CN113896831A - Double-effect inhibitor for natural gas hydrate drilling fluid and preparation method and application thereof - Google Patents
Double-effect inhibitor for natural gas hydrate drilling fluid and preparation method and application thereof Download PDFInfo
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- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
- C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
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- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/14—Clay-containing compositions
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- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
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Abstract
The invention provides a double-effect inhibitor for natural gas hydrate drilling fluid, and a preparation method and application thereof. The inhibitor drilling fluid has good compatibility and high hydrate decomposition inhibition efficiency, can obviously reduce the hydrate decomposition rate under the overheat condition, reduce the hydration dispersion degree of clay, and synergistically maintain the stability of the well wall of a hydrate stratum in the drilling process.
Description
Technical Field
The invention relates to a double-effect inhibitor for natural gas hydrate drilling fluid and a preparation method and application thereof, belonging to the technical field of sea natural gas hydrate drilling and production.
Background
Natural gas hydrate is a clathrate hydrate generally composed of more than 99% methane gas and less than 1% other hydrocarbon gases as guest molecules. The natural gas hydrate is a clean replacing energy source, a crystalline substance is formed by natural gas and water under the conditions of high pressure and low temperature, the total amount of global hydrate resources is about twice of the total amount of traditional fossil energy sources, the hydrate resource amount of the sea area of China is about 800 million tons of oil equivalent, the natural gas hydrate is an important potential high-efficiency clean oil-gas replacing resource, and the natural gas hydrate is particularly important for guaranteeing the safety of the national energy strategy. Hydrate trial mining is developed in a plurality of developed countries such as the United states, Japan, Canada and the like in recent years, and deep water natural gas hydrate trial mining in the sea area of China also makes an important breakthrough, but all the hydrate trial mining methods are far away from commercial mining methods.
The seabed natural gas hydrate is extremely sensitive to temperature and pressure, and the natural gas hydrate in the reservoir is easily decomposed due to mass and heat transfer interaction between the shaft working fluid and the natural gas hydrate in the drilling process, so that the formation stress around a well hole is redistributed, the formation strength is reduced, and the well wall instability and the reservoir damage are caused. By injecting chemical agents to stabilize the formation hydrate or reduce the decomposition rate of the hydrate, the phenomenon that the formation strength is reduced due to hydrate decomposition can be effectively inhibited. However, few studies on hydrate decomposition inhibitors are currently being made, such as: chinese patent document CN109321215A discloses a hydrate decomposition inhibitor prepared by singly using or compounding poly-3-methylene-2-pyrrolidone, lecithin and poly-N-vinyl pyrrolidone, which can avoid a series of downhole accidents caused by hydrate decomposition, wherein the decomposition inhibition efficiency of lecithin is highest, but the addition of lecithin in drilling fluid is limited by foaming phenomenon easily caused by adding lecithin into the drilling fluid, the addition of lecithin is usually not more than 0.5%, and the preparation steps of poly-3-methylene-2-pyrrolidone are complicated. Chinese patent document CN112961255A discloses a hydrate decomposition inhibitor prepared from cellulose and 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxy silane, which can improve the hydrate decomposition inhibition of a drilling fluid system and has the characteristics of simple preparation method and environmental protection. Generally, the research on the novel natural gas hydrate decomposition inhibitor is less, and the existing natural gas hydrate inhibitor has weak effect on inhibiting the hydration of clay, so that the development of the novel natural gas hydrate decomposition inhibitor has important significance.
The sea natural gas hydrate stratum is buried shallowly and has poor lithogenesis, and the clay content is up to 30 percent. When the water-sensitive clay mineral interacts with the drilling fluid, the strength of the stratum is reduced due to water absorption, and the water-sensitive clay mineral is one of the key factors influencing the stability of the well wall. Chinese patent document CN103509533A provides a hydration inhibitor suitable for shale formation, which is prepared from nonionic polyether and organic micromolecular quaternary ammonium salt, and can effectively solve the problem of borehole wall instability caused by shale hydration in the drilling process. Chinese patent document CN106190064A discloses a polyamine inhibitor, which is synthesized by reacting a low-molecular-weight amine compound with a heterocyclic compound under a set condition, has strong inhibiting capability on shale, has good compatibility with other conventional drilling fluid treating agents, and is non-toxic and environment-friendly. At present, the hydration inhibitor is mainly suitable for shale strata, and a double-effect inhibitor with hydration inhibition and hydrate decomposition inhibition functions is not provided for natural gas hydrate strata.
Therefore, the development of the double-effect inhibitor with the natural gas hydrate decomposition inhibition performance and the clay hydration inhibition performance is one of the key aspects in the technical field of natural gas hydrate drilling and production at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a double-effect inhibitor for natural gas hydrate drilling fluid and a preparation method and application thereof. After the inhibitor is added into the drilling fluid, the natural gas hydrate decomposition inhibition of the drilling fluid can be obviously improved, and the mass transfer efficiency of methane in an aqueous solution is reduced; meanwhile, the hydration dispersion degree of the clay can be inhibited, the formation crack development is reduced, and the well wall stability in the well drilling process is favorably ensured; the double-effect inhibitor has the hydrate decomposition inhibiting performance and the clay hydration inhibiting performance, and the preparation method is simple.
The technical scheme of the invention is as follows:
the double-effect inhibitor for the natural gas hydrate drilling fluid is prepared by the free radical polymerization reaction of 2-acrylamido-2-methyl-1-propanesulfonic acid and dimethyldiallylammonium chloride, and has a structure shown as the following formula I:
in the formula I, x/y is 3.5-5.
According to the invention, the preparation method of the double-effect inhibitor for the natural gas hydrate drilling fluid comprises the following steps:
(1) mixing 2-acrylamido-2-methyl-1-propanesulfonic acid with deionized water, and uniformly stirring to obtain a monomer solution;
(2) adding dimethyl diallyl ammonium chloride into the monomer solution, and uniformly stirring to obtain a monomer mixed solution;
(3) adjusting the pH value of the monomer mixed solution to 7-7.5, and introducing nitrogen; then heating to 50-60 ℃, and adding an initiator for reaction; and then drying and crushing to obtain the double-effect inhibitor for the natural gas hydrate drilling fluid.
According to the invention, the ratio of the mass of the 2-acrylamido-2-methyl-1-propanesulfonic acid to the volume of deionized water in step (1) is preferably 0.1 to 0.3g:1 mL.
According to the invention, the stirring temperature in the step (1) is preferably 10-25 ℃, the stirring speed is 200-300 rpm, and the stirring time is 5-10 minutes.
According to the invention, the stirring temperature in the step (2) is preferably 10-25 ℃, the stirring speed is 200-300 rpm, and the stirring time is 5-10 minutes.
According to the present invention, the molar ratio of the 2-acrylamido-2-methyl-1-propanesulfonic acid to the dimethyldiallylammonium chloride in the monomer mixture solution in the step (2) is preferably 3 to 5: 1.
Preferably, in the step (3), a sodium hydroxide solution with the mass fraction of 20-50% is used for adjusting the pH of the monomer mixed solution; the time for introducing the nitrogen is 30 minutes, and the air in the reaction system can be exhausted by introducing the nitrogen.
Preferably, the initiator in the step (3) is ammonium persulfate and sodium bisulfite, and the mass ratio of the ammonium persulfate to the sodium bisulfite is 2: 1; the initiator is added into the system in the form of initiator aqueous solution, firstly ammonium persulfate aqueous solution with the mass concentration of 3-4 mg/mL is added, and after 5-10 minutes, sodium bisulfite aqueous solution with the mass concentration of 1-2 mg/mL is added.
According to the invention, the mass of the initiator in the step (3) is preferably 0.15-0.50% of the total mass of the 2-acrylamido-2-methyl-1-propanesulfonic acid and the dimethyldiallylammonium chloride.
According to the invention, the reaction time in the step (3) is preferably 4-6 hours; the stirring speed in the reaction process is 200-400 rpm.
According to the invention, the drying temperature in the step (3) is preferably 80-90 ℃, and the drying time is preferably 12-24 hours.
According to the invention, the double-effect inhibitor for the natural gas hydrate drilling fluid is applied to the natural gas hydrate drilling fluid and is used for inhibiting the decomposition of natural gas hydrate and inhibiting the hydration of clay as the inhibitor; preferably, the mass concentration of the inhibitor in the drilling fluid is 0.5-3 wt%.
The invention has the following technical characteristics and beneficial effects:
1. the invention utilizes anionic monomer 2-acrylamido-2-methyl-1-propane sulfonic acid and cationic monomer dimethyl diallyl ammonium chloride to carry out free radical polymerization according to a certain proportion to prepare the double-effect inhibitor for the natural gas hydrate drilling fluid, the cationic group in the molecule of the obtained double-effect inhibitor can enhance the adsorption capacity of the polymer on the surface of the hydrate through coulomb interaction, the enrichment degree of water molecules on the surface of the hydrate is increased through a sulfonate group with strong hydration capacity, the capacity of the water molecules participating in the formation of the hydrate is improved, the activity of liquid-phase water molecules on the surface of the hydrate is reduced, the hydrate decomposition rate under the overheating condition is reduced, the decomposition of the hydrate is inhibited, and the stability of the well wall of a hydrate stratum in the drilling process is maintained.
2. The double-effect inhibitor is a zwitterionic polymer, contains quaternary ammonium salt cationic groups and sulfonic anionic groups, can achieve a better decomposition inhibition effect at a high concentration, and overcomes the foaming problem of lecithin. The cationic group of the inhibitor also enhances the inhibition capability on clay, reduces the hydration degree of the clay through adsorption, and has stronger inhibition capability than the inhibitors of the same type. The inhibitor drilling fluid has good compatibility and high hydrate decomposition inhibition efficiency, can obviously reduce the hydrate decomposition rate under the overheat condition, reduce the hydration dispersion degree of clay, and synergistically maintain the stability of the well wall of a hydrate stratum in the drilling process.
3. The 2-acrylamido-2-methyl-1-propanesulfonic acid and the dimethyl diallyl ammonium chloride monomer used in the invention have groups with opposite electric properties and are difficult to polymerize under common conditions, so that a redox initiation system is adopted in the invention, the invention has higher free radical polymerization initiation capability, and the zwitterionic polymer is successfully prepared. The ratio of the anionic monomer to the cationic monomer is controlled within the range of 3-5: 1, which is the result of optimization through a large number of experiments, although the adsorption capacity of the polymer on the surface of the hydrate can be improved by increasing the ratio of the cationic monomer, the cost for preparing the polymer and the difficulty for polymerizing the monomer can be improved by increasing the ratio of the cationic monomer; and the cation proportion is too low, so that the obtained polymer has lower performance of inhibiting the decomposition of natural gas hydrate and the hydration of clay. Therefore, the natural gas hydrate double-effect inhibitor with good performance can be prepared by selecting proper monomer ratio.
4. The double-effect inhibitor for the natural gas hydrate drilling fluid has both hydrate decomposition inhibition performance and clay hydration inhibition performance, can achieve multiple effects by only adding one additive, reduces the types of the additives, and has small influence on the performance of the natural gas hydrate drilling fluid.
Drawings
FIG. 1 is an infrared spectrum of the dual effect inhibitor for natural gas hydrate drilling fluid prepared in example 1.
Fig. 2 is a graph showing the linear expansion rates of the cores in test example 4 in pure water, the polyamine inhibitor solution, and the dual effect inhibitor solution prepared in example 1.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials and equipment are commercially available, unless otherwise specified.
Example 1
A preparation method of a double-effect inhibitor for natural gas hydrate drilling fluid comprises the following steps:
(1) mixing 17.45g of 2-acrylamido-2-methyl-1-propanesulfonic acid powder with 75mL of deionized water, stirring at a stirring speed of 200r/min at a temperature of 25 ℃ for 5 minutes, and uniformly mixing to obtain a monomer solution.
(2) 3.40g of dimethyldiallylammonium chloride is added into the monomer solution, and the monomer mixed solution is obtained after stirring for 5 minutes under the conditions that the stirring speed is 200r/min and the temperature is 25 ℃.
(3) Dropwise adding a sodium hydroxide solution with the mass fraction of 20% into the monomer mixed solution obtained in the step (2), wherein the dropwise adding time is 5min, and the pH value of the system is adjusted to 7; then, the resulting mixed solution was put into a three-necked flask, nitrogen gas was introduced thereinto for 30 minutes, and the air in the flask was purged.
(4) Weighing 0.038g of ammonium persulfate and 0.019g of sodium bisulfite initiator, and respectively dissolving in 10mL of deionized water to obtain an ammonium persulfate solution and a sodium bisulfite solution; heating the mixed solution in the three-neck flask to 60 ℃, setting the magnetic stirring speed to 200rpm, and sequentially adding an ammonium persulfate solution and a sodium bisulfite solution at intervals of five minutes under the stirring condition; continuously reacting for 4 hours under the conditions of stirring speed of 200r/min and temperature of 60 ℃; and after the reaction is finished, drying the obtained reaction liquid at 90 ℃ for 24 hours, and crushing to obtain the double-effect inhibitor for the natural gas hydrate drilling fluid.
The infrared spectrum analysis of the double effect inhibitor synthesized in this example was carried out using an infrared spectrometer (KBr pellet) of the Shimadzu IRTracer-100 model, and the results are shown in FIG. 1. As can be seen from FIG. 1, 1040cm-1And 1192cm-1Is characteristic absorption peak of sulfonate, 1544cm-11662cm, bending vibration of N-H and stretching vibration of C-N bond-1An absorption peak at which C ═ O bonds in the amide groups; 3524cm-1Stretching vibration of N-H in amide group; 2972cm-1is-CH3The asymmetric stretching vibration of (2). Therefore, the obtained double-effect inhibitor polymer contains quaternary ammonium salt cationic groups, amide groups and sulfonate anionic groups, which indicates that the target product is successfully prepared.
Example 2
A preparation method of a double-effect inhibitor for natural gas hydrate drilling fluid comprises the following steps:
(1) 15.06g of 2-acrylamido-2-methyl-1-propanesulfonic acid powder and 75mL of deionized water were mixed, stirred at a stirring rate of 200r/min at 25 ℃ for 5 minutes, and mixed uniformly to obtain a monomer solution.
(2) 2.94g of dimethyldiallylammonium chloride is added into the monomer solution, and the mixture is stirred for 5 minutes under the conditions that the stirring speed is 200r/min and the temperature is 25 ℃ to obtain a monomer mixed solution.
(3) Dropwise adding a sodium hydroxide solution with the mass fraction of 20% into the monomer mixed solution obtained in the step (2), wherein the dropwise adding time is 5min, and the pH value of the system is adjusted to 7; then, the resulting mixed solution was put into a three-necked flask, nitrogen gas was introduced thereinto for 30 minutes, and the air in the flask was purged.
(4) Weighing 0.038g of ammonium persulfate and 0.0190g of sodium bisulfite initiator, and respectively dissolving in 10mL of deionized water to obtain an ammonium persulfate solution and a sodium bisulfite solution; heating the mixed solution in the three-neck flask to 60 ℃, setting the magnetic stirring speed to 200rpm, and sequentially adding an ammonium persulfate solution and a sodium bisulfite solution at intervals of five minutes under the stirring condition; continuously reacting for 5 hours under the conditions of stirring speed of 200r/min and temperature of 60 ℃; and after the reaction is finished, drying the obtained reaction liquid at 90 ℃ for 24 hours, and crushing to obtain the double-effect inhibitor for the natural gas hydrate drilling fluid.
Example 3
A preparation method of a double-effect inhibitor for natural gas hydrate drilling fluid comprises the following steps:
(1) 11.72g of 2-acrylamido-2-methyl-1-propanesulfonic acid powder and 75mL of deionized water were mixed, stirred at a stirring rate of 200r/min at 25 ℃ for 5 minutes, and mixed uniformly to obtain a monomer solution.
(2) 2.28g of dimethyldiallylammonium chloride is added into the monomer solution, and the mixture is stirred for 5 minutes under the conditions that the stirring speed is 200r/min and the temperature is 25 ℃ to obtain a monomer mixed solution.
(3) Dropwise adding a sodium hydroxide solution with the mass fraction of 20% into the monomer mixed solution obtained in the step (2), wherein the dropwise adding time is 5min, and the pH value of the system is adjusted to 7; then, the resulting mixed solution was put into a three-necked flask, nitrogen gas was introduced thereinto for 30 minutes, and the air in the flask was purged.
(4) Weighing 0.038g of ammonium persulfate and 0.0190g of sodium bisulfite initiator, and respectively dissolving in 10mL of deionized water to obtain an ammonium persulfate solution and a sodium bisulfite solution; heating the mixed solution in the three-neck flask to 60 ℃, setting the magnetic stirring speed to 200rpm, and sequentially adding an ammonium persulfate solution and a sodium bisulfite solution at intervals of five minutes under the stirring condition; continuously reacting for 6 hours under the conditions that the stirring speed is 200r/min and the temperature is 60 ℃; and after the reaction is finished, drying the obtained reaction liquid at 90 ℃ for 24 hours, and crushing to obtain the double-effect inhibitor for the natural gas hydrate drilling fluid.
Comparative example 1
In this comparative example, lecithin, having a purity of greater than 90%, was used as a natural gas hydrate inhibitor and was provided by Shanghai Allantin Biotech Co., Ltd.
Comparative example 2
A dual effect inhibitor was prepared as described in example 1, except that: 13.61g of dimethyldiallylammonium chloride, 2-acrylamido-2-methyl-1-propanesulfonic acid and dimethyldiallylammonium chloride are added in step (2) in a molar ratio of 1: 1.
Comparative example 3
A dual effect inhibitor was prepared as described in example 1, except that: in the step (2), 1.61g of dimethyldiallylammonium chloride, 2-acrylamido-2-methyl-1-propanesulfonic acid and dimethyldiallylammonium chloride are added in a molar ratio of 10: 1.
Test example 1
Drilling fluid foaming results in a decrease in drilling fluid density and when the drilling fluid column pressure in the well is below the formation pressure, a kick or blowout is caused, thus requiring the drilling fluid additive to have a lower foaming rate. The dual-effect inhibitor prepared in example 1 and the inhibitor of comparative example 1 were added to 301mL of water to prepare an aqueous solution having a mass concentration of 0.5 wt%, and after stirring at 5000rpm for 5 minutes at high speed, the slurry inhibitor solution was removed from the stirrer, that is, the time was counted, the slurry inhibitor solution was completely introduced into a clean 500mL measuring cylinder within 20 seconds, the total volume thereof was read at 30 seconds, and the foaming ratio was calculated according to the following formula: the foaming ratio was calculated according to the following formula:
wherein A is the foaming rate in unit%;v is the volume of the inhibitor aqueous solution after high-speed stirring, and the unit is mL; v0Is the volume of water in mL.
The test results are shown in table 1.
Table 1 foaming properties of the inhibitors of example 1 and comparative example 1
| Inhibitor type | Volume of drilling fluid | Foaming ratio |
| Comparative example 1 | 328 | 8.9％ |
| Example 1 | 303 | 0.6％ |
As can be seen from Table 1, the foaming ratio of the dual effect inhibitor prepared by the present invention is significantly lower than that of the lecithin of comparative example 1. Therefore, the kinetic inhibitor of the natural gas hydrate prepared by the invention better meets the foaming performance requirement in deepwater drilling.
Test example 2
The drilling fluid compatibility test is carried out on the double-effect inhibitor prepared in the example 1.
The double-effect inhibitor prepared in the example 1 is used for preparing a marine deepwater drilling fluid base slurry, and the formula is as follows: water +4 wt% bentonite +0.35 wt% Na2CO3+1 wt% of the dual action inhibitor prepared in example 1; meanwhile, blank drilling fluid without adding a double-effect inhibitor is prepared for comparison.
The conventional performance test is carried out on the two prepared drilling fluid base slurries, and the compatibility of the double-effect inhibitor prepared by the invention in the water-based drilling fluid is evaluated. The rheological parameters and the API (American Petroleum institute) fluid loss of the drilling fluid are tested by referring to the national standard GB/T29170-2012 laboratory test for oil and gas industrial drilling fluid, and the results are shown in Table 2.
Table 2 example 1 and blank drilling fluid rheology fluid loss test
As can be seen from Table 2, the viscosity of the base slurry is increased under the influence of the zwitterionic polymer dual-effect inhibitor of the invention, and the drilling fluid compatibility is good; after the additive is added, the filtration loss reduction performance of the drilling fluid is obviously improved, the formation of a mud cake with low permeability in a stratum is facilitated, and the decomposition process of the hydrate is inhibited through the mass transfer effect of the blocking drilling fluid and the stratum.
Test example 3
The inhibitors prepared in example 1 and comparative example 1 were subjected to a test for natural gas hydrate decomposition inhibiting property.
The method comprises the following specific steps: dissolving a test sample in water to prepare an inhibitor solution with the mass concentration of 1 wt%, placing the inhibitor solution in a reaction kettle, vacuumizing the reaction kettle, and introducing methane gas to maintain the pressure at 9 MPa. After the hydrate is generated in situ in the environment with the pressure of 9MPa and the temperature of 0.5 ℃ in the reactor, the temperature is raised to 14 ℃, the temperature and pressure change condition in the hydrate reaction reactor after the temperature is raised once per minute is recorded, and the hydrate is considered to be completely decomposed after the temperature and pressure are stabilized for 30 minutes. Calculating the amount of substance of methane gas released in the hydrate decomposition process according to the temperature and pressure data recorded per minute through the Peng-Robinson equation, and expressing the average decomposition rate (mol/L) of the hydrate by using the average amount of methane gas released per hour in the whole decomposition process; the amount of the substance released by the methane gas in the reaction kettle at a certain moment is divided by the total amount of the methane gas released by the complete decomposition of the hydrate, so that the relative decomposition rate of the hydrate at a certain moment in the decomposition process can be represented.
The inhibitors prepared in example 1 and comparative example 1 were subjected to a hydrate decomposition inhibition test according to the experimental method described above, while the above experimental procedure was repeated with a blank experiment set, i.e., under pure water conditions (without addition of the inhibitor). The test results are shown in table 3. As can be seen from table 3, the decomposition rate of the hydrate was reduced by 29.5% and the complete decomposition time of the hydrate was extended by 45.7% by the effect of comparative example 1; the decomposition rate of the hydrate is reduced by 37.3% under the action of the example 1, the complete decomposition time of the hydrate is prolonged by 64%, and the action effect of the example 1 is obviously due to the lecithin.
Table 3 hydrate decomposition inhibition test of example 1 and comparative example 1
Test example 4
The dual effect inhibitor prepared in example 1 was tested for hydration inhibition and compared to a conventional hydration inhibitor polyamine product (supplied by Shandong Polyxin chemical Co., Ltd.).
The specific test steps are as follows:
130mL of water is measured, and the polyamine inhibitor and the double-effect inhibitor prepared in the example 1 are added to prepare an aqueous solution with the mass concentration of 1 wt%. 10.0g of bentonite dried at 105 ℃ is taken and put into a measuring barrel, and is compacted for 5min on a hydraulic press under the pressure of 10MPa, so as to prepare the artificial bentonite core. After the core was taken out, the polyamine inhibitor with a mass concentration of 1 wt%, the aqueous solution of the dual-effect inhibitor prepared in example 1, and pure water were added to a normal temperature and pressure linear expansion instrument, respectively, and the linear expansion height was measured. The results of the linear expansion rate test performed on pure water, the polyamine inhibitor and the dual effect inhibitor prepared in example 1 are shown in fig. 2. Compared with pure water, the expansion rate of the core in 16 hours under the action of the example 1 is obviously reduced, the effect is superior to that of polyamine of the same kind, and the prepared double-effect inhibitor can effectively play a hydration inhibition role.
Test example 5
The rolling recovery experiment is a common method for evaluating the dispersion performance of the rock and is a dynamic experiment simulating the shearing rate of the underground annular space. Measuring 6 parts of 350mL of water, adding potassium chloride into one part of the water to prepare a potassium chloride solution with the mass concentration of 3 wt%, and preparing the other four parts of the water to prepare a polyamine solution with the mass concentration of 1 wt% and the double-effect inhibitor solutions prepared in example 1, comparative example 2 and comparative example 3 with the mass concentration of 1 wt% to obtain a solution to be measured. Respectively weighing 20g of 6-10 meshes of rock debris, putting the rock debris into a roller aging furnace filled with the solution to be tested, rolling for 16h at normal temperature, taking out the rock debris, cleaning the rock debris by using standard saline water, screening, drying and weighing by using a 40-mesh standard screen, and recording the ratio of the rock debris to the initial rock debris mass as the rock debris recovery rate, wherein the results are shown in Table 4. Under the action of the double-effect inhibitor prepared in the embodiment 1 of the invention, the recovery rate of the rock sample is improved from 19.5% to 92.5%, and the hydration dispersion inhibition effect of the embodiment on the rock sample is reflected. In the comparative example 2, the proportion of the cationic monomer is too high, the difficulty of monomer polymerization is improved, the polymerization degree of the obtained product is lower, and the rock dispersion inhibiting performance is poorer; in comparative example 3, the adsorption capacity of the polymer on the clay surface was deteriorated due to the low cationic monomer ratio, and the rolling recovery was significantly lower than that of example 1.
TABLE 4 rolling recovery test data for standard rock samples
Claims (10)
1. The double-effect inhibitor for the natural gas hydrate drilling fluid is characterized by being prepared by the polymerization reaction of 2-acrylamido-2-methyl-1-propanesulfonic acid and dimethyl diallyl ammonium chloride free radical, and having a structure shown as the following formula I:
in the formula I, x/y is 3.5-5.
2. The preparation method of the double-effect inhibitor for the natural gas hydrate drilling fluid, which is disclosed by claim 1, comprises the following steps of:
(1) mixing 2-acrylamido-2-methyl-1-propanesulfonic acid with deionized water, and uniformly stirring to obtain a monomer solution;
(2) adding dimethyl diallyl ammonium chloride into the monomer solution, and uniformly stirring to obtain a monomer mixed solution;
(3) adjusting the pH value of the monomer mixed solution to 7-7.5, and introducing nitrogen; then heating to 50-60 ℃, and adding an initiator for reaction; and then drying and crushing to obtain the double-effect inhibitor for the natural gas hydrate drilling fluid.
3. The preparation method of the double-effect inhibitor for the natural gas hydrate drilling fluid, according to claim 2, is characterized in that the ratio of the mass of the 2-acrylamido-2-methyl-1-propanesulfonic acid in the step (1) to the volume of deionized water is 0.1-0.3 g:1 mL.
4. The preparation method of the double-effect inhibitor for the natural gas hydrate drilling fluid, according to claim 2, is characterized in that the stirring temperature in the step (1) is 10-25 ℃, the stirring speed is 200-300 rpm, and the stirring time is 5-10 minutes.
5. The preparation method of the double-effect inhibitor for the natural gas hydrate drilling fluid, according to claim 2, is characterized in that the stirring temperature in the step (2) is 10-25 ℃, the stirring speed is 200-300 rpm, and the stirring time is 5-10 minutes.
6. The preparation method of the double-effect inhibitor for the natural gas hydrate drilling fluid, according to claim 2, is characterized in that the molar ratio of the 2-acrylamido-2-methyl-1-propanesulfonic acid to the dimethyldiallylammonium chloride in the monomer mixed solution in the step (2) is 3-5: 1.
7. The preparation method of the double-effect inhibitor for the natural gas hydrate drilling fluid as claimed in claim 2, wherein in the step (3), a sodium hydroxide solution with the mass fraction of 20-50% is used for adjusting the pH value of the monomer mixed solution; the time for introducing nitrogen is 30 minutes.
8. The preparation method of the double-effect inhibitor for the natural gas hydrate drilling fluid as claimed in claim 2, wherein the initiator in the step (3) is ammonium persulfate and sodium bisulfite, and the mass ratio of the ammonium persulfate to the sodium bisulfite is 2: 1; the initiator is added into the system in the form of initiator aqueous solution, firstly ammonium persulfate aqueous solution with the mass concentration of 3-4 mg/mL is added, and after 5-10 minutes, sodium bisulfite aqueous solution with the mass concentration of 1-2 mg/mL is added; the mass of the initiator is 0.15-0.50% of the total mass of the 2-acrylamido-2-methyl-1-propanesulfonic acid and the dimethyl diallyl ammonium chloride.
9. The preparation method of the double-effect inhibitor for the natural gas hydrate drilling fluid as claimed in claim 2, wherein the reaction time in the step (3) is 4-6 hours; the stirring speed in the reaction process is 200-400 rpm; the drying temperature is 80-90 ℃, and the drying time is 12-24 hours.
10. The application of the double-effect inhibitor for the natural gas hydrate drilling fluid in the natural gas hydrate drilling fluid, which is used as the inhibitor for inhibiting the decomposition of natural gas hydrate and inhibiting the hydration of clay; preferably, the mass concentration of the inhibitor in the drilling fluid is 0.5-3 wt%.
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