CN115322763A - Biological acid plugging agent, preparation method thereof and application thereof in low-permeability reservoir - Google Patents
Biological acid plugging agent, preparation method thereof and application thereof in low-permeability reservoir Download PDFInfo
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Abstract
The invention provides a biological acid deblocking agent, a preparation method thereof and application thereof in a low-permeability reservoir, relating to the technical field of oilfield deblocking agents. The biological acid plugging agent provided by the invention comprises the following components in parts by weight: 10-15 parts of bioactive enzyme, 42-56 parts of acetic acid, 10-28 parts of propionic acid, 3-12 parts of complexing agent, 3-12 parts of clay stabilizer and 3-12 parts of cleanup additive. The blocking remover provided by the invention is a biological agent, can effectively remove the blocking of a low-permeability reservoir, does not damage a stratum framework while restoring the stratum permeability, and is safer and more environment-friendly; the biological enzyme activity period recorded for years greatly exceeds the validity period of the traditional chemical products; the blocking remover is low in flowback after construction, does not generate toxic and harmful gas in the traditional acid solution blocking removal process, meets the requirement of HSE working environment in oil field exploitation, is beneficial to environmental protection and saves construction cost. The biological acid plugging agent provided by the invention has a good application prospect on low-permeability reservoirs.
Description
Technical Field
The invention relates to the technical field of oilfield blocking removers, in particular to a biological acid blocking remover, a preparation method thereof and application thereof in a low-permeability reservoir.
Background
In the process of oil exploitation, due to the reasons of formation pressure reduction, temperature reduction, crude oil degassing, bacterial metabolite aggregation and the like, heavy hydrocarbons, inorganic salt scale, iron compounds, biological membranes and the like can block oil layers, particularly the permeability and porosity of low-permeability oil layers are low, and the permeability resistance is rapidly increased along with the increase of capillary acting force, so that the oil production or water injection is rapidly decreased. Therefore, the oil reservoir needs to be unplugged to restore the seepage capability of the oil reservoir and improve the recovery efficiency.
Currently, an acidification method is mainly adopted for deblocking an oil layer, and the acidification method generally adopts earth acid (mixed acid of hydrofluoric acid and hydrochloric acid) to acidify the oil layer, but most of acid liquid enters a middle-high permeable layer and only a small part of acid liquid enters a low permeable layer by adopting the method, so that the deblocking effect on the low permeable oil layer is poor; moreover, the method has short effective period, which is only about two months. In addition, hydrofluoric acid has strong corrosivity, easily causes environmental pollution, and easily causes secondary damage to the oil reservoir. The current acidification method has no ideal plugging removal effect on low-permeability reservoirs.
Disclosure of Invention
In view of the above, the present invention aims to provide a biological acid plugging agent, a preparation method thereof, and an application thereof in a low permeability reservoir. The biological acid plugging agent provided by the invention can effectively plug a low-permeability reservoir, and does not damage a stratum framework while restoring stratum permeability; the validity period is long; and the corrosion is low, so that the paint is safer and more environment-friendly.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a biological acid plugging agent which comprises the following components in parts by weight:
preferably, the biological acid-hydrolysis blocking agent comprises the following components in parts by mass:
preferably, the biologically active enzyme is SUN-Y100 bio-enzyme.
Preferably, the complexing agent is an ammonium salt complex complexing agent.
Preferably, the ammonium salt composite complexing agent is HJZ-102 ammonium salt composite complexing agent.
Preferably, the clay stabilizer is a mixture of dimethyldichlorosilane and ammonium chloride, and the mass ratio of the dimethyldichlorosilane to the ammonium chloride is 2-5.
Preferably, the cleanup additive is a cleanup additive for fracture acidizing.
The invention provides a preparation method of the biological acid deblocking agent in the technical scheme, which comprises the following steps:
mixing bioactive enzyme, acetic acid, propionic acid, a complexing agent, a clay stabilizer and a cleanup additive to obtain the biological acid deblocking agent.
The invention provides the application of the biological acid plugging agent in the technical scheme or the biological acid plugging agent prepared by the preparation method in the technical scheme in a low-permeability reservoir.
Preferably, the method of applying comprises: mixing the biological acid plugging removal agent with water to obtain a biological acid plugging removal solution; injecting the biological acidolysis plugging liquid into a low-permeability reservoir; the mass ratio of the biological acidolysis plugging agent to water is (18-57): (82-43).
The invention provides a biological acid blockage removal agent which comprises the following components in parts by weight: 10-15 parts of bioactive enzyme, 42-56 parts of acetic acid, 10-28 parts of propionic acid, 3-12 parts of complexing agent, 3-12 parts of clay stabilizer and 3-12 parts of cleanup additive. In the invention, the bioactive enzyme can change the wettability of rock (oil-wet to water-wet), degrade wax and reduce viscosity, effectively eliminate polymer and other residues attached to the surface of the rock by low-permeability reservoir rock, clean the throat and increase the permeability; the acetic acid and the propionic acid can chemically react with components such as carbonate rock, clay minerals and the like in a low-permeability reservoir to improve the permeability of an oil layer, and the acetic acid and the propionic acid are weak acids with small corrosivity, so that the destruction degree of a rock stratum is low, and the oil reservoir protection characteristic is obvious; the complexing agent, acetic acid and propionic acid act in a reservoir together and can generate a stable chelate with inorganic scale metal ions in the reservoir; the clay stabilizer can form a layer of protective film on the surface layer of an oil reservoir while the blocking remover plays a role in blocking removal, inhibits the expansion and sand production of stratum clay, prevents the migration of particles, has a good effect of stabilizing water-sensitive clay minerals, and does not cause the danger of wetting stratum oil while restoring the stratum permeability; the discharge assistant is used for returning working residual liquid from stratum. The blocking remover provided by the invention has the following beneficial effects:
(1) The blocking remover provided by the invention is a biological preparation, can effectively remove blocking of a low-permeability reservoir, has good effects of preventing swelling and stabilizing water-sensitive clay minerals, effectively eliminates blocking of polymers and inorganic scales, does not damage a stratum framework while restoring stratum permeability, has the advantages of low toxicity, low corrosivity, low odor and biodegradability, and is safer and more environment-friendly; compared with the traditional acidizing product, the blocking remover provided by the invention is not influenced by factors such as pressure, water mineralization degree, shearing, degradation and the like, and has wider application range and scene;
(2) The activity period of the biological enzyme which is recorded for years greatly exceeds the effective period of the traditional chemical product process;
(3) The blocking remover provided by the invention has no solid phase and residue in operation, is low in flowback after construction, does not generate toxic and harmful gas in the traditional acid solution blocking removal process engineering, meets the requirements of HSE working environment in oil field exploitation, is beneficial to environmental protection, and saves construction cost.
Therefore, the biological acid plugging agent provided by the invention has a good application prospect on low-permeability reservoirs.
The invention also provides a preparation method of the biological acid deblocking agent, which has simple process, easy operation and convenient large-scale production.
Drawings
FIG. 1 is a graph of the rate of loss of bio-acid deblocking fluid of different mass concentrations over time in the examples.
Detailed Description
The invention provides a biological acid plugging agent which comprises the following components in parts by weight:
the biological acid blockage removal agent comprises, by mass, 10-15 parts of bioactive enzyme, preferably 10.5-15 parts, and more preferably 10.5-12 parts. In the present invention, the biologically active enzyme is preferably SUN-Y100 bio-enzyme, which was developed by Ougi oilfield Ougi chemical company, inc., and the SUN-Y100 bio-enzyme is a protein-based catalyst. In the invention, the bioactive enzyme has the main functions of changing the wettability, degrading and reducing viscosity of the rock, effectively eliminating polymer and other residues attached to the surface of the rock by a low-permeability reservoir rock, cleaning the throat and increasing the permeability, and the specific action mechanism is as follows: the bioactive enzyme changes oil humidity into water humidity through changing rock wettability, degrading wax and reducing viscosity, reduces the flow resistance of crude oil in the gaps of a low-permeability stratum, releases the crude oil from the surfaces of rock particles, separates out from micro-gaps, and enables flowing oil drops to be gathered in the stratum; the bioactive enzyme is soluble in water and insoluble in oil, can be transported to a farther zone around a sandstone stratum in a water transportation mode, opens a new flow channel, generates a new oil storage channel in the sandstone stratum, achieves the purposes of oil displacement and yield increase, and solves the problems of strong heterogeneity, poor physical property conditions, non-development of cracks and the like of a low-permeability reservoir.
The biological acid plugging agent provided by the invention comprises 42-56 parts of acetic acid, preferably 48-56 parts of acetic acid, and more preferably 50-56 parts of acetic acid based on the mass parts of the bioactive enzyme. In the present invention, the acetic acid is a weak acid having low corrosiveness, and can effectively chemically react with components such as carbonate rock and clay mineral in the oil reservoir rock to improve the permeability of the oil reservoir.
The biological acid plugging agent provided by the invention comprises 10-28 parts of propionic acid, preferably 12-28 parts of propionic acid, and more preferably 14-20 parts of propionic acid based on the mass parts of the bioactive enzyme. In the present invention, propionic acid is a weak acid having low corrosiveness, and can chemically react with components such as carbonate rock and clay mineral in the reservoir rock to improve the permeability of the reservoir.
Based on the mass parts of the bioactive enzyme, the biological acid plugging agent provided by the invention comprises 3-12 parts of complexing agent, preferably 3.5-12 parts, and more preferably 4-10 parts. In the invention, the complexing agent is preferably an ammonium salt composite complexing agent, and in the embodiment of the invention, the ammonium salt composite complexing agent is an ammonium salt composite complexing agent of which the model is HJZ-102 and which is produced by Kaifeng City constant Polymer Biotechnology Co. In the invention, the complexing agent, acetic acid and propionic acid act in the reservoir together, and can generate stable chelate with inorganic scale metal ions in the reservoir.
The biological acid plugging agent provided by the invention comprises 3-12 parts of clay stabilizer, preferably 3.5-12 parts, more preferably 4-10 parts by mass of bioactive enzyme. In the present invention, the clay stabilizer is preferably a mixture of dimethyldichlorosilane and ammonium chloride, and the mass ratio of dimethyldichlorosilane to ammonium chloride is preferably 2 to 5, more preferably 3. According to the invention, the clay stabilizer can inhibit stratum clay expansion and clay particle migration, and can form a layer of protective film on the surface layer of an oil reservoir while the blocking remover plays a blocking removing role, so that stratum clay expansion and sand production are inhibited, particle migration is prevented, the effect of stabilizing water-sensitive clay minerals is good, and the danger of causing stratum oil wetting is avoided while stratum permeability is recovered.
Based on the mass portion of the bioactive enzyme, the biological acid blockage removal agent provided by the invention comprises 3-12 parts of a cleanup additive, preferably 3.5-12 parts, and more preferably 4-10 parts. In the invention, the cleanup additive is preferably a cleanup additive for fracture acidizing, and in the embodiment of the invention, the cleanup additive is a cleanup additive for fracture acidizing with model number CL-606, which is produced by four-dragon chemical industries, inc. in Henan. In the invention, the discharge assistant agent is used for improving the discharge rate of the working residual liquid from the stratum.
The biological acid plugging agent provided by the invention can effectively plug a low-permeability reservoir, and does not damage a stratum framework while restoring stratum permeability; the validity period is long; and the corrosion is low, so that the paint is safer and more environment-friendly.
The invention provides a preparation method of the biological acidolysis plugging agent, which comprises the following steps:
mixing bioactive enzyme, acetic acid, propionic acid, a complexing agent, a clay stabilizer and a cleanup additive to obtain the biological acid blockage removing agent.
In the invention, the mixing is carried out at normal temperature; the method of mixing is not particularly required in the present invention, and the components may be uniformly mixed by a mixing method well known to those skilled in the art.
The preparation method of the biological acid deblocking agent provided by the invention is simple in process, easy to operate and convenient for large-scale production.
The invention also provides the application of the biological acid plugging agent in the technical scheme or the biological acid plugging agent prepared by the preparation method in the technical scheme in a low-permeability reservoir. In the present invention, the permeability of the low permeability reservoir is preferably 0.1 to 50 millidarcy (mD); the method of application preferably comprises: mixing the biological acid plugging removal agent with water to obtain a biological acid plugging removal solution; injecting the biological acidolysis plugging liquid into a low permeability reservoir; the mass ratio of the biological acid plugging agent to water is preferably (18-57): (82 to 43), specifically 18. The invention has no special requirements on the mixing method of the biological acid hydrolysis plugging agent and water, and the biological acid hydrolysis plugging agent and the water can be uniformly mixed by adopting a method well known by the technical personnel in the field; the biological acid plugging removal agent and water are preferably mixed on a construction site, namely the biological acid plugging removal liquid is preferably ready to use after being prepared.
The biological acid plugging agent provided by the invention, the preparation method thereof and the application thereof in low permeability reservoirs are described in detail below with reference to the examples, but the invention is not to be construed as being limited in scope.
In each embodiment, the bioactive enzyme is SUN-Y100 biological enzyme, which is developed by the Shengli oilfield Shengli chemical industry, LLC (finite responsible corporation); the clay stabilizer is prepared by compounding dimethyl dichlorosilane and ammonium chloride according to the mass ratio of 3; the complexing agent is an ammonium salt composite complexing agent, model HJZ-102, and is produced by Kaifeng City constant polymer Biotechnology Limited; the cleanup additive is a cleanup additive for fracture acidizing, model CL-606, and is produced by four-dragon chemical industries, inc. in Henan.
Example 1
A biological acid deblocking agent is prepared by the following steps:
weighing 16g of acetic acid, 4g of propionic acid, 4g of bioactive enzyme, 4g of complexing agent, 4g of clay stabilizer and 4g of cleanup additive, and uniformly stirring at normal temperature to obtain the biological acid deblocking agent.
When in application, the biological acid plugging removal solution is prepared by fully and uniformly stirring 36g of the obtained biological acid plugging removal agent and 164g of water.
Example 2
A biological acid deblocking agent is prepared by the following steps:
weighing 32g of acetic acid, 10g of propionic acid, 6g of bioactive enzyme, 4g of complexing agent, 4g of clay stabilizer and 4g of cleanup additive, and uniformly stirring at normal temperature to obtain the biological acid deblocking agent.
When in application, 60g of the obtained biological acid deblocking agent and 140g of water are fully and uniformly stirred to prepare biological acid deblocking liquid.
Example 3
A biological acid deblocking agent is prepared by the following steps:
weighing 40g of acetic acid, 10g of propionic acid, 8g of bioactive enzyme, 4g of complexing agent, 5g of clay stabilizer and 5g of cleanup additive, and uniformly stirring at normal temperature to obtain the biological acid deblocking agent.
When in application, 72g of the biological acid plugging agent and 128g of water are fully and uniformly stirred to prepare the biological acid plugging removal liquid.
Example 4
A biological acid deblocking agent is prepared by the following steps:
weighing 50g of acetic acid, 16g of propionic acid, 12g of bioactive enzyme, 4g of complexing agent, 4g of clay stabilizer and 4g of cleanup additive, and uniformly stirring at normal temperature to obtain the biological acid deblocking agent.
When in application, 90g of the obtained biological acid plugging agent and 110g of water are fully and uniformly stirred to prepare the biological acid plugging removal liquid.
Example 5
A biological acid deblocking agent is prepared by the following steps:
weighing 56g of acetic acid, 30g of propionic acid, 16g of bioactive enzyme, 4g of complexing agent, 4g of clay stabilizer and 4g of cleanup additive, and uniformly stirring at normal temperature to obtain the biological acid deblocking agent.
When in application, 114g of the obtained biological acid plugging agent and 86g of water are fully and uniformly stirred to prepare the biological acid plugging removal solution.
The appearance and the physical and chemical properties of the biological acid plugging agent prepared in the examples 1 to 5 were tested, specifically as follows:
the appearance and physicochemical properties of the biological acid deblocking fluids prepared in examples 1 to 5 are shown in table 1:
table 1 appearance and physicochemical properties of the biological acid unblocking fluids prepared in examples 1 to 5
| Appearance of the product | Homogeneous viscous |
| pH value | |
| 2～5 | |
| Density (g/cm) 3 ) | ≥1.06 |
Table 2 shows the surface tension data measured by a surface tension meter at normal temperature when the biological acid plugging agent of example 3 is prepared into aqueous solutions of different mass concentrations:
table 2 surface tension data for the biological acid deblocking agent of example 3
The surface tension of the biological acid-hydrolysis plugging agent of other examples is tested according to the method of Table 2, and the surface tension is less than or equal to 30mN/m. The surface tension of the biological acid plugging agent prepared by the embodiment of the invention is less than or equal to 30mN/m, and the smaller the surface tension is, the smaller the contractility is, the better the wetting property is, the easier the agent is spread on the surface, and the easier the solution is to wet a solid rock stratum.
Table 3 shows the corrosion inhibition performance data of the biological acid deblocking agent of example 3 prepared into biological acid deblocking solutions with different mass concentrations, and the test method of the corrosion inhibition performance is as follows: under the condition of 70 ℃, the biological acid blockage removing liquid with different concentrations (the mass of the biological acid blockage removing agent/(the mass of the biological acid blockage removing agent + the mass of water)) is examined to influence the corrosion of the N80 coupon under the flowing state (the normal pressure dynamic corrosion performance), the experimental time is 4 hours, and 3 parallel tests are carried out on the biological acid blockage removing liquid with the same mass concentration.
Table 3 corrosion inhibition performance data of the biological acid deblocking agent of example 3 formulated into biological acid deblocking fluids of different mass concentrations
The corrosion inhibition performance of the biological acid hydrolysis blocking agent of other examples is tested according to the method in the table 3, and the average corrosivity to the N80 hanging piece is lower than 2 g/(m) 2 H). The biological acid-hydrolysis blocking agent prepared by the embodiment of the invention has low corrosion to steel, and the average corrosion is lower than 2 g/(m) 2 H) corrosion rate is less than the first-class standard of the industry (SY/T5405-2019, less than or equal to 5 g/(m) at 60 DEG C 2 H)), the corrosion inhibition performance is good.
Table 4 shows the data of the loss rate test on the rock flour, which is performed by preparing the biological acid plugging agent of example 3 into biological acid plugging removal solutions with different mass concentrations (the mass concentrations are 10%, 20%, and 40%, respectively, and are respectively recorded as 10% biological acid solution, 20% biological acid solution, and 40% biological acid solution), and the test method is as follows: in order to research the erosion effect of the biological acid plugging solution on rock powder, the dissolution rate of the biological acid plugging solution with different concentrations on the rock powder is observed under the condition of a 70 ℃ flow experiment.
Table 4 data of dissolution test results of biological acid deblocking solutions prepared from the biological acid deblocking agent of example 3 at different mass concentrations
The dissolution test result data of the biological acid plugging removal solution with different mass concentrations are plotted as a graph, and the graph is shown in figure 1.
As can be seen from table 4 and fig. 1, the biological acid plugging removal solutions with 3 concentrations all have an influence on the dissolution rate, and the higher the concentration of the biological acid solution is, the higher the dissolution rate is; the dissolution and stall speed is higher within 2 hours from the beginning, the dissolution and loss reaction is carried out within 10 hours after 2 hours, and the increase amplitude of the dissolution rate is gradually reduced along with the prolonging of time, which also shows that the biological acid blockage removing liquid has a certain retarding effect, and the low-concentration biological acid liquid has better retardance, thereby being beneficial to deep acidification of the stratum.
The application performance of the biological acid plugging removal liquid prepared from the biological acid plugging removal agent in the embodiments 1 to 5 is tested, and the method comprises the following steps:
the core used in the test experiment is taken from the same layer of two wells, 5 samples are counted, wherein the core samples taken from the first well are numbered as 1 (1) and 1 (2), the core samples taken from the second well are numbered as 2 (1), 2 (2) and 2 (3), the length of each sample is 2.9 cm-3.5 cm, and the diameter of each sample is 2.5cm. Firstly, three factors of the experiment are unified through the experiment: the injection concentration, the injection speed and the physical properties of the rock core, wherein the injection acid concentration is the concentration of the mixture ratio of the embodiment 1 to the embodiment 5 respectively; the number of levels of the acid injection rate was designed to be 0.2mL/min. The testing process is mainly divided into the following steps: 1) Measuring the porosity and permeability of the selected core, and analyzing the characteristics of a core skeleton and a throat by using a CT (computed tomography) scanner; 2) Injecting acid according to the designed injection speed, concentration and acid amount (the acid amount is set according to the volume of the core), and driving residual acid by using water; 3) And (3) measuring the porosity and permeability of the rock core after acid injection, and scanning the skeleton and throat characteristics again by using CT. The test results are shown in table 5:
TABLE 5 Change table of core permeability and porosity before and after acid injection
As can be seen from table 5, the different concentrations of the bio-acid solutions in examples 1 to 5 have a certain effect on the increase of the porosity and permeability of the core; examples 1 to 5, the concentration of the biological acid liquid is gradually increased, the acidification effect of the medium concentration is obviously better than that of the low concentration acid and the high concentration acid, the low concentration acid is as in example 1 because the acid content is low, so that the chemical reaction speed is slow, the erosion amount is small, the change of the throat is not large, and the acidification effect is relatively poor; and high concentration acid like example 5, because the reaction speed is too fast due to too high concentration of acid, fine particles generated after the skeleton particles of the core are corroded block the roar channel during migration, and the permeability change is small.
The biological acid plugging removal technology (the biological acid plugging removal solution is prepared by adopting the proportion of the biological acid plugging removal agent in the example 3 and the method of the example 3) is implemented in an Xinjiang oilfield for 24 wells, the average daily yield is 0.5t before the measures, the daily oil yield of a single well is 2t after the measures, the total effective rate is 100 percent after the measures, the cumulative yield increase is 6264t in the year, the good plugging removal effect is achieved, the flow back is small, and the specific table 6 shows.
TABLE 6 statistical table of deblocking effect of biological acid deblocking agent on Xinjiang oil field
The embodiments show that the biological acid plugging removal agent provided by the invention can effectively plug a low-permeability reservoir, has low corrosivity, and does not damage a stratum framework while restoring the stratum permeability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. The biological acid plugging agent is characterized by comprising the following components in parts by mass:
2. the biological acid plugging agent as claimed in claim 1, which comprises the following components in parts by mass:
3. the biological acid plugging agent according to claim 1 or 2, wherein the biologically active enzyme is SUN-Y100 bio-enzyme.
4. The biological acid deblocking agent according to claim 1 or 2, wherein the complexing agent is an ammonium salt complex complexing agent.
5. The biological acid plugging agent as claimed in claim 4, wherein the ammonium salt complex complexing agent is HJZ-102 ammonium salt complex complexing agent.
6. The biological acid plugging agent according to claim 1 or 2, wherein the clay stabilizer is a mixture of dimethyldichlorosilane and ammonium chloride, and the mass ratio of the dimethyldichlorosilane to the ammonium chloride is 2-5.
7. The biological acid blockage removal agent as claimed in claim 1 or 2, wherein the cleanup additive is a cleanup additive for fracture acidizing.
8. The method for preparing the biological acid deblocking agent as defined in any one of claims 1 to 7, comprising the steps of:
mixing bioactive enzyme, acetic acid, propionic acid, a complexing agent, a clay stabilizer and a cleanup additive to obtain the biological acid blockage removing agent.
9. Use of the biological acid deblocking agent of any one of claims 1 to 7 or the biological acid deblocking agent prepared by the preparation method of claim 8 in low permeability reservoirs.
10. The application according to claim 9, wherein the method of applying comprises: mixing the biological acid plugging removal agent with water to obtain a biological acid plugging removal solution; injecting the biological acidolysis plugging liquid into a low-permeability reservoir; the mass ratio of the biological acidolysis plugging agent to water is (18-57): (82-43).
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