiment 5:

[0081] (1) Add 0.1 mol of 2-cyclohexene-1-one to a four-necked flask equipped with a condenser under nitrogen protection, slowly dropwise add 50 ml of a 2 mol / L diethylphosphine isopropanol solution, and after the dropwise addition is complete, raise the temperature to 48° C., stir and keep the reaction for 8 h, and distill off the unreacted raw materials under reduced pressure;

[0082] (2) Add 130 g of ethanol, 130 g of isopropanol, and 0.1 mol of allyl bromide into the above four-necked flask, heat under reflux for 32 h, and distill under reduced pressure to obtain a yellow-brown viscous solid;

[0083] (3) then recrystallizing the solid with ethyl acetate to obtain a solid which is an unsaturated quaternary phosphonium salt;

[0084] (4) In another flask, add the above unsaturated quaternary phosphonium salt, 0.08 mol dodecyldimethylallylammonium chloride, 3.15 g OP-10, 1.09 g MS-1 and 96 g water, and heat to 53° C. while stirring. After all the solution is dissolved, add dropwise 7.3 g 12 wt % ammonium persulfate solution and 7.3 g 6 wt % sodium sulfite solution. After the addition is complete, continue stirring for 2 h, heat to 80° C., and continue reacting for 2 h to obtain a viscous liquid;

[0085] (5) Granulate the viscous liquid to obtain light yellow particles of 1-4 mm, thus obtaining polymer fungicide product E.

[0086] Example 6

[0087] (1) Add 0.1 mol of 2-cyclohexene-1-one to a four-necked flask equipped with a condenser under nitrogen protection, slowly dropwise add 55 ml of a 2 mol / L diethylphosphine isopropanol solution, and after the dropwise addition is complete, raise the temperature to 48° C., stir and keep the reaction for 8 h, and distill off the unreacted raw materials under reduced pressure;

[0088] (2) Add 150 g of ethanol, 110 g of isopropanol, and 0.11 mol (maximum 0.1) of propylene bromide into the above four-necked flask, heat under reflux for 32 h, and distill under reduced pressure to obtain a yellow-brown viscous solid;

[0089] (3) then recrystallizing the solid with ethyl acetate to obtain a solid which is an unsaturated quaternary phosphonium salt;

[0090] (4) In another flask, add the above-mentioned unsaturated quaternary phosphonium salt, 0.075 mol dodecyldimethylallylammonium chloride, 2.96 g OP-10, 1.09 g MS-1 and 86 g water, and heat to 53° C. while stirring. After all the solution is dissolved, add dropwise 7.3 g 11 wt % ammonium persulfate solution and 7.3 g 5.5 wt % sodium sulfite solution. After the addition is complete, continue stirring for 2 h, heat to 80° C., and continue to react for 2 h to obtain a viscous liquid;

[0091] (5) Granulate the viscous liquid to obtain light yellow particles of 1-4 mm, thus obtaining polymer fungicide product F.

[0092] Example 7

[0093] (1) Add 0.1 mol of 2-cyclohexene-1-one to a four-necked flask equipped with a condenser under nitrogen protection, slowly dropwise add 52 ml of a 2 mol / L diethylphosphine isopropanol solution, and after the dropwise addition is complete, raise the temperature to 48° C., stir and keep the reaction for 8 h, and distill off the unreacted raw materials under reduced pressure;

[0094] (2) Add 100 g of ethanol, 170 g of isopropanol, and 0.1 mol of propylene bromide into the above four-necked flask, heat under reflux for 36 h, and distill under reduced pressure to obtain a yellow-brown viscous solid;

[0095] (3) then recrystallizing the solid with ethyl acetate to obtain a solid which is an unsaturated quaternary phosphonium salt;

[0096] (4) In another flask, add the above-mentioned unsaturated quaternary phosphonium salt, 0.09 mol dodecyldimethylallylammonium chloride, 3.15 g OP-10, 1.59 g MS-1 and 86 g water, and heat to 53° C. while stirring. After all the solution is dissolved, add dropwise 8 g 11 wt % ammonium persulfate solution and 8 g 5.5 wt % sodium bisulfite solution. After the addition is complete, continue stirring for 1 h, heat to 80° C., and continue to react for 2 h to obtain a viscous liquid;

[0097] (5) Granulate the viscous liquid to obtain light yellow particles of 1-4 mm, thus obtaining the polymer fungicide product G.

[0098] Example 8

[0099] (1) Add 0.1 mol of 2-cyclohexene-1-one to a four-necked flask equipped with a condenser under nitrogen protection, slowly dropwise add 53 ml of a 2 mol / L diethylphosphine isopropanol solution, and after the dropwise addition is complete, raise the temperature to 48° C., stir and keep the reaction for 8 h, and distill off the unreacted raw materials under reduced pressure;

[0100] (2) Add 50 g of ethanol, 210 g of isopropanol, and 0.1 mol of allyl bromide into the above four-necked flask, heat under reflux for 32 h, and distill under reduced pressure to obtain a yellow-brown viscous solid;

[0101] (3) then recrystallizing the solid with ethyl acetate to obtain a solid which is an unsaturated quaternary phosphonium salt;

[0102] (4) In another flask, add the above unsaturated quaternary phosphonium salt, 0.085 mol dodecyldimethylallylammonium chloride, 2.33 g OP-10, 1.85 g MS-1 and 86 g water, and heat to 53° C. while stirring. After all the mixture is dissolved, add dropwise 8.2 g 10 wt % ammonium persulfate solution and 8.2 g 5 wt % sodium sulfite solution. After the addition is complete, continue stirring for 1 h, heat to 80° C., and continue reacting for 2 h to obtain a viscous liquid.

[0103] (5) Granulate the viscous liquid to obtain light yellow particles of 1-4 mm, thus obtaining the polymer fungicide product H.

[0104] Example 9 Indoor sterilization effect evaluation

[0105] Add 500ml of untreated water sample after oil-water separation from a joint station of Dongxin Oil Production Plant of Shengli Oilfield into a series of narrow-necked bottles, of which SRB (sulfate-reducing bacteria) content is 1100 / ml, TGB (saprophytic bacteria) content is 45 / ml, and FB (iron bacteria) content is 45 / ml. Add different concentrations of A, B, C, D, E, F, G, H and bactericide, shake well, place in a 52℃ oven, take samples after 1h, use the three-tube method MPN to detect the remaining bacterial content, and calculate the bactericidal rate. The SRB bactericidal results are shown in Table 1, the TGB bactericidal results are shown in Table 2, and the FB bactericidal results are shown in Table 3.

[0106] Table 1 SRB sterilization results (sterilization rate, %)

[0107] Concentration, mg / L 10 15 20 30 A 90 99.7 100 100 B 95.9 99.8 100 100 C 97.3 99.8 100 100 D 97.7 99.9 100 100 E 98.2 99.9 100 100 F 97.7 99.8 100 100 G 98.2 99.9 100 100 H 98.2 99.9 100 100 Dichlorophen 0 0 55.6 90 1227 0 72.73 90 99.93

[0108] From Table 1 we can see that:

[0109] The bactericide AH of the present invention has a sterilization rate of more than 90% on SRB when the concentration is 10 mg / L, and the highest rate is 98.2%; the bactericidal rate of SRB is 100% when the concentration is 20 mg / L or above; while the bactericidal rates of dichlorophen and 1227 on SRB are 0 and 0 respectively when the concentration is 10 mg / L, and 55.6% and 90% respectively when the concentration is 20 mg / L. Compared with the existing bactericides, the bactericidal effect of the present invention on SRB is good.

[0110] Table 2 TGB sterilization results (sterilization rate, %)

[0111]

[0112]

[0113] From Table 2 we can see that:

[0114] The bactericide AH of the present invention has a bactericidal rate of more than 94.5% on TGB when the concentration is 10 mg / L, and the highest is 99.3%; the bactericidal rate of TGB is 100% when the concentration is 20 mg / L or above; while the bactericidal rates of dichlorophen and 1227 on TGB are 0 and 0 respectively when the concentration is 10 mg / L, and 64.4% and 97.6% respectively when the concentration is 20 mg / L. Compared with the existing bactericides, the bactericidal effect of the present invention on TGB is good.

[0115] Table 3FB sterilization results (sterilization rate, %)

[0116]

[0117]

[0118] From Table 3 we can see that:

[0119] The bactericide AH of the present invention has a bactericidal rate of more than 97% on FB when the concentration is 10 mg / L, and the highest is 99.3%; the bactericidal rate of FB is 100% when the concentration is 20 mg / L or above; while the bactericidal rates of dichlorophen and 1227 on FB are 0 and 72.7% respectively when the concentration is 10 mg / L, and are 90% and 100% respectively when the concentration is 20 mg / L.

[0120] Example 10 Evaluation of indoor flocculation effect

[0121] The oily wastewater evaluated indoors is produced water from a block of Binnan Oil Production Plant in Shengli Oilfield, with a suspended matter content of 86 mg / L. The suspended matter removal rate test method refers to the "QSH 1020

[0122] 1356-2016 General Technical Requirements for Flocculants for Conventional Produced Water Treatment in Oilfields”, and the test results are shown in Table 4.

[0123] Table 4 Flocculation effect (flocculation rate, %)

[0124]

[0125]

[0126] From Table 4 we can see that:

[0127] The flocculation rate of the fungicide AH of the present invention reaches more than 85% when the concentration is 10 mg / L, and the highest reaches 89.4%, while the flocculation rate of the comparative example PAC is 66.6%, which is significantly lower than that of the present invention.

[0128] Example 11 Field Application

[0129] A field test was carried out at a joint station of Gudao Oil Production Plant, with a treatment scale of 100m 3 / d, the inlet water SRB (sulfate reducing bacteria) content is 45 / ml, TGB (saprophytic bacteria) content is 11 / ml, FB (iron bacteria) content is 11 / ml, and the suspended matter content is 89mg / L. The oily sewage from the joint station is treated by using the E of the present invention. The dosage of E is 15kg / d, and the dosage concentration is 15mg / L. After treatment, the SRB, TGB, and FB contents are all 0, and the sterilization rate is 100%; the suspended matter content is 6.8mg / L, and the flocculation rate is 92.6%. The field test effect is good.

[0130] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for synthesizing a polymer bactericide for oilfield reinjection water, characterized in that: The synthesis method comprises: under nitrogen protection and in the presence of an organic solvent, 2-cyclohexene-1-one and a secondary phosphine undergo an addition reaction to obtain a tertiary phosphine; secondly, in the presence of a solvent and under reflux, the tertiary phosphine and a halogenated propylene undergo a quaternization reaction to obtain an unsaturated quaternary phosphonium salt; and finally, under the action of an initiator and a reducing agent, the unsaturated quaternary phosphonium salt and an unsaturated quaternary ammonium salt undergo a polymerization reaction.

2. The method for synthesizing a polymer bactericide for oilfield reinjection water according to claim 1, characterized in that: Based on 1 mole of 2-cyclohexene-1-one, the usage of the secondary phosphine, halogenated propylene and unsaturated quaternary ammonium salt are 0.9-1.2 mole, 0.9-1 mole and 0.5-2 mole respectively.

3. A method for synthesizing a polymer bactericide for oilfield reinjection water as claimed in claim 2, characterized in that: Based on 1 mole of 2-cyclohexene-1-one, the usage of the secondary phosphine, halogenated propylene and unsaturated quaternary ammonium salt are 0.95-1.1 mole, 0.95-1 mole and 0.5-1.5 mole respectively.

4. The method for synthesizing a polymer bactericide for oilfield reinjection water according to claim 1, characterized in that: The organic solvent is ethanol or isopropanol.

5. The method for synthesizing a polymer bactericide for oilfield reinjection water according to claim 1, characterized in that: The addition reaction time is 6-12 hours, and the temperature is 45-50°C.

6. A method for synthesizing a polymer bactericide for oilfield reinjection water as claimed in claim 5, characterized in that: The addition reaction time is 6-10 hours, and the temperature is 45-48°C.

7. The method for synthesizing a polymer bactericide for oilfield reinjection water as claimed in claim 1, characterized in that: The solvent is one or more of methanol, ethanol, propanol, butanol and isopropanol.

8. A method for synthesizing a polymer bactericide for oilfield reinjection water as claimed in claim 7, characterized in that: The solvent is ethanol, isopropanol or a mixture of the two in any ratio.

9. The method for synthesizing a polymer bactericide for oilfield reinjection water according to claim 1, characterized in that: The mass ratio of the solvent to 2-cyclohexene-1-one is 20-30:

1.

10. The method for synthesizing a polymer bactericide for oilfield reinjection water according to claim 1, characterized in that: The quaternization reaction time is 24-48 hours.

11. A method for synthesizing a polymer bactericide for oilfield reinjection water as claimed in claim 10, characterized in that: The quaternization reaction time is 32-42 hours.

12. The method for synthesizing a polymer bactericide for oilfield reinjection water according to claim 1, characterized in that: The initiator is one of sodium persulfate, potassium persulfate and ammonium persulfate, and the mass concentration of the initiator solution is 10-20%.

13. A method for synthesizing a polymer bactericide for oilfield reinjection water as claimed in claim 1, characterized in that: The weight ratio of the initiator solution to 2-cyclohexene-1-one is 0.5-1:

1.

14. The method for synthesizing a polymer bactericide for oilfield reinjection water according to claim 1, characterized in that: The reducing agent is sodium sulfite or potassium sulfite, and the mass concentration of the reducing agent solution is 5-10%.

15. The method for synthesizing a polymer bactericide for oilfield reinjection water according to claim 1, characterized in that: The weight ratio of the reducing agent solution to 2-cyclohexene-1-one is 0.5-1:

1.

16. A method for synthesizing a polymer bactericide for oilfield reinjection water as claimed in claim 1, characterized in that: The polymerization reaction temperature is 50-80°C and the reaction time is 2-5h.

17. A method for synthesizing a polymer bactericide for oilfield reinjection water as claimed in claim 16, characterized in that: The polymerization reaction includes two stages carried out sequentially, the reaction temperature of the first stage is 50-55°C and the time is 1-3h, and the reaction temperature of the second stage is 70-80°C and the time is 1-2h.

18. A polymer fungicide for oilfield reinjection water, characterized in that: The molecular structure of the bactericide is as follows: Where: m = 50-1000, n = 50-1000, R 1 is a C1-C4 alkyl group, R 2 C1-C 18 wherein X is one of chlorine, bromine and iodine, and Y is chlorine or bromine.

19. The polymer fungicide for oilfield reinjection water according to claim 18, characterized in that: Said m=100-500, n=100-500.

20. The polymer fungicide for oilfield reinjection water according to claim 18, characterized in that: The R 2 C1-C 12 of alkyl.

21. The polymer fungicide for oilfield reinjection water according to claim 20, characterized in that: The R 2 C6-C 10 of normal alkyl.

22. The polymer fungicide for oilfield reinjection water according to claim 18, characterized in that: The X is chlorine or bromine.

23. Use of the polymer fungicide for oilfield reinjection water as claimed in any one of claims 18 to 22 in oilfield wastewater treatment.

24. The use according to claim 23, characterized in that The application is application in oilfield reinjection water treatment.

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