High-strength high-temperature acid fracturing temporary plugging agent and preparation method and application thereof
Technical Field
The invention relates to the technical field of oilfield water shutoff agents, in particular to a high-strength high-temperature acid fracturing temporary plugging agent and a preparation method and application thereof.
Background
With the continuous approach of large quantities of mature oil fields to the dead-run period, even though water flooding development is carried out, only 25-35% of underground crude oil can be obtained, and a large number of reservoirs which are not used or oil layers with lower exploitation degree are still required to be further exploited. The conventional water injection exploitation has low recovery efficiency, and with the long-term continuous exploitation of the water injection oil field, the problems that the comprehensive water content of the oil field rises in the middle and later stages of the exploitation, the operations such as well workover, well killing, sand washing and the like are frequent, the workover fluid leaks into the stratum to cause pollution, the exploitation benefit of the oil field is gradually deteriorated and the like also occur. Therefore, most oil fields adopt short-term temporary plugging of certain layers of an operation well, so that crude oil of a target layer is produced to improve the recovery rate of the crude oil.
In recent years, a horizontal well staged fracturing technology enables shale oil and shale gas to be effectively developed, a bridge plug perforation combined operation technology is a standard technology for shale oil and shale gas horizontal well fracturing, and the technology is adopted by 90% of shale gas horizontal wells in the United states and more than 95% of shale gas horizontal wells in China. However, the researches of microseismic wave monitoring, fluid production profile testing, tracer testing and the like show that about 1/3 perforation clusters are not fractured and transformed or are insufficient, and the unmodified perforation clusters do not contribute to the yield. The shale gas has the characteristics of large horizontal stress difference, single fracture form after fracturing and difficulty in forming complex fractures. Shale oil and shale gas production is controlled by the complexity of artificial fractures and effective reconstruction volumes, i.e. "fracture control production". How to solve the problems of low transformation efficiency and poor uniformity of perforation clusters and improve the complexity of cracks is one of the problems faced by the traditional shale gas fracturing transformation.
The temporary plugging diversion fracturing technology can solve the problems, liquid diversion is caused by temporary plugging agent plugging, the net pressure in a crack is improved, perforating clusters which are not fully modified are opened, liquid and sand are fed into the unmodified perforating clusters, the contact maximization of a shaft and an oil-gas reservoir is realized, and the recovery ratio is improved. The technology mainly comprises two processes of seam turning and in-seam turning, and the core is to use temporary plugging agents with different particle sizes to plug perforation holes, seam mouths or natural fractures. In the hydraulic fracturing process, a temporary plugging agent is added to form a bridge plug in a main crack channel, and after the pressure is increased, a new branch crack or more micro cracks are pressed open. Through various crack steering, the complexity of the crack is increased, the modification volume is increased, and the modification efficiency of the perforation cluster is improved.
The temporary plugging agents adopted at present are water-soluble temporary plugging agents, and the raw materials are composite products of soluble (degradable) high molecular polymers. However, in the high-temperature and high-acid oil-gas well environment, the water-soluble temporary plugging agent is easy to break through by acid liquor, the dissolution speed is high, the bearing strength is greatly reduced, and the plugging performance is low; in the blockage removing process, the soluble (degradable) high molecular polymer is easy to carbonize and is not easy to remove blockage. Therefore, the current temporary plugging agent cannot play a normal plugging and de-plugging role in a high-temperature and high-acid-oil environment, and directly influences the effect of plugging measures and the petroleum output.
CN110669482A discloses an acidity-controllable temporary plugging agent and a preparation method thereof, wherein the acidity-controllable temporary plugging agent takes polylactic acid and polyglycolic acid as base materials, titanate ester as an exchange catalyst, phosphate ester and phosphate ester as exchange inhibitors, and one or a mixture of more of phenyl tosylate, dimethyl oxalate and diethyl oxalate as an accelerator and a neutralization filler. The preparation method of the temporary blocking agent with controllable acidity comprises the steps of mixing polylactic acid, polyglycolic acid and a transesterification catalyst, then melting, blending and granulating at 190-270 ℃ to obtain premixed particles; and mixing the premixed particles with a transesterification inhibitor, an accelerant and a neutralizing filler, then melting, mixing and granulating at 160-180 ℃, and finally obtaining the temporary plugging agent with controllable acidity. The temporary plugging agent with controllable acidity takes degradable polylactic acid and polyglycolic acid as resin matrixes, and finally reacts to form water-soluble salt and carbon dioxide under an acidic condition, so that automatic plugging removal can be realized without flowback operation; the polyglycolic acid and the polylactic acid are added for blending modification, which not only keeps the high strength performance of the polylactic acid, but also overcomes the defects that the polylactic acid is difficult to break and the dissolution (degradation) speed is slow.
However, the temporary plugging agent with controllable acidity has the following defects:
(1) the temporary plugging agent is obtained by blending and modifying organic matters, the strength is increased limitedly, and the pressure-bearing strength of the temporary plugging agent is not high;
(2) in the preparation process of the temporary plugging agent, secondary blending and granulation processing are needed, and the processing technology is relatively complex;
(3) the dissolution (degradation) rate is more than or equal to 85% after 6h, the dissolution (degradation) rate can reach 100% after 24h, the dissolution (degradation) speed before 6h is too high, the dissolution (degradation) speed after 6h is too low, the actual requirements of low dissolution (degradation) speed before plugging and high dissolution (degradation) speed after plugging are not met.
Therefore, the temporary plugging agent which has high pressure-bearing strength, controllable dissolving time and simple processing technology and is suitable for high-temperature and high-acid oil and gas well environment is a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a high-strength high-temperature acid-fracturing temporary plugging agent to solve the problem that the temporary plugging agent is low in pressure-bearing strength.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-strength high-temperature acid fracturing temporary plugging agent comprises the following components in parts by weight:
the principle and the advantages of the scheme are as follows: the temporary plugging agent of the scheme takes environment-friendly resin polyvinyl alcohol and polylactic acid as base materials, is matched with inorganic salt, composite plasticizer, silane coupling agent, cross-linking agent and auxiliary modifier, and is modified through blending, extrusion and processing to obtain the high-strength high-temperature acid pressure temporary plugging agent.
1. By adding inorganic salt, the solubility of the temporary plugging agent under an acidic condition is improved, and the dissolution time of the temporary plugging agent is effectively regulated and controlled so as to meet the requirement of rapid construction;
2. by adding the composite plasticizer, the intermolecular force of the polyvinyl alcohol and the polylactic acid can be destroyed, the melting plasticizing processing temperature is reduced, the compatibility between inorganic salt and polymers is improved, the mechanical property between the polymers is improved, and the pressure-bearing property of the temporary plugging agent is improved;
3. by adding the cross-linking agent, the silane coupling agent and the auxiliary modifier, certain cross-linking effect can be generated in molecules and among molecules in the dissolving process, and bridging effect is generated among temporary plugging particles, so that the swollen temporary plugging agent is cross-linked and agglomerated, and the plugging performance of the temporary plugging agent is improved; the construction risk caused by the fact that the pure organic resin temporary plugging agent becomes soft and sticky quickly in the high-temperature acid dissolution process, the gel is carbonized and cannot be completely dissolved is overcome.
4. The density of the high-strength high-temperature acid fracturing temporary plugging agent is 1.30-1.50g/cm3The grain diameter is 7-10 meshes, 10-20 meshes, 20-80 meshes and 80-140 meshes, the bearing strength is more than or equal to 40MPa, the application temperature is 90-150 ℃, and the bearing strength of the simulated sand-filling pipe at room temperature reaches 48.9 MPa.
In conclusion, the high-strength high-temperature acid fracturing temporary plugging agent has high pressure-bearing strength; the initial dissolution rate is low, and the swelling temporary plugging agent is crosslinked into a cluster along with the dissolution of the temporary plugging agent under the acidic condition, so that the plugging performance of the temporary plugging agent is improved; the dispersibility is good in the dissolving process; the later dissolution speed is high; high temperature resistance; the raw materials are cheap and easy to obtain; the preparation process is simple and convenient for grinding.
Preferably, as an improvement, the inorganic salt comprises 2-6 parts of calcium carbonate and an inorganic salt component A, and the inorganic salt component A is selected from one or more of 5-15 parts of sodium chloride, 5-10 parts of potassium chloride and 1-5 parts of sodium carbonate.
Has the advantages that: the dissolving performance of the temporary plugging agent under an acidic condition can be adjusted by sodium chloride, potassium chloride, sodium carbonate and calcium carbonate, the dissolving time of the temporary plugging agent can be effectively adjusted, and the complete dissolving time of the temporary plugging agent can be adjusted and controlled by the using amount and the proportion of inorganic salt; the time for completely dissolving the temporary plugging agent with different particle sizes is equivalent, the reservoir with pores of different sizes is satisfied, and the application range is wider; meanwhile, the calcium carbonate can improve the bearing strength of the temporary plugging agent.
Preferably, as a modification, the composite plasticizer is at least two selected from neopentyl glycol 0.01-0.05 part, pentaerythritol 0.01-0.05 part and triethanolamine 0.02-0.06 part.
Has the beneficial effects that: neopentyl glycol, pentaerythritol and triethanolamine play a synergistic role in the melt plasticizing performance of the temporary plugging agent.
Preferably, as an improvement, the silane coupling agent is selected from one or more of KH 5500.02-0.1 part, KH 5600.02-0.1 part and KH 7920.02-0.1 part.
Has the advantages that: along with the dissolution of the temporary plugging agent, the silane coupling agent is hydrolyzed to generate silicon hydroxyl which generates hydrogen bond action with hydroxyl on polyvinyl alcohol and carboxyl of polylactic acid, so that a certain crosslinking action is generated in the dissolution process of the temporary plugging agent, and the plugging performance of the temporary plugging agent is improved; and the blocking performance of the temporary blocking agent is further improved by interaction with the modifier.
Preferably, as a modification, the crosslinking agent is one or two selected from 0.02-0.1 part of phenolic resin and 0.02-0.1 part of chitosan.
Has the advantages that: after the temporary plugging agent particles are swelled, the phenolic resin, the chitosan and the additive generate an intramolecular or intermolecular hydrogen bond crosslinking effect, so that a certain crosslinking network is formed in a system, the temporary plugging agent is crosslinked into clusters, the pressure-bearing strength of the product is improved, and the plugging performance of the temporary plugging agent for acid fracturing is improved. When the temporary plugging agent is heated, the chitosan melts and can further plug the leakage when expanding in water, so that the leakage plugging effect of the product is improved, and the chitosan can be degraded, so that the recovery effect of the product is better.
Preferably, as an improvement, the auxiliary modifier is one or two selected from 0.1-0.5 part of acrylamide and 0.1-0.5 part of starch adhesive.
Has the advantages that: starch adhesive is prepared by using starch as raw material and connecting the raw materials together by virtue of adhesive property. The starch adhesive, the water and the acrylamide can form a pasty system with high viscosity, so that the composite structure of the resin material is enhanced, the fracture property of the product is reduced, the bonding property of the product is enhanced, the pressure-bearing strength of the temporary plugging agent is improved, and the plugging property of the temporary plugging agent is improved; and the blocking performance of the temporary blocking agent can be further improved by interaction with a silane coupling agent.
Preferably, as an improvement, the feed additive further comprises an antioxidant, wherein the antioxidant is selected from one or two of 10100.02-0.1 part of antioxidant and 1680.02-0.1 part of antioxidant.
Has the advantages that: antioxidants can improve the processability of degradable polymers at high temperatures.
The application also provides a preparation method of the high-strength high-temperature acid fracturing temporary plugging agent, which comprises the following steps:
(1) mixing materials: mixing the components in parts by weight, drying and cooling to obtain a mixture;
(2) extruding and granulating: performing melt extrusion on the mixture obtained in the step (1), cooling and granulating to form temporary plugging particles;
(3) and (3) grinding, namely crushing the temporary plugging particles obtained in the step (2), and grinding into finished products with different meshes.
Has the beneficial effects that: according to the scheme, the degradable plastic is modified through simple extrusion processing according to the properties of the components in the formula, and the degradable plastic can be used for temporary fracturing plugging in a high-temperature, high-pressure and high-acid environment; the preparation method is simple, the required raw materials are simple and easy to purchase, and the cost is controllable.
Preferably, as an improvement, the drying temperature in the step (1) is 80-90 ℃, and the drying time is 2-3 h;
in the step (2), the melt extrusion temperature is 180-220 ℃, the melt extrusion time is 50-200s, and the particle size of the temporary plugging particles is 2-4 mm;
the mesh number in the step (3) is one or more of 7-10 meshes, 10-20 meshes, 20-80 meshes and 80-140 meshes.
The invention also provides a high-strength high-temperature acid fracturing temporary plugging agent and application of the preparation method of the high-strength high-temperature acid fracturing temporary plugging agent in water plugging of oil fields.
Drawings
FIG. 1 is a diagram of high-strength high-temperature acid fracturing temporary plugging agents of different mesh sizes prepared in example 3 of the present invention,
wherein, A is a 7-10 mesh finished product prepared by the first group, B is a 10-20 mesh finished product prepared by the second group, C is a 20-80 mesh finished product prepared by the third group, and D is an 80-120 mesh finished product prepared by the fourth group.
Detailed Description
The following is further detailed by way of specific embodiments: in the embodiment, the raw materials are all industrial grade, and the particle sizes of the polylactic acid and the polyvinyl alcohol are 2-3 mm. The skilled in the art can buy products of different manufacturers and specifications according to actual conditions, and the source of each raw material does not influence the realization of the technical effect of the invention.
Melt extrusion refers to a process of melt-plasticizing a raw material and extruding the melt-plasticized material to form a shape.
Example one preparation of high-strength high-temperature acid fracturing temporary plugging agent containing inorganic salts in different proportions
(1) Mixing materials: weighing 300g of polyvinyl alcohol, 250g of polylactic acid, 0.2g of neopentyl glycol, 0.1g of pentaerythritol, 0.2g of triethanolamine, inorganic salt (prepared according to the proportion in Table 1), 1.0g of chitosan, 0.5g of silane coupling agent KH5500.5 g, 5.0g of starch adhesive and 0.5g of antioxidant 1010, uniformly mixing, drying at 80 ℃ for 3h, removing residual trace moisture in the material, and then cooling to room temperature in a dryer to obtain a mixture;
(2) and (3) extruding and granulating: putting the mixture obtained in the step (1) into an SJZS-10B miniature double-screw extruder for melting and plasticizing, and extruding the melted and plasticized material to form an extruded strip, wherein the melting and extruding temperature is 180-190 ℃, and the melting and extruding time is 50-60 s; cooling the extruded strips to room temperature by an SFS-120 type air-cooled conveyor, and cutting the extruded strips into temporary plugging particles of 2mm by an SQS-180 type micro granulator;
(3) grinding: a DE-300g universal high-speed pulverizer is used for grinding 2mm of temporary plugging particles into a finished product with 7-10 meshes. And detecting the solubility and the bearing strength of the prepared temporary plugging agent finished product. The specific detection method comprises the following steps:
dissolution time test method: preparing 200ml of 5% HCl solution in a beaker, adding 10g of the prepared temporary plugging agent, stirring to uniformly disperse the temporary plugging agent, sealing the temporary plugging agent with a preservative film, placing the beaker in a constant-temperature drying box which is respectively heated to 90 ℃ and 150 ℃ to heat, and recording the time for the temporary plugging agent to be completely dissolved.
The dissolution rate measuring method comprises the following steps: preparing 200ml of 5% HCl solution in a beaker, adding 10g of prepared temporary plugging agent, stirring to uniformly disperse the temporary plugging agent, sealing with a preservative film, placing the beaker in a constant-temperature drying box heated to 90 ℃, heating, and detecting the dissolution rate within 2 h. Wherein the dissolution rate is (weight before dissolution-weight after dissolution)/mass before dissolution × 100%.
And testing the pressure-bearing strength of the simulated sand-packed pipe by adopting an LDY-IV type multifunctional core displacement device at room temperature. The results are shown in Table 1.
TABLE 1 influence of inorganic salts of different proportions on the solubility and bearing strength of temporary plugging agents
As can be seen from the above table, with the increase of the calcium carbonate portion, the solubility of the temporary plugging agent under acidic conditions is increased, the dissolution time is gradually shortened, and the bearing strength is remarkably improved; when the ratio of sodium chloride: potassium chloride: sodium carbonate: the calcium carbonate component ratio is 5: 5: 2: at 8 (not shown in Table 1), the calcium carbonate component is too high to be extruded and granulated smoothly; with increasing sodium chloride and potassium chloride composition, the solubility increased, but the increase in bearing strength was insignificant. Therefore, the dissolving performance of the temporary plugging agent can be adjusted by adjusting the contents and the mixture ratio of sodium chloride, potassium chloride, sodium carbonate and calcium carbonate; the bearing strength of the temporary plugging agent can be enhanced by improving the content of calcium carbonate. The dissolution rate of each group for 2h is less than 20%, which indicates that the dissolution rate in the early stage is low, and the plugging property can be fully exerted in the period; the complete dissolution time can be regulated and controlled by adjusting the proportion of the inorganic salt, and the construction requirement is met.
EXAMPLE two preparation of high-Strength high-temperature acid fracturing temporary plugging agent containing composite plasticizers in different proportions
(1) Mixing materials: weighing 300g of polyvinyl alcohol, 250g of polylactic acid, a composite plasticizer (prepared according to the mixture ratio in Table 2), 50g of sodium chloride, 50g of potassium chloride, 20g of sodium carbonate, 60g of calcium carbonate, 0.2g of chitosan, 0.5g of a silane coupling agent KH5500.5g, 5.0g of a starch adhesive and 10100.5 g of an antioxidant, uniformly mixing, drying for 2h at 90 ℃, removing residual trace moisture in the material, and then cooling to room temperature in a dryer to obtain a mixture; the steps (2) and (3) are the same as in the first embodiment. And the processability of the prepared temporary plugging agent is detected. The results are shown in Table 2.
TABLE 2 influence of different compounding ratios of composite plasticizer on the processability of temporary plugging agent
From the above table, it can be seen that: the plasticizer group is not added, and extrusion granulation cannot be carried out; with the increase of the content of the added single plasticizer group, the mixture can be extruded for granulation, but the fluidity is poor; compared with a single plasticizer, the composite plasticizer has the advantages that under the same content, the plasticizing effect of the degradable resin is more sufficient, the fluidity is better, and smooth extrusion granulation can be realized. The combined application of the components in the composite plasticizer has better plasticizing effect on the temporary plugging agent, and the components have synergistic enhancement effect.
EXAMPLE III preparation of high Strength high temperature acid fracturing temporary plugging Agents of different mesh counts
(1) Mixing materials: weighing 200g of polyvinyl alcohol, 400g of polylactic acid, 0.1g of neopentyl glycol, 0.5g of pentaerythritol, 0.2g of triethanolamine, inorganic salt (prepared according to the proportion in Table 3), 0.5g of chitosan, 0.2g of silane coupling agent KH5600.2 g, 2.0g of starch adhesive and 0.2g of antioxidant 168, uniformly mixing, drying at 85 ℃ for 2.5h, removing residual trace moisture in the material, and cooling to room temperature in a dryer to obtain a mixture;
(2) extruding and granulating: putting the mixture obtained in the step (1) into an SJZS-10B miniature double-screw extruder for melting and plasticizing, and extruding the melted and plasticized material to form an extruded strip, wherein the melting and extruding temperature is 180-; the melt extrusion time is 100-110S, the extruded strips are cooled to room temperature by an SFS-120 type air-cooled conveyor, and are cut into temporary plugging particles with the particle size of 4mm by an SQS-180 type micro-granulator;
(3) grinding: using a universal high speed pulverizer model DE-300g, 4mm of the temporary plugging granules were ground to different mesh sizes of finished product (as shown in Table 3). And detecting the solubility of the prepared temporary plugging agent. The results are shown in Table 3. The obtained temporary plugging agent is shown in figure 1, wherein A is a first group, B is a second group, C is a third group, and D is a fourth group.
TABLE 3 dissolution time of different mesh numbers of temporary plugging agents
As can be seen from Table 3, the dissolution times of the temporary plugging agents with different particle sizes can be made equal by adjusting the mixture ratio of the inorganic salts. For the temporary plugging agent with large particle size, the addition amount of the inorganic salt can be increased to improve the dissolution property of the temporary plugging agent. For the temporary plugging agent with small particle size, the addition amount of the inorganic salt can be reduced, so that the dissolution performance of the temporary plugging agent is equivalent to that of the temporary plugging agent with large particle size. Therefore, the temporary plugging agent is suitable for reservoirs with different pore sizes and has wider application range.
EXAMPLE four preparation of high Strength high temperature acid fracturing temporary plugging agent
(1) Mixing materials: weighing 350g of polyvinyl alcohol, 200g of polylactic acid, 0.5g of neopentyl glycol, 0.2g of pentaerythritol, 0.5g of triethanolamine, 80g of sodium chloride, 100g of potassium chloride, 50g of sodium carbonate, 40g of calcium carbonate, 1.0g of chitosan, 1.0g of silane coupling agent KH7921.0g of starch adhesive and 10101.0 g of antioxidant, uniformly mixing, drying at 80 ℃ for 2.8h, removing residual trace moisture in the material, and cooling to room temperature in a dryer to obtain a mixture;
(2) extruding and granulating: putting the mixture obtained in the step (1) into an SJZS-10B miniature double-screw extruder for melting and plasticizing, extruding the melted and plasticized material to form an extrusion strip, wherein the melting and extruding temperature is 180-;
(3) grinding: using a DE-300g type universal high-speed pulverizer to pulverize the temporary plugging particles with the particle size of 3mm into a finished product with the particle size of 20-80 meshes.
The detection proves that the bearing strength is 45MPa, and the complete dissolution time in 5% HCl solution is 5.5h at 150 ℃.
EXAMPLE V preparation of high-Strength high-temperature acid fracturing temporary plugging agent
(1) Mixing materials: weighing 450g of polyvinyl alcohol, 150g of polylactic acid, 0.2g of pentaerythritol, 0.3g of triethanolamine, 50g of sodium chloride, 50g of potassium chloride, 20g of sodium carbonate, 40g of calcium carbonate, 0.2g of chitosan, 1.0g of silane coupling agent KH560, 5.0g of starch adhesive and 1680.5 g of antioxidant, uniformly mixing, drying at 85 ℃ for 2.5h, removing residual trace moisture in the material, and then cooling to room temperature in a dryer to obtain a mixture;
(2) extruding and granulating: putting the mixture obtained in the step (1) into an SJZS-10B miniature double-screw extruder for melting and plasticizing, extruding the melted and plasticized material to form an extrusion strip, wherein the melting and extruding temperature is 180-220 ℃, the melting and extruding time is 200s, cooling the extrusion strip to room temperature by an SFS-120 type air-cooled conveyor, and cutting the extrusion strip into 3mm temporary plugging particles by an SQS-180 type miniature granulator;
(3) grinding: the temporary plugging particles with the diameter of 3mm are crushed into finished products with the mesh size of 80-140.
The detection proves that the bearing strength is 43MPa, and the complete dissolution time in 5% HCl solution is 5.3h at 150 ℃.
Comparative example 1
The difference from the fourth embodiment is that: no starch binder was added.
Comparative example No. two
The difference from the fourth embodiment is that: no silane coupling agent KH792 is added.
Test example plugging Performance test
And (3) taking the temporary plugging agent prepared in the first and second comparative examples to perform plugging strength test, testing the pressure-bearing strength of the simulated sand-packed pipe by adopting an LDY-IV type multifunctional core displacement device at room temperature, and evaluating the performance of the plugging strength of the temporary plugging agent. The results are shown in Table 4.
TABLE 4 test of bearing strength
Group of
|
Bearing strength (MPa)
|
Comparative example 1
|
32
|
Comparative example No. two
|
28 |
As can be seen from the above table, the pressure-bearing strength of the temporary plugging agent of the embodiment with the silane coupling agent KH792 and the starch binder added simultaneously is 45MPa, which is obviously superior to that of the comparative example group with only one raw material added, and the combined action of the silane coupling agent and the starch binder is demonstrated to improve the pressure-bearing strength of the temporary plugging agent, so that the plugging performance of the temporary plugging agent is improved, and the silane coupling agent KH792 and the starch binder have synergistic effect.
The foregoing is merely an example of the present invention and common general knowledge in the art of designing and/or characterizing particular aspects and/or features is not described in any greater detail herein. It should be noted that, for those skilled in the art, without departing from the technical solution of the present invention, several variations and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.