CN110776890B - High-strength gel profile control water shutoff agent - Google Patents
High-strength gel profile control water shutoff agent Download PDFInfo
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- CN110776890B CN110776890B CN201810856402.XA CN201810856402A CN110776890B CN 110776890 B CN110776890 B CN 110776890B CN 201810856402 A CN201810856402 A CN 201810856402A CN 110776890 B CN110776890 B CN 110776890B
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- control water
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a high-strength gel profile control water shutoff agent, and relates to the technical field of petrochemical industry. The method has the characteristics of simple preparation process, simple and convenient field operation, high strength of formed gel, firm plugging removal, salt resistance, long effective period and controllable gelling time, can achieve the aims of plugging a high-permeability layer in a stratum and adjusting the water absorption profile of a water injection well at a deep part, and improves the petroleum recovery ratio.
Description
Technical Field
The invention relates to a high-strength gel profile control water shutoff agent, belonging to the profile control water shutoff technology of oil field oil layers.
Background
China is one of countries with high proportion of water injection development oil fields in the world, the reserves for water drive account for more than 60% of the total reserves, and the water drive development oil field plays a significant role in oil development in China. With the water drive development entering the later stage, the injected water has serious ineffective channeling along the large pore passage due to the aggravation of reservoir heterogeneity, so that the water drive development effect is further deteriorated, and the oil well produces a large amount of water, so that the stable production foundation of the oil field is weakened.
In the prior art, aiming at the problems of low efficiency and ineffective circulation of large-pore injected water, various researches on a plugging control system are developed in each oil field, and polymer gels are profile control water plugging agents which are used most at home and abroad and have the widest application. Among them, the polymer gel profile control agent using hydrolyzed polyacrylamide as a main agent is most used, such as: publication No. CN105860946A discloses a profile control and water shutoff system with controllable low-temperature gelling, which mainly comprises hydrolyzed polyacrylamide, paraformaldehyde, resorcinol and m-phenylenediamine; publication No. CN106634907A discloses a polyethyleneimine profile-enhancing and water-plugging agent, which comprises partially hydrolyzed polyacrylamide, cross-linking agent polyethyleneimine, gel-forming delaying agent, stabilizing agent and the like; publication No. CN 102816558A discloses a deep profile control water shutoff agent, which comprises partially hydrolyzed polyacrylamide, potassium dichromate, sodium sulfite, hexamethylenetetramine, phenol and ammonium chloride; however, such profile control agents have some drawbacks: firstly, as the used hydrolyzed polyacrylamide is mostly a high molecular weight polymer, the powder needs to be added into water for dissolution in advance when in use, long-time stirring is needed for dissolution, and the field operation is complicated; secondly, the viscosity shear loss rate is high in the injection process after the polymer is dissolved, and the gelling property and the strength are influenced; and thirdly, the salt resistance of the hydrolyzed polyacrylamide gel is poor, and the stability of the hydrolyzed polyacrylamide gel in a high-salt stratum is poor.
Disclosure of Invention
The invention aims to provide a profile control water plugging agent which can overcome the defects of the prior art, is shear-resistant, simple in construction process, high in gelling strength and strong in salt resistance, and can be suitable for large pore channels.
The invention provides a high-strength gel profile control water shutoff agent, which comprises the following components in percentage by weight:
acrylamide monomer: 1% -10%;
cationic monomer: 0.1% -5%;
initiator: 0.05% -0.5%;
crosslinking agent A: 0.05% -0.4%;
a crosslinking agent B: 0.01% -0.05%;
clay: 0.05% -0.4%;
a stabilizer: 0.01% -0.05%;
a regulator: 0.1% -0.4%;
the balance of water; the sum of all the components is 100 percent.
Preferably, the high-strength gel profile control water shutoff agent is characterized in that: the weight percentages of the components are as follows:
acrylamide monomer: 3% -7%;
cationic monomer: 0.5% -3%;
initiator: 0.05% -0.2%;
crosslinking agent A: 0.1% -0.2%;
a crosslinking agent B: 0.01% -0.04%;
clay: 0.1% -0.4%;
a stabilizer: 0.01% -0.05%;
a regulator: 0.2% -0.3%;
the balance of water; the sum of all the components is 100 percent.
The cationic monomer is as follows: at least one of dimethyldiallylammonium chloride, acryloyloxyethyltrimethylammonium chloride, trimethylallylammonium chloride and triethylallylammonium chloride.
The initiator is at least one of azobisisobutyramidine hydrochloride, ammonium persulfate and azobisisobutyramidine hydrochloride.
The cross-linking agent A is at least one of hexamethylenetetramine, formaldehyde and paraformaldehyde.
The cross-linking agent B is at least one of phenol, hydroquinone, resorcinol and sodium salicylate.
The stabilizer is at least one of thiourea and sodium sulfite.
The regulator is at least one of ammonium chloride, ammonium formate, ammonium acetate, ammonium oxalate and ammonium sulfate.
The invention also relates to a preparation method of the high-strength gel profile control water shutoff agent, which comprises the following steps:
(1) adding clay into water, stirring, adding cationic monomer, stirring for 0.5-1 hr, adding acrylamide and initiator, and stirring;
(2) adding the cross-linking agent A, the cross-linking agent B, the stabilizing agent and the regulator, and uniformly mixing to obtain the profile control water shutoff agent.
The invention has the advantages that the clay is introduced into the profile control water shutoff agent, the cationic monomer can be inserted into the clay lamellar structure, the cationic monomer and the acrylamide monomer are polymerized in the stratum to form a clay intercalation polymer, and the intercalation polymer forms organic-inorganic composite gel under the action of the cross-linking agent. The profile control water shutoff system is convenient to prepare on site, simple in construction process, excellent in injection performance, high in strength of the formed composite gel and controllable in gelling time; the performance is stable under high mineralization degree.
Detailed Description
The invention is further illustrated by the following examples, which are intended to provide a better understanding of the invention and are not intended to limit the scope of the invention.
Example 1
Adding 0.10g of clay into 95.85g of clear water, uniformly stirring, adding 0.50g of dimethyldiallylammonium chloride, continuously stirring for 0.5h, then adding 3.00g of acrylamide monomer, 0.05g of azobisisobutyronitrile hydrochloride, 0.28g of 37% formaldehyde aqueous solution, 0.01g of hydroquinone, 0.01g of thiourea and 0.2g of ammonium chloride, and uniformly stirring to obtain the profile control and plugging agent, wherein the gelling time of the system at 50 ℃ is 10d, the strength of the formed gel can reach grade I by adopting an visual code method, and the gel is not dehydrated for 180 days.
Example 2
Adding 0.40g of clay into 88.62g of clean water, uniformly stirring, adding 3.00g of dimethyldiallylammonium chloride, continuously stirring for 1h, then adding 7.00g of acrylamide monomer, 0.05g of ammonium persulfate, 0.54g of 37% formaldehyde aqueous solution, 0.04g of hydroquinone, 0.05g of sodium sulfite and 0.3g of ammonium chloride, and uniformly stirring to obtain the profile control water plugging agent, wherein the gelling time of the system at 90 ℃ is 5d, the gel strength formed by adopting visual code evaluation can reach J level, and the gel is not dehydrated for 180 days.
Example 3
Adding 0.20g of clay into 87.83g of clean water, uniformly stirring, adding 1.00g of acryloyloxyethyl trimethyl ammonium chloride, continuously stirring for 1h, then adding 10.00g of acrylamide monomer, 0.20g of azodiisobutymidine hydrochloride, 0.41g of 37% formaldehyde aqueous solution, 0.01g of resorcinol, 0.05g of thiourea and 0.30g of ammonium formate, and uniformly stirring to obtain the profile control and water plugging agent, wherein the gelling time of the system at 50 ℃ is 5d, the strength of the formed gel can reach J grade by adopting a visual code method, and the gel is not dehydrated for 180 days.
Example 4
Adding 0.10G of clay into 88.94G of clear water, uniformly stirring, adding 5.00G of trimethyl allyl ammonium chloride, continuously stirring for 1h, then adding 5.00G of acrylamide monomer, 0.10G of azobisisobutyronitrile imidazoline hydrochloride, 0.40G of hexamethylenetetramine, 0.01G of sodium salicylate, 0.05G of thiourea and 0.20G of ammonium acetate, uniformly stirring to obtain the profile control water plugging agent, wherein the gelling time of the system at 90 ℃ is 10d, the gel strength formed by adopting a visual code method can reach grade G, and grade 180 days are not dehydrated.
Example 5
Adding 0.05G of clay into 98.04G of clean water, uniformly stirring, adding 0.10G of triethyl allyl ammonium chloride, continuously stirring for 1h, then adding 1.00G of acrylamide monomer, 0.05G of ammonium persulfate, 0.40G of paraformaldehyde, 0.01G of phenol, 0.05G of thiourea and 0.30G of ammonium oxalate, uniformly stirring to obtain the profile control water plugging agent, wherein the gelling time of the system at 50 ℃ is 5d, the gel strength of the formed gel can reach grade G by adopting a visual code method, and the gel is not dehydrated for grade 180 days.
Example 6
Adding 0.40g of clay into 88.62g of clear water, uniformly stirring, adding 3.00g of triethylallylammonium chloride, continuously stirring for 1h, then adding 7.00g of acrylamide monomer, 0.10g of azodiisobutyramidine hydrochloride, 0.54g of 37% formaldehyde aqueous solution, 0.04g of resorcinol, 0.05g of sodium sulfite and 0.30g of ammonium sulfate, uniformly stirring to obtain the profile control water plugging agent, wherein the gelling time of the system at 90 ℃ is 2d, the gel strength formed by adopting a visual code method can reach J, and the water is not dehydrated for 180 days.
Example 7
Adding 0.30g of clay into 88.92g of clean water, uniformly stirring, adding 3.00g of dimethyldiallylammonium chloride, continuously stirring for 1h, then adding 7.00g of acrylamide monomer, 0.20g of azodiisobutyramidine hydrochloride, 0.20g of paraformaldehyde, 0.04g of resorcinol, 0.04g of thiourea and 0.30g of ammonium chloride, and uniformly stirring to obtain the profile control and water plugging agent, wherein the gelling time of the system at 50 ℃ is 2d, the gel strength formed by adopting a visual code method can reach J level, and the gel is not dehydrated for 180 days.
Example 8
Adding 0.10g of clay into 95.85g of brine with total mineralization of 60000mg/L (wherein the total content of calcium ions and magnesium ions is 5000 mg/L), uniformly stirring, adding 0.50g of dimethyldiallylammonium chloride, continuously stirring for 0.5h, then adding 3.00g of acrylamide monomer, 0.05g of azobisisobutyronitrile hydrochloride, 0.28g of formaldehyde aqueous solution with the concentration of 37%, 0.01g of hydroquinone, 0.01g of thiourea and 0.2g of ammonium chloride, uniformly stirring to obtain the profile control water plugging agent, wherein the gel forming time of the system at 50 ℃ is 11d by visual observation, the gel strength formed by adopting a code method can reach grade I, and the grade 180 days is not dehydrated.
Example 9
Adding 0.40g of clay into 88.62g of brine with total mineralization of 60000mg/L (wherein the total content of calcium ions and magnesium ions is 5000 mg/L), uniformly stirring, adding 3.00g of dimethyldiallylammonium chloride, continuously stirring for 1h, then adding 7.00g of acrylamide monomer, 0.05g of ammonium persulfate, 0.54g of formaldehyde aqueous solution with the concentration of 37%, 0.04g of hydroquinone, 0.05g of sodium sulfite and 0.3g of ammonium chloride, uniformly stirring to obtain the profile control water plugging agent, wherein the gelling time of the system at 90 ℃ is 6d, the gel strength of the formed gel can reach J level by adopting a visual code method, and the gel is not dehydrated for 180 days.
Example 10
Adding 0.20g of clay into 87.83g of brine with total mineralization of 60000mg/L (wherein the total content of calcium ions and magnesium ions is 5000 mg/L), uniformly stirring, adding 1.00g of acryloyloxyethyl trimethyl ammonium chloride, continuously stirring for 1h, then adding 10.00g of acrylamide monomer, 0.20g of azodiisobutylamine hydrochloride, 0.41g of formaldehyde aqueous solution with the concentration of 37%, 0.01g of resorcinol, 0.05g of thiourea and 0.30g of ammonium formate, uniformly stirring to obtain the profile control water plugging agent, wherein the gelling time of the system at 50 ℃ is 7d, the gel strength of the formed gel can reach J grade by adopting a visual code method, and the gel is not dehydrated for 180 days.
EXAMPLE 11
Adding 0.10G of clay into 88.94G of saline water with total mineralization of 60000mg/L (wherein the total content of calcium ions and magnesium ions is 5000 mg/L), uniformly stirring, adding 5.00G of trimethyl allyl ammonium chloride, continuously stirring for 1h, then adding 5.00G of acrylamide monomer, 0.10G of azobisisobutyric imidazoline hydrochloride, 0.40G of hexamethylenetetramine, 0.01G of sodium salicylate, 0.05G of thiourea and 0.20G of ammonium acetate, uniformly stirring to obtain the profile control water plugging agent, wherein the gelling time of the system at 90 ℃ is 12d, the gel strength of the formed gel can reach grade G by adopting a visual code method, and the grade 180 days is not dehydrated.
EXAMPLE 12
Adding 0.05G of clay into 98.04G of brine with total mineralization of 60000mg/L (wherein the total content of calcium ions and magnesium ions is 5000 mg/L), uniformly stirring, adding 0.10G of triethylallylammonium chloride, continuously stirring for 1h, then adding 1.00G of acrylamide monomer, 0.05G of ammonium persulfate, 0.40G of paraformaldehyde, 0.01G of phenol, 0.05G of thiourea and 0.30G of ammonium oxalate, uniformly stirring to obtain the profile control water plugging agent, wherein the gelling time of the system at 50 ℃ is 7d, the gel strength of the formed gel can reach grade G as evaluated by a visual code method, and the grade 180 days are not dehydrated.
EXAMPLE 13
Adding 0.40g of clay into 88.62g of brine with total mineralization of 60000mg/L (wherein the total content of calcium ions and magnesium ions is 5000 mg/L), uniformly stirring, adding 3.00g of triethylallylammonium chloride, continuously stirring for 1h, then adding 7.00g of acrylamide monomer, 0.10g of azodiisobutyl amidine hydrochloride, 0.54g of formaldehyde aqueous solution with the concentration of 37%, 0.04g of resorcinol, 0.05g of sodium sulfite and 0.30g of ammonium sulfate, uniformly stirring to obtain the profile control and water plugging agent, wherein the gelling time of the system at 90 ℃ is 3d, the gel strength formed can reach J by adopting a visual code method, and the system does not dehydrate in 180 days.
EXAMPLE 14
Adding 0.30g of clay into 88.92g of brine with total mineralization of 60000mg/L (wherein the total content of calcium ions and magnesium ions is 5000 mg/L), uniformly stirring, adding 3.00g of dimethyldiallylammonium chloride, continuously stirring for 1h, then adding 7.00g of acrylamide monomer, 0.20g of azodiisobutyl amidine hydrochloride, 0.20g of paraformaldehyde, 0.04g of resorcinol, 0.04g of thiourea and 0.30g of ammonium chloride, uniformly stirring to obtain the profile control water plugging agent, wherein the gelling time of the system at 50 ℃ is 4d, the gel strength of the formed gel can reach J grade by adopting a visual code method, and the water is not dehydrated for 180 days.
Claims (5)
1. A high-strength gel profile control water shutoff agent is characterized in that: the weight percentages of the components are as follows:
acrylamide monomer: 1% -10%;
cationic monomer: 0.1% -5%;
initiator: 0.05% -0.5%;
crosslinking agent A: 0.05% -0.4%;
a crosslinking agent B: 0.01% -0.05%;
clay: 0.05% -0.4%;
a stabilizer: 0.01% -0.05%;
a regulator: 0.1% -0.4%;
the balance of water; the sum of all the components is 100 percent;
the cationic monomer is as follows: at least one of dimethyldiallylammonium chloride, acryloyloxyethyltrimethylammonium chloride, trimethylallylammonium chloride and triethylallylammonium chloride;
the cross-linking agent A is at least one of hexamethylenetetramine, formaldehyde and paraformaldehyde; the cross-linking agent B is at least one of phenol, hydroquinone, resorcinol and sodium salicylate;
the regulator is at least one of ammonium chloride, ammonium formate, ammonium acetate, ammonium oxalate and ammonium sulfate.
2. The high-strength gel profile control water shutoff agent of claim 1, which is characterized in that: the weight percentages of the components are as follows:
acrylamide monomer: 3% -7%;
cationic monomer: 0.5% -3%;
initiator: 0.05% -0.2%;
crosslinking agent A: 0.1% -0.2%;
a crosslinking agent B: 0.01% -0.04%;
clay: 0.1% -0.4%;
a stabilizer: 0.01% -0.05%;
a regulator: 0.2% -0.3%;
the balance of water; the sum of all the components is 100 percent.
3. The high-strength gel profile control water shutoff agent according to claim 1 or 2, which is characterized in that: the initiator is at least one of azobisisobutyramidine hydrochloride, ammonium persulfate and azobisisobutyramidine hydrochloride.
4. The high-strength gel profile control water shutoff agent according to claim 1 or 2, which is characterized in that: the stabilizer is at least one of thiourea and sodium sulfite.
5. The preparation method of the high-strength gel profile control water shutoff agent as claimed in claim 1 or 2, which is characterized by comprising the following steps: (1) adding clay into water, stirring, adding cationic monomer, stirring for 0.5-1 hr, adding acrylamide and initiator, and stirring; (2) adding the cross-linking agent A, the cross-linking agent B, the stabilizing agent and the regulator, and uniformly mixing to obtain the profile control water shutoff agent.
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| CN114316932B (en) * | 2020-10-09 | 2023-05-09 | 中国石油化工股份有限公司 | High-temperature-resistance resident plugging agent |
| CN113214816A (en) * | 2021-05-14 | 2021-08-06 | 西南石油大学 | Variable-viscosity slippery water and preparation method thereof |
| CN115991980A (en) * | 2021-10-19 | 2023-04-21 | 中国石油化工股份有限公司 | Profile control agent for oilfield water injection well and preparation method thereof |
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| US6767867B2 (en) * | 2001-04-16 | 2004-07-27 | Halliburton Energy Services, Inc. | Methods of treating subterranean zones penetrated by well bores |
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| CN103570859A (en) * | 2013-10-09 | 2014-02-12 | 中国石油化工股份有限公司 | Inorganic montmorillonoid composited cross-linked polymer microsphere as well as preparation method and application thereof |
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