CN114805672B - Degradable temporary plugging agent for oil-gas well as synthetic method and application thereof - Google Patents
Degradable temporary plugging agent for oil-gas well as synthetic method and application thereof Download PDFInfo
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Abstract
The invention discloses a degradable temporary plugging agent for an oil-gas well as a synthesis method and application thereof. The method comprises the following steps: adding tributyl phosphine, 1, 4-dichloro-2-butene, isopropanol and p-hydroxyanisole into a first reactor 1, replacing air in the reactor with nitrogen, and stirring for dissolving to obtain a solution; distilling the solution under reduced pressure, recrystallizing, and making solid; purging the 2 nd reactor by nitrogen, sequentially adding butenyl tributyl dichloro bis-quaternary phosphonium salt, naphthyl methacrylate, 3- (2-amino-5-bromo-3- (trifluoromethyl) phenyl) methyl acrylate, 3- [ (3-acrylamidopropyl) dimethyl ammonium ] propionate and bisphenol A glycerol diacrylate, stirring to obtain an emulsion, and adjusting the pH value; and (3) dropwise adding an initiator and a reducing agent solution, heating, and reacting to obtain the degradable temporary plugging agent. The temporary plugging agent has the advantages of simple synthesis method, no by-product, large water absorption capacity, strong anti-shearing capability, automatic plugging removal and the like.
Description
Technical Field
The invention belongs to the technical field of tertiary oil recovery, relates to a high molecular polymer and a preparation method thereof, and particularly relates to a degradable temporary plugging agent for an oil-gas well as a synthesis method and application thereof.
Background
In the middle and later stages of oil field development, excessive water production of an oil well is one of the serious problems in oil field development, the average water content of the oil field reaches over 80 percent, the water content of some old oil fields in the east reaches over 90 percent, high water content brings many hazards to oil field development and production, difficulty is increased for secondary and tertiary development of low-permeability and ultra-low-permeability oil wells, and an effective and economic water plugging scheme is very important to select.
The temporary plugging agent is a chemical agent with temporary plugging effect and is used for protecting a non-target layer from being damaged by operation in the oil-water well operation. In the construction process, the temporary plugging agent is added into the stratum in real time, particles enter the stratum according to the principle that fluid flows towards the direction with the minimum resistance, a filter cake bridging crack or a high permeable layer which is higher than the fracture pressure and is generated in a high permeable zone can be formed, so that subsequent working fluid cannot enter the crack and the high permeable zone, and then the fracturing fluid enters a high stress zone or a pressure difference value promotes the generation of a new crack.
The performance of the temporary plugging agent is directly related to the later-stage yield of the oil-gas well, and if the temporary plugging agent cannot be degraded quickly, the temporary plugging agent is filled between propping agents for a long time, so that the normal permeation of oil gas is prevented, and the yield is reduced. The temporary plugging agent realizes self-degradation after construction is finished, and has no pollution, self-cleaning and little formation damage. CN112920327A discloses a preparation method of a temporary plugging agent, which comprises the following steps: A) mixing acrylamide and sodium alginate in water, sequentially adding a cross-linking agent and an initiator, and carrying out polymerization reaction to obtain sodium alginate/acrylamide hydrogel; the cross-linking agent is one or more of N, N-methylene bisacrylamide, N' -diallyl tartaric acid diamide, divinylbenzene, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate; the mass ratio of the acrylamide to the cross-linking agent is 100: (0.01 to 1); B) and B) soaking the sodium alginate/acrylamide hydrogel obtained in the step A) in a zirconium salt solution, and drying to obtain the temporary plugging agent. The temporary plugging agent can effectively reduce the expansion multiple of the temporary plugging agent; and the temporary plugging agent after swelling has higher toughness and strength, and can realize better plugging effect on cracks. However, the temporary plugging agent is difficult to realize self-degradation in the later period, secondary construction is needed, and the workload is increased for the site.
CN112457450A discloses an amphoteric temporary plugging agent and a preparation method thereof, wherein the raw materials for preparing the amphoteric temporary plugging agent comprise the following components in parts by weight: 50-60 parts of deionized water; 20-30 parts of zwitterionic polymer; 0.5-1 part of zwitterionic crosslinking agent; 0.3-0.5 part of zwitterionic initiator by weight; 10-20 parts of carboxymethyl cellulose. The main raw materials of the amphoteric temporary plugging agent prepared by the method are industrial products, the cost is low, the amphoteric temporary plugging agent can be widely used in operation, and meanwhile, after temporary plugging is completed, smooth flowback is realized by utilizing the molecular structure of a polymer to be matched with a flowback technology, so that the amphoteric temporary plugging agent has low damage to a stratum. However, the product of the temporary plugging agent after degradation has higher oil-water interfacial tension, which is not beneficial to later flowback.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a degradable temporary plugging agent for an oil-gas well as a synthesis method and application thereof. The temporary plugging agent has the advantages of simple synthesis method, no by-product, large water absorption capacity, high strength, strong shear resistance, automatic plugging removal and the like.
In order to achieve the above object:
the invention discloses a method for synthesizing a degradable temporary plugging agent for an oil-gas well, which comprises the following steps:
(1) adding tributyl phosphine, 1, 4-dichloro-2-butene, isopropanol and p-hydroxyanisole into a reactor 1, introducing nitrogen, displacing air in the reactor, stirring for dissolving, heating, refluxing and preserving heat to obtain a butenyl tributyl dichloro bis-quaternary phosphonium salt solution;
(2) distilling the solution under reduced pressure to dryness to obtain viscous brown solid, recrystallizing with ethyl acetate, and oven drying at 90-100 deg.C to obtain butenyl tributyl dichloro bis-quaternary phosphonium salt solid;
(3) purging the reactor 2 for 2-3min by nitrogen, sequentially adding the butenyl tributyl dichloro bis-quaternary phosphonium salt, naphthyl methacrylate, 3- (2-amino-5-bromo-3- (trifluoromethyl) phenyl) methyl acrylate, 3- [ (3-acrylamidopropyl) dimethyl ammonium ] propionate, bisphenol A glycerol diacrylate, nonylphenol polyoxyethylene ether, alkylphenol ether sodium sulfosuccinate and water, ensuring micro-positive pressure by nitrogen, starting stirring until all raw materials are completely uniform emulsion, and adjusting the pH to 6-7 by using 10wt% of sodium hydroxide solution;
(4) heating the emulsion to 40-45 ℃, slowly dripping an initiator solution in an elevated tank, dripping a reducing agent solution, heating the reaction in the dripping process, automatically increasing the temperature, heating to 60-65 ℃ after finishing dripping, continuously stirring for 2-3h, and carrying out polymerization reaction to form a high-viscosity polymer, namely the degradable temporary plugging agent.
In the present invention, it is preferable that the 1, 4-dichloro-2-butene, naphthyl methacrylate, methyl 3- (2-amino-5-bromo-3- (trifluoromethyl) phenyl) acrylate, 3- [ (3-acrylamidopropyl) dimethylammonium ] propionate, and bisphenol a glycerol diacrylate are used in amounts of 0.5 to 0.55 parts by mole, 0.2 to 2 parts by mole, 0.5 to 5 parts by mole, 0.2 to 2 parts by mole, and 0.5 to 5 parts by mole, respectively, based on 1 part by mole of tributylphosphine.
Preferably, in the step (1), the weight ratio of the isopropanol, the p-hydroxyanisole and the tributylphosphine is 10-20: 0.001-0.002: 1.
preferably, in the step (1), the reflux heat preservation time is 24-48 h; more preferably, the reflux incubation time is 32-40 h.
In the present invention, preferably, in step (3), the weight ratio of nonylphenol polyoxyethylene ether, sodium alkylphenol ether sulfosuccinate, water and tributylphosphine is 0.5-2: 0.2-0.5: 40-60: 1.
in the invention, preferably, in the step (4), the initiator is one of potassium persulfate, ammonium persulfate and sodium persulfate; more preferably potassium or ammonium persulfate.
Preferably, in the step (4), the weight ratio of the initiator solution to tributylphosphine is 2-4: 1, the mass concentration of the initiator solution is 5-10%.
In the present invention, preferably, in step (4), the reducing agent is sodium sulfite or sodium thiosulfate.
Preferably, in the step (4), the weight ratio of the reducing agent solution to tributylphosphine is 3-5: 1, the mass concentration of the reducing agent solution is 3-5%.
The invention also discloses a degradable temporary plugging agent prepared by the synthesis method, wherein the molecular structural formula of the degradable temporary plugging agent is as follows:
wherein:
a=200-5000；
b=50-1000；
c=200-5000；
d=50-1000；
e=50-1000；
f=200-5000；
g=50-1000；
h=200-5000；
i=50-1000；
j=50-1000。
the molecular weight of the degradable temporary plugging agent is 500000-10000000.
The reaction equation of the synthesis of the degradable temporary plugging agent is as follows:
the third purpose of the invention discloses the application of the degradable temporary plugging agent in oil and gas wells, in particular the application in oil and gas well fracturing. The specific application is not particularly required, and can be a conventional application mode in the field, and the detailed description is not repeated.
The invention relates to a water-phase five-membered high polymer which takes butenyl tributyl dichloro bis-quaternary phosphonium salt, naphthyl methacrylate, 3- (2-amino-5-bromo-3- (trifluoromethyl) phenyl) methyl acrylate and 3- [ (3-acrylamidopropyl) dimethyl ammonium ] propionate as polymer raw materials and takes bisphenol A glycerol diacrylic acid as a cross-linking agent. The acrylic acid, the amide and other groups have better water absorption, and the volume of the product can be increased after water absorption, so that the blocking spread volume is increased; the naphthalene ring and the benzene ring have stable structures, so that the hardness of the product can be improved, and the shear resistance of the temporary plugging agent can be improved; quaternary ammonium salt, quaternary phosphonium salt and carboxylate are good surfactants, which are beneficial to improving the blocking rate by infiltrating a hydrophobic section of a stratum, fluorine surfactants are introduced into molecules, so that the surface tension and the interfacial tension are greatly reduced, the wettability and the permeability are improved, the whole molecules can be seamlessly connected with the surface of a rock, and the blocking rate is greatly improved; nonylphenol polyoxyethylene ether and alkylphenol ether sodium sulfosuccinate are typical nonionic and anionic surfactants, so that the polymerization quality and uniformity can be improved, the molecular weight of a polymer is increased, the hydrophobic section of a infiltrated stratum is favorably improved, the blockage rate is favorably improved, and flowback blockage removal after temporary blockage construction is favorably realized; the bisphenol A glycerol diacrylate belongs to a cross-linking agent, the whole molecule can be changed into a two-dimensional and three-dimensional network structure from a one-dimensional linear structure, the outer layer of the whole molecule is hydrophobic, the flow resistance of water is increased, the blocking capacity is improved, the inner layer is in close contact with rocks, the blocking rate is improved, the molecular weight is greatly increased due to the two-dimensional and three-dimensional structures, the swept volume is increased, and the blocking capacity of the molecule is improved. In addition, a plurality of monomers contain acrylate, can be hydrolyzed at high temperature, and the degradation time of molecules is controlled by adjusting the adding amount of the acrylate.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the temporary plugging agent is synthesized by a one-pot method, the raw materials are easy to obtain, the synthesis process is simple, and no by-product is generated;
(2) the temporary plugging agent can control the degradation time by adjusting the proportion of the raw material formula, the degradation time is controlled to be 10-66h, and the construction process is simple;
(3) the blockage rate and the permeability recovery rate of the invention are high and both reach more than 99 percent.
Drawings
FIG. 1 shows a temporary plugging agent H according to the present invention 2 Red of (D)An external spectrum.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
Example 1
(1) Adding 1mol of tributyl phosphine, 0.55mol of 1, 4-dichloro-2-butene, 2020g of isopropanol and 0.2g of p-hydroxyanisole into a 1 st reactor, introducing nitrogen, displacing air in the reactor, stirring for dissolving, heating, refluxing and preserving heat for 24 hours to obtain a butenyl tributyl bis-quaternary phosphonium chloride solution;
(2) distilling the solution under reduced pressure to dryness to obtain viscous brown solid, recrystallizing with ethyl acetate, and oven drying at 90 deg.C to obtain butenyl tributyl dichloro bis-quaternary phosphonium salt solid;
(3) purging the 2 nd reactor with nitrogen for 2min, sequentially adding the butenyl tributyl dichloro bis-quaternary phosphonium salt, 2mol of naphthyl methacrylate, 5mol of 3- (2-amino-5-bromo-3- (trifluoromethyl) phenyl) methyl acrylate, 2mol of 3- [ (3-acrylamidopropyl) dimethyl ammonium ] propionate, 0.5mol of bisphenol A glycerol diacrylate, 125g of nonylphenol polyoxyethylene ether, 74g of sodium alkylphenol ether sulfosuccinate, 8080g of water, ensuring micro-positive pressure by nitrogen, starting stirring until all raw materials are completely uniform emulsion, and adjusting the pH value with 10wt% of sodium hydroxide solution to 6-7;
(4) heating the emulsion to 40 ℃, slowly dropwise adding 404g of 10wt% ammonium persulfate solution into an overhead tank, simultaneously dropwise adding 606g of 5wt% sodium sulfite solution, heating to 60 ℃ after the dropwise adding process, continuously stirring for 2.5 hours, and carrying out polymerization reaction to form a high-viscosity polymer, namely the degradable temporary plugging agent H 1 。
Example 2
(1) Adding 1mol of tributyl phosphine, 0.5mol of 1, 4-dichloro-2-butene, 3000g of isopropanol and 0.25g of p-hydroxyanisole into a 1 st reactor, introducing nitrogen, displacing air in the reactor, stirring for dissolving, heating, refluxing and preserving heat for 48 hours to obtain a butenyl tributyl dichloro bis-quaternary phosphonium salt solution;
(2) distilling the solution under reduced pressure to dryness to obtain viscous brown solid, recrystallizing with ethyl acetate, and drying at 100 deg.C to obtain butenyl tributyl dichloride bis-quaternary phosphonium salt solid;
(3) purging the 2 nd reactor for 2min by using nitrogen, sequentially adding the butenyl tributyl dichloride bis-quaternary phosphonium salt, 0.2mol of naphthyl methacrylate, 0.5mol of 3- (2-amino-5-bromo-3- (trifluoromethyl) phenyl) methyl acrylate, 0.2mol of 3- [ (3-acrylamidopropyl) dimethyl ammonium ] propionate, 5mol of bisphenol A glycerol diacrylate, 101g of nonylphenol polyoxyethylene ether, 101g of alkylphenol ether sodium sulfosuccinate and 12120g of water, ensuring micro-positive pressure by using nitrogen, starting stirring until all raw materials are completely uniform emulsion, and adjusting the pH to 6-7 by using 10wt% of sodium hydroxide solution;
(4) heating the emulsion to 45 ℃, slowly dropwise adding 520g of 5wt% ammonium persulfate solution into the elevated tank, simultaneously dropwise adding 720g of 3wt% sodium sulfite solution, heating to 62 ℃ after the dropwise adding process, continuously stirring for 3H, and carrying out polymerization reaction to form a high-viscosity polymer, namely the degradable temporary plugging agent H 2 。
Example 3
(1) Adding 1mol of tributyl phosphine, 0.52mol of 1, 4-dichloro-2-butene, 2890g of isopropanol and 0.3g of p-hydroxyanisole into a 1 st reactor, introducing nitrogen, displacing air in the reactor, stirring for dissolving, heating, and carrying out reflux heat preservation for 30 hours to obtain a butenyl tributyl dichloro bis-quaternary phosphonium salt solution;
(2) distilling the solution under reduced pressure to dryness to obtain viscous brown solid, recrystallizing with ethyl acetate, and oven drying at 100 deg.C to obtain butenyl tributyl dichloro bis-quaternary phosphonium salt solid;
(3) purging the reactor 2 for 2min by nitrogen, sequentially adding the butenyl tributyl dichloro bis-quaternary phosphonium salt, 2mol of naphthyl methacrylate, 2mol of 3- (2-amino-5-bromo-3- (trifluoromethyl) phenyl) methyl acrylate, 2mol of 3- [ (3-acrylamidopropyl) dimethyl ammonium ] propionate, 2mol of bisphenol A glycerol diacrylate, 188g of nonylphenol polyoxyethylene ether, 40.4g of alkylphenol ether sodium sulfosuccinate and 11010g of water, starting stirring until all raw materials are completely uniform under the micro-positive pressure, and adjusting the pH value to 6-7 by using 10wt% of sodium hydroxide solution;
(4) heating the emulsion to 42 ℃, slowly dropwise adding 725g of 9wt% potassium persulfate solution into the elevated tank, simultaneously dropwise adding 860g of 4wt% sodium sulfite solution, heating to 63 ℃ in the dropwise adding process, continuously stirring for 2 hours, and performing polymerization reaction to form a high-viscosity polymer, namely the degradable temporary plugging agent H 3 。
Example 4
(1) Adding 1mol of tributyl phosphine, 0.53mol of 1, 4-dichloro-2-butene, 3020g of isopropanol and 0.32g of p-hydroxyanisole into a 1 st reactor, introducing nitrogen, displacing air in the reactor, stirring for dissolving, heating, and carrying out reflux heat preservation for 40h to obtain a butenyl tributyl dichloro bis-quaternary phosphonium salt solution;
(2) distilling the solution under reduced pressure to dryness to obtain viscous brown solid, recrystallizing with ethyl acetate, and oven drying at 95 deg.C to obtain butenyl tributyl dichloro bis-quaternary phosphonium salt solid;
(3) purging the reactor 2 for 3min by nitrogen, sequentially adding the butenyl tributyl dichloro bis-quaternary phosphonium salt, 1.0mol of naphthyl methacrylate, 3mol of 3- (2-amino-5-bromo-3- (trifluoromethyl) phenyl) methyl acrylate, 0.8mol of 3- [ (3-acrylamidopropyl) dimethyl ammonium ] propionate, 3mol of bisphenol A glycerol diacrylate, 285g of nonylphenol polyoxyethylene ether, 75g of sodium alkylphenol ether sulfosuccinate and 7860g of water, starting stirring until all raw materials are completely uniform emulsion, and adjusting the pH value to 6-7 by using 10wt% of sodium hydroxide solution;
(4) heating the emulsion to 43 ℃, slowly dropwise adding 668g of 8wt% potassium persulfate solution into the elevated tank, and simultaneously dropwise adding 1010g of 5wt% sodium thiosulfate solution into the elevated tankIn the adding process, the reaction releases heat, the temperature is automatically increased, simultaneously, after the dropwise adding is finished, the temperature is increased to 65 ℃, the stirring is continued for 2 hours, and the high-viscosity polymer formed by the polymerization reaction is the degradable temporary plugging agent H 4 。
Example 5
(1) Adding 1mol of tributyl phosphine, 0.50mol of 1, 4-dichloro-2-butene, 3580g of isopropanol and 0.4g of p-hydroxyanisole into a 1 st reactor, introducing nitrogen, displacing air in the reactor, stirring for dissolving, heating, and carrying out reflux heat preservation for 36 hours to obtain a butenyl tributyl dichloro bis-quaternary phosphonium salt solution;
(2) distilling the solution under reduced pressure to dryness to obtain viscous brown solid, recrystallizing with ethyl acetate, and oven drying at 98 deg.C to obtain butenyl tributyl dichloro bis-quaternary phosphonium salt solid;
(3) purging the reactor 2 for 3min by nitrogen, sequentially adding the butenyl tributyl dichloro bis-quaternary phosphonium salt, 1.5mol of naphthyl methacrylate, 2.5mol of 3- (2-amino-5-bromo-3- (trifluoromethyl) phenyl) methyl acrylate, 1.2mol of 3- [ (3-acrylamidopropyl) dimethyl ammonium ] propionate, 1mol of bisphenol A glycerol diacrylate, 404g of nonylphenol polyoxyethylene ether, 80g of sodium alkylphenol ether sulfosuccinate and 9000g of water, ensuring micro-positive pressure by nitrogen, starting stirring until all raw materials are completely uniform emulsion, and adjusting the pH to 6-7 by using 10wt% of sodium hydroxide solution;
(4) heating the emulsion to 42 ℃, slowly dropwise adding 560g of 6wt% sodium persulfate solution into the elevated tank, simultaneously dropwise adding 850g of 3wt% sodium thiosulfate solution, heating to 62 ℃ in the dropwise adding process, continuously stirring for 3H after the dropwise adding is finished, and performing polymerization reaction to form a high-viscosity polymer, namely the degradable temporary plugging agent H 5 。
Example 6
(1) Adding 1mol of tributylphosphine, 0.54mol of 1, 4-dichloro-2-butene, 4040g of isopropanol and 0.35g of p-hydroxyanisole into a 1 st reactor, introducing nitrogen, displacing air in the reactor, stirring for dissolving, heating, and carrying out reflux heat preservation for 36 hours to obtain a butenyl tributyl dichloro bis-quaternary phosphonium salt solution;
(2) distilling the solution under reduced pressure to dryness to obtain viscous brown solid, recrystallizing with ethyl acetate, and oven drying at 92 deg.C to obtain butenyl tributyl dichloro bis-quaternary phosphonium salt solid;
(3) purging the reactor 2 for 3min by nitrogen, sequentially adding the butenyl tributyl dichloro bis-quaternary phosphonium salt, 1.2mol of naphthyl methacrylate, 2mol of 3- (2-amino-5-bromo-3- (trifluoromethyl) phenyl) methyl acrylate, 1mol of 3- [ (3-acrylamidopropyl) dimethyl ammonium ] propionate, 4mol of bisphenol A glycerol diacrylate, 320g of nonylphenol polyoxyethylene ether, 65g of alkylphenol ether sodium sulfosuccinate and 9500g of water, starting stirring until all raw materials are completely uniform under the micro-positive pressure, and adjusting the pH value to 6-7 by using 10wt% of sodium hydroxide solution;
(4) heating the emulsion to 45 ℃, slowly dropwise adding 808g of 7wt% sodium persulfate solution into an elevated tank, simultaneously dropwise adding 913g of 4wt% sodium thiosulfate solution, heating to 64 ℃ in the dropwise adding process, continuously stirring for 2 hours, and carrying out polymerization reaction to form a high-viscosity polymer, namely the degradable temporary plugging agent H 6 。
Test example 1 measurement of expansion factor
Adding 100000mg/L of sodium chloride solution into a series of pressure-resistant wide-mouth bottles respectively, heating the wide-mouth bottles to 90 ℃ in an oil bath, adding a temporary plugging agent, heating the wide-mouth bottles to 90 ℃ in the oil bath, taking out the glass bottles at intervals, pouring the temporary plugging agent into a standard sieve for filtering, putting the filtered water back into the wide-mouth bottles, quickly weighing the mass of the temporary plugging agent, putting the temporary plugging agent back into the wide-mouth bottles, keeping the temperature constant at 90 ℃, calculating the expansion multiple n, and obtaining a test result shown in table 1.
n=m 1 /m 0
In the formula (I), the compound is shown in the specification,
n: expansion times;
m 1 : mass, g, of the temporary plugging agent after expansion;
m 0 : mass of temporary plugging agent, g.
TABLE 1 test results of expansion factor at different times
As can be seen from table 1: temporary plugging agent H 1 -H 6 The expansion times at different times are different, the expansion times are increased along with the extension of time, the expansion times are more than 10 times at 15min, and the expansion times of PLA are 5.9 times; the expansion multiple is more than 20 times at 60min, and the expansion multiple of PLA is 11.8 times; the expansion factor at 150min is greater than 24 times, while the expansion factor of PLA is 13.5 times. The expansion times of the temporary plugging agent PLA are obviously lower than that of the temporary plugging agent of the invention, and the difference of the expansion times is more obvious along with the extension of time.
Test example 2 determination of degradation time
After the test of the test example 1 is continuously performed for 150min, the temporary plugging agent basically does not absorb water any more, the temporary plugging agent is continuously placed in a wide-mouth bottle, after a period of time, the temporary plugging agent is gradually dissolved, the time after the temporary plugging agent is completely dissolved is the degradation time of the temporary plugging agent, and the test results are shown in table 2.
TABLE 2 test results of degradation time, surface tension, temporary plugging rate, and permeability recovery rate
As can be seen from Table 2, there is a significant difference in the degradation time of the temporary plugging agent, the longest H 1 66H, shortest H 2 Is 10 h. The more bisphenol A glycerol diacrylate is added, the easier it is to dissolve and the shorter the degradation time, and vice versa.
Therefore, the degradation time can be determined according to the construction operation requirement when the temporary plugging agent is applied on site, so that the proportion of the bisphenol A glycerol diacrylic acid of the temporary plugging agent can be selected, and the degradation time of the temporary plugging agent can be controlled between 10 and 66 hours.
Test example 3 measurement of surface tension
After the samples in test example 2 were completely degraded, the surface tension of the solution was measured by a ring pulling method, and the results are shown in table 2.
As can be seen from table 2: temporary plugging agent H 1 -H 6 The surface tension is less than 25mN/m, the PLA surface tension is 40.2mN/m, and the temporary plug is used for temporary pluggingThe agent surface tension is significantly lower than commercially available PLA.
Test example 4 determination of temporary plugging Rate and Permeability recovery
The temporary plugging rate and the permeability recovery rate are tested by referring to Q/SH 10202187-2018 Universal technical Condition of Water-soluble temporary plugging agent, and the test results are shown in Table 2.
As can be seen from table 2: temporary plugging agent H 1 -H 6 The temporary plugging rate is more than 99 percent, wherein H 1 、H 5 、H 6 The temporary plugging rate reaches 100% at most, and the temporary plugging rate of PLA is 92.8%; temporary plugging agent H 1 -H 6 The permeability recovery rates of the composite are all more than 99 percent, wherein H 1 、H 4 、H 5 The highest permeability recovery rate of the PLA reaches 100 percent, and the permeability recovery rate of the PLA is 91.2 percent. The temporary plugging rate and the permeability recovery rate of the temporary plugging agent are obviously higher than those of the temporary plugging agent PLA. The temporary plugging agent has good temporary plugging and deblocking effects.
Test example 5 test of blocking Strength
At 90 ℃, manually constructing a sealing rock core by adopting different permeability, squeezing 1PV 10g/L of temporary plugging agent concentration, and testing the sealing strength of the sealing agent, wherein the test results are shown in a table 3.
Table 3 core plugging strength test results for different permeabilities
As can be seen from table 3:
(1) for low permeability cores, temporary plugging agent H 1 -H 6 The plugging strength of (2) is more than 70MPa, wherein H 1 The highest pressure can reach 80.2MPa, and the plugging strength of PLA is 5.2MPa, which is obviously lower than that of the invention;
(2) for highly permeable cores, temporary plugging agent H 1 -H 6 The plugging strength of (A) is more than 50MPa, wherein H 6 The highest reaches 63.7MPa, and the plugging strength of PLA is 4.7MPa, which is obviously lower than that of the invention.
Test example 6 Infrared Spectroscopy characterization
Product H by infrared spectroscopy 2 The characterization was performed and the results are shown in fig. 1.
As can be seen from FIG. 1, 3480cm -1 Is in an amide
The stretching vibration absorption peak of (1); 1680cm -1 Is in an amide
A key expansion vibration absorption peak; 1590cm -1 Is in an amide
A bending vibration absorption peak of (2); 1416cm -1 Is in an amide
The stretching vibration absorption peak of (1); 1210cm -1 Is in an amide
The stretching vibration absorption peak of (1); 1108cm -1 Is in phenol
The stretching vibration absorption peak of (1); 1010cm -1 Is that
The stretching vibration absorption peak of (1); 975cm -1 Is in quaternary ammonium salt
A key expansion vibration absorption peak.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (8)
1. A synthetic method of a degradable temporary plugging agent for an oil-gas well comprises the following steps:
(1) adding tributyl phosphine, 1, 4-dichloro-2-butene, isopropanol and p-hydroxyanisole into a reactor 1, introducing nitrogen, displacing air in the reactor, stirring for dissolving, heating, refluxing and preserving heat to obtain a butenyl tributyl dichloro bis-quaternary phosphonium salt solution;
(2) distilling the solution under reduced pressure to dryness to obtain viscous brown solid, recrystallizing with ethyl acetate, and oven drying at 90-100 deg.C to obtain butenyl tributyl dichloride bis-quaternary phosphonium salt solid;
(3) purging the reactor 2 for 2-3min by nitrogen, sequentially adding the butenyl tributyl dichloro bis-quaternary phosphonium salt, naphthyl methacrylate, 3- (2-amino-5-bromo-3- (trifluoromethyl) phenyl) methyl acrylate, 3- [ (3-acrylamidopropyl) dimethyl ammonium ] propionate, bisphenol A glycerol diacrylate, nonylphenol polyoxyethylene ether, alkylphenol ether sodium sulfosuccinate and water, ensuring micro-positive pressure by nitrogen, starting stirring until all raw materials are completely uniform emulsion, and adjusting the pH to 6-7 by using 10wt% of sodium hydroxide solution;
(4) heating the emulsion to 40-45 ℃, slowly dripping an initiator solution into the head tank, dripping a reducing agent solution into the head tank, reacting to release heat in the dripping process, automatically increasing the temperature, heating to 60-65 ℃ after dripping, continuously stirring for 2-3 hours, and carrying out polymerization reaction to form a high-viscosity polymer, namely the degradable temporary plugging agent;
the 1, 4-dichloro-2-butene, the naphthyl methacrylate, the methyl 3- (2-amino-5-bromo-3- (trifluoromethyl) phenyl) acrylate, the 3- [ (3-acrylamidopropyl) dimethylammonium ] propionate and the bisphenol A glycerol diacrylate are used in an amount of 0.5 to 0.55 parts by mole, 0.2 to 2 parts by mole, 0.5 to 5 parts by mole, 0.2 to 2 parts by mole and 0.5 to 5 parts by mole, respectively, based on 1 part by mole of tributylphosphine.
2. The synthesis method according to claim 1, wherein in the step (1), the weight ratio of isopropanol, p-hydroxyanisole and tributylphosphine is 10-20: 0.001-0.002: 1.
3. the synthesis method according to claim 1, wherein in the step (1), the reflux incubation time is 24-48 h.
4. The synthesis method according to claim 1, wherein in the step (3), the weight ratio of nonylphenol polyoxyethylene ether, alkylphenol ether sodium sulfosuccinate, water and tributylphosphine is 0.5-2: 0.2-0.5: 40-60: 1.
5. the synthesis method according to claim 1, wherein in the step (4), the initiator is one of potassium persulfate, ammonium persulfate and sodium persulfate, and the weight ratio of the initiator solution to tributylphosphine is 2-4: 1, the mass concentration of the initiator solution is 5-10%.
6. The synthesis method according to claim 1, wherein in the step (4), the reducing agent is sodium sulfite or sodium thiosulfate, and the weight ratio of the reducing agent solution to tributylphosphine is 3-5: 1, the mass concentration of the reducing agent solution is 3-5%.
7. The degradable temporary plugging agent prepared by the synthesis method according to any one of claims 1 to 6, wherein the molecular structural formula of the degradable temporary plugging agent is as follows:
wherein:
a=200-5000；
b=50-1000；
c=200-5000；
d=50-1000；
e=50-1000；
f=200-5000；
g=50-1000；
h=200-5000；
i=50-1000；
j=50-1000；
the molecular weight of the degradable temporary plugging agent is 500000-10000000.
8. The use of a degradable plug according to claim 7 wherein said use is in an oil and gas well.
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