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WO2018171812A1 - Agent d'obturation en caoutchouc auto-expansible sélectif pour l'huile/l'eau d'un réservoir fracturé de type cave, son procédé de préparation et son application - Google Patents

Agent d'obturation en caoutchouc auto-expansible sélectif pour l'huile/l'eau d'un réservoir fracturé de type cave, son procédé de préparation et son application Download PDF

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Publication number
WO2018171812A1
WO2018171812A1 PCT/CN2018/082860 CN2018082860W WO2018171812A1 WO 2018171812 A1 WO2018171812 A1 WO 2018171812A1 CN 2018082860 W CN2018082860 W CN 2018082860W WO 2018171812 A1 WO2018171812 A1 WO 2018171812A1
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WO
WIPO (PCT)
Prior art keywords
parts
rubber
agent
self
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2018/082860
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English (en)
Chinese (zh)
Inventor
李再峰
李亮
张潇
王建海
陈康
周晓燕
任波
郭娜
伍亚军
马淑芬
刘广燕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northwest Branch Co Technology Research Institute Of Petroleum Engineering Sinopec
Qingdao University of Science and Technology
Original Assignee
Northwest Branch Co Technology Research Institute Of Petroleum Engineering Sinopec
Qingdao University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Northwest Branch Co Technology Research Institute Of Petroleum Engineering Sinopec, Qingdao University of Science and Technology filed Critical Northwest Branch Co Technology Research Institute Of Petroleum Engineering Sinopec
Publication of WO2018171812A1 publication Critical patent/WO2018171812A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls

Definitions

  • the present application belongs to the field of functional polymer materials, and in particular relates to a cement-water selective self-expanding rubber plugging agent for a fracture-cavity reservoir, a preparation method thereof and an application thereof.
  • Carbonate reservoirs have huge oil and gas reserves, of which more than 30% are fracture-cavity reservoirs.
  • This type of oil and gas reservoir consists of karst caves, fractures and dissolved pores. It is multi-synchronous by crustal tectonic movement, karst superimposed structure and multi-stage accumulation.
  • the reservoir reservoir forms a discontinuous spatial distribution and reservoir heterogeneity. Extremely strong, the matrix does not have the ability to store and seep, the oil-water system is extremely complex, and the development of carbonate reservoirs has high technical difficulty.
  • the fracture-cavity reservoirs of carbonate rocks in Tahe Oilfield are mostly high-temperature (above 100°C) and high-salt (100000mg/L) reservoirs.
  • the heterogeneity is strong, the relationship between underground oil and water is complicated, and the effluent interval is difficult to determine.
  • the conventional water shutoff process has poor adaptability; the fracture-cavity reservoir circulation channel has strong conductivity, low formation pressure gradient, ultra-deep reservoir and high temperature and high salt (buried depth is 5000-7500m, temperature is 120-140°C, mineralization
  • the characteristics of 210-240g / L) seriously restrict the effective application of conventional high-strength or selective plugging agents.
  • polymer microspheres are often used for water shutoff and flood control, but the problem is that the polymer microspheres used for water shutoff are generally small in size (calculated in nm), and the microsphere technology is not suitable for large pore blocking, such as
  • the fracture-cavity reservoirs like the northwestern oilfields in China are not well adapted in the high-permeability zone; 2 the previous microspheres have a gel as the core in the water-bearing reservoirs, which has an impact on the long-term stability of the reservoir;
  • the raw materials of the ball come from organic chemical monomers, the cost is high, and the cost of synthesis and application of the microspheres is relatively high.
  • phenolic resins have been widely used in water shutoff in oil fields.
  • the pre-shrinkage liquid of the thermosetting phenolic resin is first mixed with the curing agent, and then extruded into the water layer, and under the action of the curing agent and the formation temperature, the resin can be crosslinked to form an insoluble and insoluble resin under a period of time. Structure to block the water layer.
  • the advantage of the resin type plugging agent is that it can be injected into the formation pores and generate sufficient plugging strength to block the formation of cracks, pores, holes and other types of geological conditions.
  • the blocking agent After the chemical curing of the resin, the blocking agent forms a chemical bond with the sand surface, thereby blocking the formation, affecting the oil production of the oil passage, and affecting the oil recovery. Therefore, the development of a new high-temperature deep plugging agent is a necessary means to solve the high-temperature, high-salt oil layer production and increase injection.
  • the invention provides a cement-water selective self-expanding rubber plugging agent for a fracture-cavity reservoir, a preparation method thereof and an application thereof.
  • an aspect of the present invention provides a fracture-cavity oil-water selective self-expanding rubber blocking agent comprising the following raw materials by weight: 100 parts of nitrile rubber, 50-110 parts of water absorbing resin, and oil 5-15 parts of the swelling resin, 15-30 parts of the reinforcing agent, 0.5-2 parts of the softening agent, 2-5 parts of the accelerator, 3-6 parts of the zinc oxide, and 0.5-3.5 parts of the vulcanizing agent.
  • the following raw materials are included in the following parts by weight: 100 parts of nitrile rubber, 70-90 parts of water absorbing resin, 8-10 parts of oil swellable resin, 20-30 parts of reinforcing agent, 1.0-2 parts of softening agent, accelerator It is 3-5 parts, 4-6 parts of zinc oxide, and 1.0-2.5 parts of a vulcanizing agent.
  • the water absorbing resin is one of sodium polystyrene sulfonate, sodium polyvinyl sulfonate or sodium polyallylate sulfonate or a mixture thereof.
  • the oil-swellable resin is one of a hydrogenated petroleum resin, a phenol resin, a styrene-butadiene rubber or a polyethylene resin or a mixture thereof.
  • the vulcanizing agent is benzoyl peroxide, dicumyl peroxide or a mixture thereof.
  • the reinforcing agent is carbon black 550, white carbon black or a mixture thereof.
  • the softening agent is stearic acid and the accelerator is zinc oxide.
  • Another aspect of the present application provides a method for preparing a fracture-cavity oil-water selective self-expanding rubber plugging agent according to any one of the above aspects, comprising the steps of:
  • the obtained vulcanized rubber strip is mechanically pulverized, and the particles are classified by sieving to obtain a self-expanding rubber blocking agent having different particle diameters.
  • the self-expanding rubber blocking agent has a particle size ranging from 0.5 to 1.5 mm.
  • a further aspect of the present application provides a cement-water selective self-expanding rubber plugging agent for a fracture-cavity reservoir according to any one of the above technical solutions at a temperature of 120 ° C to 140 ° C and a mineralization degree of ⁇ 20 ⁇ 10 4 mg. /L application in the deep part of the fracture-cavity carbonate reservoir.
  • the self-expanding rubber plugging agent for oil-water selective self-expanding rubber plugging agent provided in this application is made of nitrile rubber as matrix material, supplemented by reinforcing agent, water absorbing resin, oil swellable resin, etc. It has the characteristics of high mechanical strength, strong mineralization resistance, high toughness, high volume expansion ratio, non-precipitation and self-adhesive properties.
  • the rubber plugging agent provided by the present application slowly expands with water, and the oil-swelling resin is slowly released and released under the action of a small amount of oil to precipitate on the surface of the particles, and the particles form an effective adhesion at a high temperature, and form a high temperature resistance after being expanded by water absorption.
  • the salt-resistant high-strength expansion elastomer effectively blocks large cracks and blocks the water passage. It can be effectively used in deep cavernous carbonate reservoirs with a temperature of 130 °C and a salinity of ⁇ 20 ⁇ 10 4 mg/L. Blocked.
  • the rubber plugging agent provided in this application is the best measure to reduce water, stabilize oil and water, and improve oil recovery. It has broad application prospects, good economic benefits and practical application value.
  • the embodiment of the present application provides a cement-water selective self-expanding rubber plugging agent for a fracture-cavity oil reservoir, comprising the following raw materials by weight: 100 parts of nitrile rubber, 50-110 parts of water absorbing resin, and 5-15 parts of oil swellable resin.
  • the reinforcing agent is 15-30 parts
  • the softener is 0.5-2 parts
  • the accelerator is 2-5 parts
  • the zinc oxide is 3-6 parts
  • the vulcanizing agent is 0.5-3.5 parts.
  • the formula of the oil-water selective self-expanding rubber plugging agent for the fracture-cavity reservoir is made of a nitrile rubber as a base material, supplemented by a water absorbing resin, an oil swellable resin, a reinforcing agent, a softening agent, a vulcanizing agent and a promoter. It is prepared by vulcanization after mixing and mixing. It has the characteristics of high mechanical strength, strong mineralization resistance, high toughness, high volume expansion ratio, non-precipitation and self-adhesive properties.
  • the different components in the rubber plugging agent are selectively expanded under the action of water or oil in the deep oil and water system of the oil reservoir, and the sealing of the rubber plugging agent is exerted as much as possible. effect.
  • the specific action process is as follows: after the rubber plugging agent is in contact with water, the water molecules are combined with the hydrophilic groups of the water absorbing resin in the rubber to cause the rubber plugging agent to slowly expand, and the water molecules gradually penetrate from the rubber surface to the rubber inside until the rubber blocking agent The expansion balance is fully achieved; during the expansion of the rubber, the oil-swelling resin inside the rubber is deposited along the expanded passage to the surface of the rubber particles, and is slowly released and swollen under the action of a small amount of oil, when the temperature is higher than that of the polymer resin.
  • the expanded rubber particles When the transition temperature is close to the viscous flow temperature, the expanded rubber particles gradually form an effective adhesion, forming a larger particle group plugging system, further improving the sealing effect on water.
  • the rubber plugging agent provided by the embodiment of the present invention forms a high-strength expansion elastic body resistant to high temperature and salt after encountering water, effectively blocking large cracks, sealing the water outlet channel, and can be effectively used for seams with high temperature, high salt and high salinity.
  • the cave type carbonate reservoir is deeply blocked.
  • the reservoir oil-water selective self-expanding rubber blocking agent may further comprise the following raw materials by weight: 100 parts of nitrile rubber, 70-90 parts of water absorbing resin, 8-10 parts of oil swellable resin, reinforcing
  • the agent is 20-30 parts
  • the softener is 1.0-2 parts
  • the accelerator is 3-5 parts
  • the zinc oxide is 4-6 parts
  • the vulcanizing agent is 1.0-2.5 parts.
  • the rubber plugging agent prepared by the formula has more advantages in mechanical strength, mineralization resistance, toughness and volume expansion ratio, and can be more effectively applied to high temperature, high salt and high salinity fractured hole type carbonate oil. The deep part of the reservoir is blocked.
  • the water absorbing resin is one or more of sodium polystyrene sulfonate, sodium polyvinyl sulfonate, and sodium polyallylate sulfonate.
  • the hydrophilic functional group of sodium polystyrene sulfonate, sodium polyvinyl sulfonate, and sodium polyallylate sulfonate used is a sulfonic acid group, which does not form a chemical crosslink with calcium magnesium divalent cation. The bond loses its hydrophilicity and can exhibit water swelling in mineralized water of 200,000 mineralization and has good salt tolerance.
  • the above water absorbing resin also has good compatibility with the oil swellable resin styrene butadiene rubber. It is to be understood that the present embodiment is not limited to the water absorbing resin exemplified, and may be a resin having a similar function as known to those skilled in the art.
  • the oil-swellable resin is one or more of a hydrogenated petroleum resin, a phenolic resin, a styrene-butadiene rubber, and a polyethylene resin. It will be understood that this embodiment is not limited to the listed oil-swellable resins, but may be a resin having a similar function as known to those skilled in the art.
  • the vulcanizing agent is one or both of benzoyl peroxide and dicumyl peroxide.
  • the reinforcing agent is one or both of carbon black 550 and white carbon black.
  • the softening agent is stearic acid and the accelerator is zinc oxide. It will be understood that the above examples are not limited to the listed vulcanizing agents, reinforcing agents, softening agents, and accelerators, but may also be compounds having similar functional functions well known to those skilled in the art.
  • the embodiment of the present application further provides a method for preparing a fracture-cavity oil-water selective self-expanding rubber plugging agent according to any one of the above embodiments, comprising the following steps:
  • the obtained vulcanized rubber strip is mechanically pulverized, and the particles are classified by sieving to obtain a self-expanding rubber blocking agent having different particle diameters.
  • the present embodiment provides a preparation method of the rubber plugging agent mentioned in the above embodiment, which is obtained by kneading the above components, followed by vulcanization to obtain a desired vulcanized rubber strip, and then mechanical vibration is used as needed.
  • the pulverized method fractionates the pulverized particles to obtain a rubber plugging agent having a particle diameter ranging from 0.5 to 1.5 mm. It is prepared into plugging agents of different particle sizes, mainly to meet the needs of crack size sealing of different reservoirs in deep cavernous carbonate reservoirs, so as to reduce water effluent, stabilize oil and water control, and improve oil recovery. purpose.
  • the embodiment of the present application further provides a cement-water selective self-expanding rubber plugging agent for a fracture-cavity reservoir according to any one of the above embodiments, at a temperature of 120 ° C to 140 ° C, a salinity of ⁇ 20 ⁇ 10 4 mg / Application of L in the deep part of the fracture-cavity carbonate reservoir.
  • the rubber plugging agent provided by the above embodiments has the characteristics of high mechanical strength, strong mineralization resistance, high toughness, high volume expansion ratio, non-precipitation and self-adhesive property, and can slowly expand when exposed to water, and the oil swellable resin is in a small amount of oil.
  • the slow release and swelling are deposited on the surface of the particles, and the particles form an effective adhesion at high temperature.
  • a high-strength gel with high temperature and salt resistance can be formed. Therefore, it can effectively block large cracks and block the outlet passage, especially for deep blockage of fracture-cavity carbonate reservoirs with high temperature, high salt and high salinity.
  • the depth of the deep part of the reservoir is greater than or equal to 3000 m.
  • nitrile rubber 100 parts is put into the open mill for mastication of raw rubber.
  • the measured parts in the formulation system are weighed according to Table 1, and then the weighed reinforcing agent, water absorbing resin, softener, accelerator, and oxidation are weighed one by one.
  • Zinc, oil-swelling resin and vulcanizing agent are sequentially added to the open mill for kneading and mixing, and the rubber mixture is processed and cold-set for 24 hours.
  • the rubber compound was placed in a mold, and the rubber was vulcanized by a flat vulcanizing machine at 10 MPa and 170 ° C to obtain a vulcanized rubber.
  • the prepared vulcanizate was mechanically pulverized by a pulverizer, and sieved by a vibrating sieve to obtain rubber particles having different particle diameters.
  • the preparation method was the same as that of Example 1, except that the parts by weight of the components to be added were different.
  • the parts by mass added to each component are shown in Table 1.
  • the preparation method was the same as that of Example 1, except that the parts by weight of the components to be added were different.
  • the parts by mass added to each component are shown in Table 1.
  • the preparation method was the same as that of Example 1, except that the parts by weight of the components to be added were different.
  • the parts by mass added to each component are shown in Table 1.
  • nitrile rubber 100 parts is placed in an open mill for mastication, then 60 parts of superabsorbent resin sodium polyacrylate, 0.5 part of softener, 3 parts of accelerator, 3 parts of zinc oxide, reinforcing agent 20, vulcanizing agent 1
  • the mixture was sequentially added to an open mill for kneading, and the rubber mixture was processed and cold-sealed for 24 hours.
  • the rubber compound was placed in a mold, and the rubber was vulcanized by a flat vulcanizing machine at 10 MPa and 170 ° C to obtain a vulcanized rubber.
  • the prepared vulcanizate was mechanically pulverized by a pulverizer, and sieved by a vibrating sieve to obtain rubber particles having different particle diameters.
  • the preparation method was the same as in Comparative Example 1, except that the parts by weight of the components to be added were different.
  • the parts by mass added to each component are shown in Table 1.
  • Nitrile rubber 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Reinforcing agent 15 20 25 30 20 20 20 Water absorbing resin 50 70 90 110 60 80 Softener 0.5 1.0 1.5 2 0.5 1.0 Accelerator 2 3 4 5 3 4 Zinc oxide 3 4 5 6 3 5 Oil swelling resin 5 8 10 15 0 0 Vulcanizing agent 0.5 1.0 2.5 3.5 1 1
  • the water absorbing resin used in the formulation example provided by the present application is sodium polystyrene sulfonate, which has good salt tolerance, and the volume expansion ratio in mineralized water of 200,000 mineralization is between 250 and 310%,
  • the water absorbing resin used in the ratio is sodium polyacrylate, which hardly expands in mineralized water of 200,000 mineralization and has poor salt tolerance.
  • oil-swelling resin is also used in the formulation of the present application, so that the rubber particles have the adhesion property in the mineralized water at 130 ° C after expansion, and further improve the sealing effect on water, while the particles processed in the proportional ratio do not have water in the water of 130 ° C. Adhesion.

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  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

L'invention concerne un agent d'obturation en caoutchouc auto-expansible sélectif pour l'huile/l'eau d'un réservoir fracturé de type cave, son procédé de préparation et son application. L'agent d'obturation comprend les matières premières suivantes, en parties en poids : 100 parties de caoutchouc nitrile, 50 à 110 parties d'une résine hydroabsorbante, 5 à 15 parties d'une résine gonflant dans l'huile, 15 à 30 parties d'un agent de renforcement, 0,5 à 2 parties d'un plastifiant, 2 à 5 parties d'un accélérateur, 3 à 6 parties d'oxyde de zinc et 0,5 à 3,5 parties d'un agent de vulcanisation. L'agent d'obturation peut être appliqué pour réaliser une obturation profonde d'un réservoir fracturé de roche de carbonate de type cave, à minéralisation élevée, à haute teneur en sel et à haute température.
PCT/CN2018/082860 2018-01-15 2018-04-12 Agent d'obturation en caoutchouc auto-expansible sélectif pour l'huile/l'eau d'un réservoir fracturé de type cave, son procédé de préparation et son application Ceased WO2018171812A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810035650.8A CN108300436B (zh) 2018-01-15 2018-01-15 一种缝洞型油藏油水选择性自膨胀橡胶堵剂、其制备方法及其应用
CN201810035650.8 2018-01-15

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CN119735761A (zh) * 2024-12-26 2025-04-01 中国石油大学(华东) 一种油水相渗强选择性堵剂及其制备方法和应用

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CN110922948B (zh) * 2018-09-20 2022-03-29 中国石油天然气股份有限公司 堵水剂及其制备方法
CN111117581B (zh) * 2019-12-30 2022-06-03 中国石油天然气股份有限公司 一种封堵高角度裂缝的长效封固剂及制备方法
CN111485864B (zh) * 2020-04-30 2022-08-30 中国石油天然气股份有限公司 一种长效封固高角度裂缝的水力压裂方法
CN114427375B (zh) * 2020-09-21 2024-06-25 中国石油化工股份有限公司 一种溶洞油藏密度选择性堵水体系及其制备方法
CN114456778A (zh) * 2020-10-21 2022-05-10 中国石油化工股份有限公司 一种钻井液堵漏材料
CN114479800A (zh) * 2020-11-12 2022-05-13 中国石油化工股份有限公司 一种耐超高温颗粒堵剂及制备方法
CN113736438B (zh) * 2021-09-06 2022-09-23 东营方立化工有限公司 一种修井用承压可降解暂堵剂及其制备方法和用途

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CN119735761A (zh) * 2024-12-26 2025-04-01 中国石油大学(华东) 一种油水相渗强选择性堵剂及其制备方法和应用

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