CN111154477B - Efficient retarded solid acid system without damage to reservoir - Google Patents
Efficient retarded solid acid system without damage to reservoir Download PDFInfo
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- CN111154477B CN111154477B CN202010078920.0A CN202010078920A CN111154477B CN 111154477 B CN111154477 B CN 111154477B CN 202010078920 A CN202010078920 A CN 202010078920A CN 111154477 B CN111154477 B CN 111154477B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/725—Compositions containing polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
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Abstract
The invention relates to a high-efficiency slow solid acid system without damage to a reservoir, which consists of an acidic substance and a natural polymer easy to degrade, wherein the acidic substance is one or a mixture of two of glycolic acid and lactic acid in any proportion, and the natural polymer is one or a mixture of more of guar gum, starch, carboxymethyl cellulose, hydroxypropyl carboxymethyl cellulose and locust bean gum in any proportion. The retarded solid acid system is prepared by the following process: mixing an acidic substance and a natural polymer according to the mass ratio of 0.2-1.2: 1, uniformly mixing to obtain particles with the particle size of 20-70 meshes, placing the particles in a coating pot, scattering zinc acetate powder, rotating the coating pot at the speed of 100-300 revolutions per minute, simultaneously irradiating by using an infrared lamp, and spraying 92-98 percent glycolic acid aqueous solution by using a spray gun for 60-90 minutes. According to the invention, acidic substances are input into the stratum in a wrapping manner, so that the retarding capacity is greatly enhanced, no corrosion inhibitor is required to be added, and the coating is easy to degrade, is beneficial to environmental protection and has wide market application prospect.
Description
Technical Field
The invention belongs to an efficient retarded solid acid system without damage to a reservoir in the technical field of oil and gas yield increase transformation.
Background
The carbonate rock oil and gas reservoirs are widely distributed and have large reserve potential in the global scope. But the carbonate reservoir has strong heterogeneity, complex geological conditions and low construction yield. At present, a mature acidification/acid fracturing technology becomes one of leading technologies for building, increasing and stabilizing yield of a carbonate reservoir. At present, the carbonate rocks with recoverable value are proved to have the characteristics of compact matrix, no oil and discontinuous reservoir body distribution at home, long seams are required to be manufactured through acid fracturing, the utilization efficiency of acid liquor is improved, the modification volume is increased, more effective reservoir bodies are communicated, and the retarding performance of the acid liquor becomes the key of the yield-increasing modification effect of the carbonate rock reservoir.
The existing acid liquor with high-temperature retarding performance comprises emulsified acid, gelled acid and cross-linked acid, and although the acid liquor systems can have certain retarding performance by increasing the viscosity of the systems, the acid liquor can inevitably undergo chemical reaction as long as contacting rocks, the filtration control rate is always low, and a large amount of acid liquor in a near-wellbore area is consumed, so that the effective action distance of the acid liquor is limited, and the requirement of making long joints is difficult to meet. And the entry of the high molecular compound in the acidification process is difficult to avoid generating residues, and certain damage can be caused to a reservoir. In recent years, scholars at home and abroad propose to wrap solid hydrochloric acid, nitric acid, citric acid and the like by using a certain wrapping material, separate the solid acid from a carrying fluid, lay the solid acid in a fracturing fracture, and control the dissolution performance of the wrapping material through temperature and time to achieve the purpose of increasing the effective acting distance of the acid solution.
The patent application 'coated acid for increasing effective distance of acid fracturing' (CN201910338078.7) discloses a solid coated retarded acid system, which utilizes an acidic carrying fluid to carry the coated acid into a stratum so as to increase the effective acting distance of the acid; a solid acid fracturing process (CN201210285611.6) adopts water insoluble solid acid at normal temperature, and carries fluid with certain viscosity into stratum to release and erode stratum rock under stratum condition, thus realizing deep acidification and increasing effective action distance of acid liquid.
The two acid systems can improve the effective acting distance of acidification of the deep stratum of the carbonate rock to a certain extent. However, the solid acid system still uses traditional hydrochloric acid as a main component, and the hydrochloric acid reacts with the carbonate rock more violently and rapidly, and the effect is limited. And hydrochloric acid is liquid, and a complex granulation process needs to be carried out before the coating.
Disclosure of Invention
The invention aims to provide a high-efficiency retarding solid acid system which has no harm to a reservoir, and consists of an acidic substance and an easily degradable natural polymer, wherein the acidic substance is input into a stratum in a wrapping mode, the retarding capability is greatly enhanced, the acidic substance can not react with a pipe column in the conveying process, a corrosion inhibitor is not required to be added, and the system is easy to degrade, can not cause damage to the stratum, is beneficial to environmental protection and has wide market application prospect.
In order to achieve the technical purpose, the invention adopts the following technical scheme.
An efficient slow-speed solid acid system without damage to reservoir is composed of an acidic substance and easily degradable natural polymer.
The acidic substance is one or a mixture of two of glycolic acid and lactic acid in any proportion, and the natural polymer is one or a mixture of more of guar gum, starch, carboxymethyl cellulose, hydroxypropyl carboxymethyl cellulose and locust bean gum in any proportion.
The high-efficiency retarded solid acid system is prepared by the following steps: mixing solid acidic substance and natural polymer according to the mass ratio of 0.2-1.2: 1, uniformly mixing, extruding by an extruding machine to prepare particles with the particle size of 20-70 meshes; putting the prepared granules into a coating pot, scattering zinc acetate powder, wherein the mass of the zinc acetate powder is 0.001-0.005% of that of the acidic substance, starting the coating pot to rotate at the speed of 100 plus one minute and 300 revolutions per minute, simultaneously irradiating by an infrared lamp, spraying 92-98% glycolic acid aqueous solution by a spray gun after rotating for 10-30 minutes, stopping spraying after 60-90 minutes, and continuing rotating for 30-60 minutes to obtain the coated slow solid acid.
In the acidification process, in order to effectively reduce the reaction speed of acid rocks and prolong acid corrosion cracks, the contact between acid and carbonate rocks is the most effective method for isolating. The acid substance glycolic acid (or lactic acid) in the present invention is a strong acid, can undergo an erosion reaction with carbonate rock, is in a solid state at normal temperature, and is easily granulated. Glycolic acid and a natural polymer are mixed and granulated to reduce the amount of glycolic acid used, taking advantage of the fact that glycolic acid does not chemically react with the natural polymer in an anhydrous state. Glycolic acid is easy to polymerize under the catalysis of zinc acetate, and during the preparation process, glycolic acid sprayed on the surfaces of glycolic acid and natural polymer particles is polymerized under the catalysis to generate a polyglycolic acid membrane which tightly wraps the mixture of glycolic acid and natural polymer. During the acidification construction, the polyglycolic acid can not react with the rock, but after the polyglycolic acid reaches the position needing acidification, the polyglycolic acid is hydrolyzed by the polyglycolic acid and is decomposed into glycolic acid, and meanwhile, the internal glycolic acid is released to react with the rock. Glycolic acid reacts with carbonate rock to form a complex, avoiding precipitation of high concentrations of calcium ions. All components of solid acid entering the well can be degraded into small molecular compounds, and natural polymers can be degraded into various monosaccharides, so that the solid acid is easy to flow back and cannot damage the stratum.
Compared with the prior art, the invention has the following beneficial effects:
(1) acidic substances are input into the stratum in a wrapped mode, so that the retarding capacity is greatly enhanced;
(2) the reaction with the pipe column can not occur in the conveying process, so that the addition of the corrosion inhibitor is saved;
(3) aiming at the superiority of a reservoir stratum at the temperature of more than 160 ℃, the protection of a tubular column in the acidification process of the high-temperature reservoir stratum is always a technical problem, and the solid acid can be used for well solving the problem;
(4) the conventional hydrochloric acid system has extremely high reaction speed at such high temperature, and the solid acid has obvious speed-slowing effect;
(5) all components of solid acid entering the well can be degraded into small molecular compounds, so that the stratum cannot be damaged;
(6) glycolic acid reacts with carbonate rock to form a complex, avoiding precipitation of metal ions.
Detailed Description
The present invention is further illustrated below by examples to facilitate understanding of the invention by those skilled in the art. It is to be understood that the invention is not limited in scope to the specific embodiments, but is intended to cover various modifications within the spirit and scope of the invention as defined and defined by the appended claims, as would be apparent to one of ordinary skill in the art.
Preparation of high-efficiency slow solid acid system
Example 1
2kg of solid glycolic acid and 10kg of guar gum were stirred and mixed uniformly, and the outlet size of the extruder was controlled to obtain 20-mesh granules. Putting the granules into a coating pan, adding 0.02g zinc acetate, starting the coating pan, rotating at 100 rpm, irradiating the coating pan with infrared lamp, rotating for 15min, spraying 95% glycolic acid water solution from the spray gun outlet, rotating while spraying for 60min, and stopping. Rotating for 40min to obtain coated solid acid.
Example 2
5kg of solid lactic acid and 10kg of starch are stirred and mixed uniformly, and the outlet size of an extruding machine is controlled to obtain 40-mesh granules. Putting the granules into a coating pan, adding 0.1g zinc acetate, starting the coating pan, rotating at 300 r/min, irradiating the coating pan with infrared lamp, rotating for 20min, spraying 96% glycolic acid water solution from the spray gun outlet, rotating while spraying for 80min, and stopping. Rotating for 60min to obtain coated solid acid.
Example 3
8kg of solid glycolic acid was mixed with 6kg of locust bean gum and 4kg of hydroxypropyl carboxymethyl cellulose with stirring, and the outlet size of the extruder was controlled to obtain 70-mesh granules. Putting the granules into a coating pan, adding 0.32g zinc acetate, starting the coating pan, rotating at 200 r/min, irradiating the coating pan with infrared lamp, rotating for 30min, spraying 95% glycolic acid water solution from the spray gun outlet, rotating while spraying for 90min, and stopping. Rotating for 30min to obtain coated solid acid.
Example 4
12kg of solid glycolic acid was mixed with 5kg of carboxymethyl cellulose and 5kg of guar gum under stirring, and the outlet size of the extruder was controlled to obtain 50 mesh granules. Putting the granules into a coating pan, adding 0.6g zinc acetate, starting the coating pan, rotating at 300 r/min, irradiating the coating pan with infrared lamp, rotating for 30min, spraying 98% glycolic acid water solution from the spray gun outlet, rotating while spraying for 80min, and stopping. Rotating for 50min to obtain coated solid acid.
Example 5
2kg of solid glycolic acid, 9kg of lactic acid, 2kg of locust bean gum and 8kg of starch were stirred and mixed uniformly, and the outlet size of the extruder was controlled to obtain 40-mesh granules. Putting the granules into a coating pan, adding 0.33g zinc acetate, starting the coating pan, rotating at 300 r/min, irradiating the coating pan with infrared lamp, rotating for 30min, spraying 98% glycolic acid water solution from the spray gun outlet, rotating while spraying for 80min, and stopping. Rotating for 50min to obtain coated solid acid.
Example 6
6kg of solid glycolic acid, 1kg of lactic acid and 8kg of locust bean gum were uniformly mixed with stirring, and the outlet size of the extruder was controlled to obtain 40-mesh granules. Putting the granules into a coating pan, adding 0.35g zinc acetate, starting the coating pan, rotating at 300 r/min, irradiating the coating pan with infrared lamp, rotating for 30min, spraying 98% glycolic acid water solution from the spray gun outlet, rotating while spraying for 80min, and stopping. Rotating for 50min to obtain coated solid acid.
Second, the slow performance test of the high-efficiency slow solid acid system
The retardation performance of the solid acid of the invention is tested according to the standard evaluation method of retardation acid energy SY/T5886-. Weighing 2.5g of carbonate rock powder, putting the carbonate rock powder into a beaker, adding 50ml of 20% hydrochloric acid into a comparison sample, and reacting for 15 min; as the solid acid provided by the invention has the coating degradation time of more than 40min, the sample reaction time is 60 min. 22g of the solid acid of the invention and 30ml of water were added to the test sample, which was taken out, filtered, dried, weighed, and the reaction amount and the corrosion rate were calculated (the results are shown in the following table). Tests show that the retarding performance of the invention has great advantages compared with 20% hydrochloric acid.
| Sample (I) | Reaction time/min | Rock reaction amount/g | Corrosion rate/% |
| 20％HCl | 15 | 2.500 | 100 |
| Example 1 | 60 | 0.393 | 15.72 |
| Example 2 | 60 | 0.464 | 18.56 |
| Example 3 | 60 | 0.499 | 19.96 |
| Example 4 | 60 | 0.702 | 28.08 |
| Example 5 | 60 | 0.638 | 25.52 |
| Example 6 | 60 | 0.565 | 22.60 |
Claims (1)
1. A high-efficiency slow solid acid system without damage to a reservoir is composed of an acidic substance and a natural polymer which is easy to degrade, wherein the acidic substance is one or a mixture of two of glycolic acid and lactic acid in any proportion, and the natural polymer is one or a mixture of more of guar gum, starch, carboxymethyl cellulose, hydroxypropyl carboxymethyl cellulose and locust bean gum in any proportion; the high-efficiency retarded solid acid system is prepared by the following steps: mixing solid acidic substance and natural polymer according to the mass ratio of 0.2-1.2: 1, uniformly mixing, extruding by an extruding machine to prepare particles with the particle size of 20-70 meshes; putting the prepared granules into a coating pot, scattering zinc acetate powder, wherein the mass of the zinc acetate powder is 0.001-0.005% of that of the acidic substance, starting the coating pot to rotate at the speed of 100 plus one minute and 300 revolutions per minute, simultaneously irradiating by an infrared lamp, spraying 92-98% glycolic acid aqueous solution by a spray gun after rotating for 10-30 minutes, stopping spraying after 60-90 minutes, and continuing rotating for 30-60 minutes to obtain the coated slow solid acid.
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