CN106350044B - Low-toxicity environment-friendly polymer cross-linking agent for profile control - Google Patents
Low-toxicity environment-friendly polymer cross-linking agent for profile control Download PDFInfo
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- CN106350044B CN106350044B CN201610619444.2A CN201610619444A CN106350044B CN 106350044 B CN106350044 B CN 106350044B CN 201610619444 A CN201610619444 A CN 201610619444A CN 106350044 B CN106350044 B CN 106350044B
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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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Abstract
The invention provides a low-toxicity environment-friendly polymer cross-linking agent for profile control, which comprises the following components in parts by weight: 30-50 parts of distilled water; 30-50 parts of polyvinylamine; 5-15 parts of citric acid; 5-15 parts of sodium bisulfite. Compared with the prior art, the low-toxicity environment-friendly polymer cross-linking agent for profile control, which is created by the invention, has the following advantages: (1) compared with a phenolic resin system cross-linking agent, the cross-linking agent has no toxic and harmful reaction substances, no flammable and explosive source, and simple and safe production process and site construction; (2) the cost of the invention is far lower than that of the cross-linking agent of the polyethyleneimine system, and the invention can be widely applied in large dose, and is economical and practical; (3) the viscosity of the water-soluble gel obtained by mixing the low-toxicity environment-friendly polymer cross-linking agent with the partially hydrolyzed polyacrylamide polymer aqueous solution with the mass concentration of 3 per mill is more than 7500mPa.s, and the profile control effect is good.
Description
Technical Field
The invention belongs to the technical field of oil-water well profile control and water shutoff in oil exploitation, and particularly relates to a low-toxicity environment-friendly polymer cross-linking agent for profile control, which is used for profile control and water shutoff of oil-water wells in oil exploitation in oil fields and is cross-linked with a high-molecular polymer to form a water-soluble polymer gel profile control agent.
Background
At present, most oil fields in China are in the middle and later stages of development, especially after long-time water flooding or polymer flooding, dominant channeling channels far larger than original pores of a stratum generally appear in a mining stratum, so that subsequent water injection or polymer injection directly enters the oil wells through the dominant channeling channels and effective flooding cannot be realized. The oil-water well profile control and water shutoff technology is used for plugging the dominant cross flow channel in the stratum, expanding the effective swept volume of water injection or polymer injection, effectively displacing the oil-containing part in the stratum and achieving the purposes of increasing oil and reducing water.
The water soluble gel is one of the most commonly used profile control agents for profile control and water shutoff of oil-water wells, and mainly comprises a high molecular polymer and a cross-linking agent for the polymer. Through the cross-linking reaction of the polymer in the water-soluble gel and the cross-linking agent, the gel with certain strength is formed in the formation dominant cross flow channel, and the cross flow of water injection or polymer injection in the formation dominant cross flow channel can be effectively blocked.
The water-soluble gel has good stratum injectivity and low cost, and is particularly suitable for the use requirements of deep profile control and water plugging of oil-water wells and large dosage. However, with the improvement of national environmental protection requirements for oil exploitation, the advantage of low cost of water-soluble gel is difficult to maintain, and a polymer cross-linking agent used in large quantities in the past has high toxicity of a high-valence heavy metal chromium ion system and serious pollution to stratum, so that the oil-water well profile control and water plugging market must be gradually withdrawn.
The prior art relatively mature chromium-free polymer cross-linking agent mainly comprises a phenolic resin system and a polyethyleneimine system, but has the following problems: (1) the phenolic resin system needs to use a large amount of toxic and harmful substances such as formaldehyde, phenol, resorcinol and the like in the production and preparation process. Whether production personnel or oil-water well profile control and water shutoff site construction personnel need to make strict protective measures, so that a larger toxic risk exists; (2) the polyethyleneimine system belongs to a low-toxicity environment-friendly polymer cross-linking agent, has the advantages of stable gelling and high gelling strength, but has the over-high cost of 14-16 ten thousand yuan/ton, and cannot be widely applied in large dose.
In conclusion, the research and development and the application of the low-cost, low-toxicity and environment-friendly polymer cross-linking agent are the inevitable trend of profile control and water plugging of various oil-water wells in the oil field in the future.
Disclosure of Invention
In view of the above, in order to meet the technical requirements of the water-soluble gel for profile control and water shutoff of the oil-water well on the low-cost, low-toxicity and environment-friendly polymer cross-linking agent, the invention develops the low-toxicity and environment-friendly polymer cross-linking agent for profile control, and can effectively overcome or improve the defects of the existing profile control technology products.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a low-toxicity environment-friendly polymer cross-linking agent for profile control comprises the following components in parts by weight: 30-50 parts of distilled water; 30-50 parts of polyvinylamine; 5-15 parts of citric acid; 5-15 parts of sodium bisulfite.
Further, the low-toxicity environment-friendly polymer cross-linking agent for profile control comprises the following components in parts by weight: 35-45 parts of distilled water; 35-45 parts of polyvinylamine; 7-12 parts of citric acid; 7-12 parts of sodium bisulfite.
The invention also discloses a preparation method of the low-toxicity environment-friendly polymer cross-linking agent, which comprises the steps of weighing the required raw material components according to the raw material proportion, mixing distilled water, polyvinylamine, citric acid and sodium bisulfite in a proper container, and uniformly stirring to prepare a mixed solution, namely the low-toxicity environment-friendly polymer cross-linking agent for profile control.
Furthermore, the low-toxicity environment-friendly polymer cross-linking agent for profile control is used for preparing water-soluble gel for profile control after being uniformly stirred with partially hydrolyzed polyacrylamide polymer aqueous solution with the mass concentration of 3 per mill.
Furthermore, the mixing volume ratio of the cross-linking agent to the partially hydrolyzed polyacrylamide polymer aqueous solution with the mass concentration of 3 per mill is (0.3-0.6): 100.
compared with the prior art, the low-toxicity environment-friendly polymer cross-linking agent for profile control, which is created by the invention, has the following advantages:
(1) compared with a phenolic resin system cross-linking agent, the cross-linking agent has no toxic and harmful reaction substances, no flammable and explosive source, and simple and safe production process and site construction;
(2) the cost of the invention is 3-4 ten thousand yuan/ton which is far lower than 14-16 ten thousand yuan/ton of the polyethyleneimine system cross-linking agent, and the invention can be widely applied in large dose and is economical and practical;
(3) the low-toxicity environment-friendly polymer cross-linking agent disclosed by the invention is mixed with a partially hydrolyzed polyacrylamide polymer aqueous solution with the mass concentration of 3 per mill to obtain the water-soluble gel with the viscosity of more than 7500mPa.s and a better profile control effect.
Detailed Description
Unless otherwise defined, terms used herein have meanings that are conventionally understood by those skilled in the art, and some terms used herein are defined as follows in order to facilitate understanding of the present invention.
As used in the specification and in the claims, the singular form of "a", "an", and "the" include plural references unless the context clearly dictates otherwise. For example, the term "cell" includes a plurality of cells, including mixtures thereof.
All numerical designations such as pH, temperature, time, concentration, including ranges, are approximations. It is to be understood, although not always explicitly stated that all numerical designations are preceded by the term "about". It is also to be understood that, although not always explicitly recited, the reagents described herein are merely exemplary and equivalents thereof are known in the art.
Unless otherwise indicated, all starting materials referred to herein are commercially available.
The invention will be described in detail with reference to the following examples.
Example 1:
(1) raw materials (all commercial industrial products): 4.4g of distilled water, 3.5g of polyvinylamine, 1.2g of citric acid and 0.9g of sodium bisulfite; the components are mixed and stirred uniformly (without adding sequence) in a proper container to obtain a mixed solution, namely the low-toxicity environment-friendly polymer cross-linking agent.
(2) 500mL of partially hydrolyzed polyacrylamide polymer aqueous solution with the mass concentration of 3 per mill is arranged indoors, and the initial viscosity of the polymer aqueous solution is measured to be 470mPa.s by using a DV-II + Pro Brookfield rotational viscometer and a 5# rotor at the rotating speed of 5 rpm.
(3) Taking 0.5mL of the low-toxicity environment-friendly polymer cross-linking agent of the product, taking 100mL of the aqueous solution of the polymer in the step (2), dropwise adding the cross-linking agent into the aqueous solution of the polymer, uniformly stirring, pouring into a closed storage tank, placing in a UFE500 constant temperature incubator, maintaining for 5 days at the constant temperature of 55 ℃, and measuring the viscosity of the water-soluble gel after cross-linking of the polymer to be 6500mPa.s by using a DV-II + Pro type BROOKFIELD rotational viscometer and the rotation speed of 5# rotor at 5 rpm; maintaining at constant temperature of 55 deg.C for 15 days to obtain water-soluble gel viscosity of 7630 mPa.s; maintaining at constant temperature of 55 deg.C for 30 days, and measuring viscosity of water-soluble gel to 7745 mPa.s.
Example 2:
(1) raw materials (all commercial industrial products): 3.7g of distilled water, 4.5g of polyvinylamine, 0.7g of citric acid and 1.1g of sodium bisulfite; the components are mixed and stirred uniformly (without adding sequence) in a proper container to obtain a mixed solution, namely the low-toxicity environment-friendly polymer cross-linking agent.
(2) 500mL of partially hydrolyzed polyacrylamide polymer aqueous solution with the mass concentration of 3 per mill is arranged indoors, and the initial viscosity of the polymer aqueous solution is measured to be 480mPa.s by using a DV-II + Pro BROOKFIELD rotational viscometer and the rotation speed of a 5# rotor at 5 rpm.
(3) Taking 0.5mL of the low-toxicity environment-friendly polymer cross-linking agent of the product, taking 100mL of the aqueous solution of the polymer in the step (2), dropwise adding the cross-linking agent into the aqueous solution of the polymer, uniformly stirring, pouring into a sealed storage tank, placing in a UFE500 thermostat, maintaining for 5 days at the constant temperature of 55 ℃, and measuring the viscosity of the water-soluble gel after cross-linking of the polymer to be 7500mPa.s by using a DV-II + Pro type BROOKFIELD rotational viscometer and the rotation speed of 5# rotor at 5 rpm; maintaining at constant temperature of 55 deg.C for 15 days to obtain water soluble gel viscosity of 8010 mPa.s; maintaining at constant temperature of 55 ℃ for 30 days, and measuring the viscosity of the water-soluble gel to be 8105 mPa.s.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (5)
1. The low-toxicity environment-friendly polymer cross-linking agent for profile control is characterized by comprising the following components in parts by weight: 30-50 parts of distilled water; 30-50 parts of polyvinylamine; 5-15 parts of citric acid; 5-15 parts of sodium bisulfite.
2. The low toxicity environment-friendly polymer crosslinking agent according to claim 1, wherein: the coating comprises the following components in parts by weight: 35-45 parts of distilled water; 35-45 parts of polyvinylamine; 7-12 parts of citric acid; 7-12 parts of sodium bisulfite.
3. The method for preparing the low-toxicity environment-friendly polymer cross-linking agent according to claim 1, wherein: weighing the required raw material components according to the raw material proportion, mixing distilled water, polyvinylamine, citric acid and sodium bisulfite in a proper container, and uniformly stirring to prepare a mixed solution, namely the low-toxicity environment-friendly polymer cross-linking agent for profile control.
4. The use of a low-toxicity, environmentally friendly polymeric crosslinker for profile control according to claim 1, characterized in that: the cross-linking agent is prepared into water-soluble gel for profile control after being uniformly stirred with partially hydrolyzed polyacrylamide polymer aqueous solution with the mass concentration of 3 per mill.
5. Use of a low-toxicity environment-friendly polymer cross-linking agent for profile control according to claim 4, characterized in that: the mixing volume ratio of the cross-linking agent to the partially hydrolyzed polyacrylamide polymer aqueous solution with the mass concentration of 3 per mill is (0.3-0.6): 100.
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| CN201610619444.2A CN106350044B (en) | 2016-07-27 | 2016-07-27 | Low-toxicity environment-friendly polymer cross-linking agent for profile control |
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| CN111334267B (en) * | 2018-12-18 | 2022-12-09 | 中国石油化工股份有限公司 | Profile control agent and preparation method and application thereof |
Citations (3)
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|---|---|---|---|---|
| CN103614123A (en) * | 2013-10-21 | 2014-03-05 | 中国石油大学(华东) | Polyethyleneimine jelly profile-control water-blocking agent |
| CN103937474A (en) * | 2014-03-24 | 2014-07-23 | 四川仁智油田技术服务股份有限公司 | Environment-friendly high strength profile control water shut-off agent and preparation method thereof |
| CN104987857A (en) * | 2015-06-25 | 2015-10-21 | 中国石油天然气股份有限公司 | High-salt-resistant self-tackifying hydrophobically associating polymer gel plugging agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9175206B2 (en) * | 2012-04-24 | 2015-11-03 | Halliburton Energy Services, Inc. | Gellable treatment fluids having adjustable gel times and methods associated therewith |
| US20140076562A1 (en) * | 2012-09-14 | 2014-03-20 | Sumit Bhaduri | Method of Reducing Water or Gas Permeability in a Subterranean Formation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614123A (en) * | 2013-10-21 | 2014-03-05 | 中国石油大学(华东) | Polyethyleneimine jelly profile-control water-blocking agent |
| CN103937474A (en) * | 2014-03-24 | 2014-07-23 | 四川仁智油田技术服务股份有限公司 | Environment-friendly high strength profile control water shut-off agent and preparation method thereof |
| CN104987857A (en) * | 2015-06-25 | 2015-10-21 | 中国石油天然气股份有限公司 | High-salt-resistant self-tackifying hydrophobically associating polymer gel plugging agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 耐温抗盐凝胶调剖剂研究进展;胡绍彬 等;《当代化工》;20150228;第44卷(第2期);第263-267页 * |
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Effective date of registration: 20201102 Address after: 300000 No. three, Dagang Oilfield, Binhai New Area, Tianjin Patentee after: DAGANG OILFIELD GROUP Co.,Ltd. Patentee after: CHINA NATIONAL PETROLEUM Corp. Address before: 300280 Dagang three, Binhai New Area, Tianjin Patentee before: DAGANG OILFIELD GROUP Co.,Ltd. |
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