CN103694974A - Chromium-free crosslinking system - Google Patents
Chromium-free crosslinking system Download PDFInfo
- Publication number
- CN103694974A CN103694974A CN201310652407.8A CN201310652407A CN103694974A CN 103694974 A CN103694974 A CN 103694974A CN 201310652407 A CN201310652407 A CN 201310652407A CN 103694974 A CN103694974 A CN 103694974A
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- Prior art keywords
- chromium
- additive
- linking agent
- linking
- polyacrylamide
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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
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a chromium-free crosslinking system which comprises the following components in percentage by weight: 0.2-0.6wt% of crosslinking agent host, 0.1-0.3wt% of additive, 0.3-0.6wt% of polymer and the balance of water. The crosslinking agent can be aluminium citrate, polyhydroxymelamine etherate and low-crosslinking degree phenolic resin; the additive is thiourea; and the polymer is polyacrylamide. The chromium-free crosslinking system provided by the invention has the beneficial effects that the formed gel has certain viscosity and strength as well as fluidity and stability under certain pressure.
Description
Technical field
The invention belongs to petroleum chemistry technical field, especially relate to a kind of Chrome-free cross-linking system.
Background technology
In recent years, the development of the crosslinking technological of polymkeric substance is very fast, and existing many different linking agent products come out, and are widely applied in oil field.
The linking agent of different structure, different performance, various processes, different prices has occupied one seat in oilfield chemistry field, has also promoted the development of oil field at home chemical agent.The linking agent using has air aldehyde resin class, polyvalent metal ion etc.Aldehydes and the general temperature of resene linking agent are difficult to plastic lower than 40 ℃ or gelation time is longer, and the gel-strength of the low formation of polymer concentration is not high; Metal ion class blocking agent plastic wider range, gel-strength is high, but gelation time is short, and operability is poor.
In theory, metallic cation more than trivalent can with polyfunctional compound generation crosslinking reaction, valence state is higher, plastic tendency is stronger.The metallic-ion crosslinking agents such as chromium, aluminium, titanium, zirconium and iron are all the focuses of Recent study, but at home and abroad in oil field, linking agent or organometallic aluminium and the organo-metallic chromium system of Chang Shiyong.
Because the optimum response pH value of Tiorco 677 ion crosslinking agent is 5～6, unstable under alkaline condition.China's terrestrial facies become the primitive water of oily reservoir to take Sodium Hydrogen Carbonate type as main, pH value is 8～9, under such condition, aluminum crosslinker system is easily decomposed, generate aluminum hydroxide precipitation, therefore, Tiorco 677 linking agent system is only applicable to the environment of the Oil Reservoir Types such as external marine petroleum reservoir and China Zhongyuan Oil Field, in the most of oil reservoir condition and range of Er China, can not reach best plastic condition, and application is subject to restriction to a certain extent.Compare with aluminium system, the applicable elements of organic chromium system is comparatively extensive, and applicable pH range is 6～10, and the best is 8～9, and the salinity of tolerance and temperature are all very high.The gel-formation power of organic chromium system is main relevant with state of aggregation (monomer, dimer or tripolymer) and the ligand structure thereof of chromium.But chromium metal pair environment is unfriendly, toxic.
Country advocates the sustainable development of environmental protection and the energy, researchs and develops a kind of chromium-free environment-friendly, plastic temperature range linking agent wider, that polymkeric substance working concentration is low is necessary for this reason.
Summary of the invention
The object of this invention is to provide a kind of Chrome-free cross-linking system, the different reservoir profiles that satisfied temperature is 40-150 ℃, the technical requirements of water blockoff.
Technical scheme of the present invention is: Chrome-free cross-linking system, consists of by mass percentage: linking agent host 0.2～0.6wt%, additive 0.1～0.3wt%, polymer loading are at 0.3～0.6wt%%, and surplus is water.Described linking agent can be Tiorco 677, poly-hydroxy trimeric cyanamide etherate, low crosslinking degree resol, and described additive is thiocarbamide, and described polymkeric substance is polyacrylamide.
Advantage and positively effect that the present invention has are: this programme has good gel-forming property, what in plastic system, have lower polymkeric substance and a linking agent critically becomes gum concentration to form to take intermolecular cross-linking as main partial 3 d reticulated structure, formed gel has certain gluing, intensity, and there is mobility and the stability under certain pressure, there is good compatibleness with multiple polymers, can be effectively, improve significantly the viscosity of polymers soln, improve the temperature resistance of polymkeric substance, anti-salt, anti-shear performance, the applicable elements of cross-linking system is extensive, applicable pH value scope 6～10, gelation time is adjustable, in consumption and handiness, all there is higher choice.
Embodiment
Embodiment 1, under 50 ℃ of conditions, in the on-the-spot water of 500g, under stirring, electric mixer 400r slowly adds 1.5g polyacrylamide, stir 2h, add 1.0g Tiorco 677, stir 15min, then add 0.75g thiocarbamide, stir 15min, aqueous solution pH is 6.9, and when gelation time is 2h, gelling strength is 10000mPas.
Embodiment 2, under 100 ℃ of conditions, in the on-the-spot water of 500g, under stirring, electric mixer 400r slowly adds 2.5g polyacrylamide, stir 2h, add 1.5g poly-hydroxy trimeric cyanamide etherate, stir 15min, then add 2.5g thiocarbamide, stir 15min, aqueous solution pH is 8.0, and when gelation time is 2h, gelling strength is 8000mPas.
Embodiment 3, under 130 ℃ of conditions, in 500g sodium-chlor water, under stirring, electric mixer 400r slowly adds 1.75g polyacrylamide, stir 2h, add 1.75g low crosslinking degree resol, stir 15min, then add 1.75g thiocarbamide, stir 15min, aqueous solution pH is 6.7, and when gelation time is 2h, gelling strength is 8000mPas.
Above one embodiment of the present of invention are had been described in detail, but described content is only preferred embodiment of the present invention, can not be considered to for limiting practical range of the present invention.All equalization variations of doing according to the present patent application scope and improvement etc., within all should still belonging to patent covering scope of the present invention.
Claims (4)
1. Chrome-free cross-linking system, consists of: linking agent host 0.2～0.6wt%, additive 0.1～0.3wt%, polymer loading are at 0.3～0.6wt%%, and surplus is water by mass percentage.
2. Chrome-free cross-linking system according to claim 1, is characterized in that: linking agent host is Tiorco 677, and additive is thiocarbamide, and polymkeric substance is polyacrylamide.
3. Chrome-free cross-linking system according to claim 1, is characterized in that: linking agent host is poly-hydroxy trimeric cyanamide etherate, and additive is thiocarbamide, and polymkeric substance is polyacrylamide.
4. Chrome-free cross-linking system according to claim 1, is characterized in that: linking agent host is low crosslinking degree resol, and additive is thiocarbamide, and polymkeric substance is polyacrylamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310652407.8A CN103694974A (en) | 2013-12-04 | 2013-12-04 | Chromium-free crosslinking system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310652407.8A CN103694974A (en) | 2013-12-04 | 2013-12-04 | Chromium-free crosslinking system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103694974A true CN103694974A (en) | 2014-04-02 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310652407.8A Pending CN103694974A (en) | 2013-12-04 | 2013-12-04 | Chromium-free crosslinking system |
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| CN (1) | CN103694974A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178098A (en) * | 2014-08-01 | 2014-12-03 | 克拉玛依市正诚有限公司 | High-strength gel profile control and plugging agent as well as preparation method and application method thereof |
| CN104403053A (en) * | 2014-11-14 | 2015-03-11 | 天津大港油田滨港集团博弘石油化工有限公司 | Polymer water-plugging precrosslinked oil displacement profile control agent for oil recovery and preparation method thereof |
| CN105860947A (en) * | 2016-04-19 | 2016-08-17 | 中国石油天然气股份有限公司 | Slowly-degradable high-temperature-resistant high-salinity profile control agent and preparation method thereof |
| CN106675540A (en) * | 2016-11-21 | 2017-05-17 | 山东诺尔生物科技有限公司 | Temperature-resistant salt-resistant profile control plugging agent and preparation method thereof |
| CN107365573A (en) * | 2017-06-13 | 2017-11-21 | 中国石油天然气集团公司 | A kind of preparation method and application of middle low-temperature environment-friendly crosslinking agent |
| CN109364418A (en) * | 2018-11-26 | 2019-02-22 | 山东科技大学 | A kind of plastigel material for preventing and treating spontaneous combustionof coal |
| CN111087990A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | High-temperature-resistant gel plugging agent composition and preparation method and application thereof |
| CN113249103A (en) * | 2021-06-01 | 2021-08-13 | 中国石油大学(华东) | Seawater-based polyacrylamide high-temperature jelly profile control system |
Citations (5)
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| CN1278545A (en) * | 2000-03-24 | 2001-01-03 | 大庆油田有限责任公司采油工艺研究所 | Flowable depth profile control agent |
| CN1810918A (en) * | 2006-01-19 | 2006-08-02 | 大庆石油学院 | Intramolecular Al cross-linked polymer gel and its prepn |
| CN101148582A (en) * | 2007-09-07 | 2008-03-26 | 成都理工大学 | Hydrophobic association micro-crosslinking polymer oil displacement agent and preparation method thereof |
| CN101255260A (en) * | 2008-04-22 | 2008-09-03 | 王志鹏 | Heatproof salt-resistant cross-linking polymer system |
| US20110180256A1 (en) * | 2008-10-13 | 2011-07-28 | M-I L.L.C. | Chrome free water-based wellbore fluid |
-
2013
- 2013-12-04 CN CN201310652407.8A patent/CN103694974A/en active Pending
Patent Citations (5)
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| CN1278545A (en) * | 2000-03-24 | 2001-01-03 | 大庆油田有限责任公司采油工艺研究所 | Flowable depth profile control agent |
| CN1810918A (en) * | 2006-01-19 | 2006-08-02 | 大庆石油学院 | Intramolecular Al cross-linked polymer gel and its prepn |
| CN101148582A (en) * | 2007-09-07 | 2008-03-26 | 成都理工大学 | Hydrophobic association micro-crosslinking polymer oil displacement agent and preparation method thereof |
| CN101255260A (en) * | 2008-04-22 | 2008-09-03 | 王志鹏 | Heatproof salt-resistant cross-linking polymer system |
| US20110180256A1 (en) * | 2008-10-13 | 2011-07-28 | M-I L.L.C. | Chrome free water-based wellbore fluid |
Non-Patent Citations (3)
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| 刘庆旺等: "《弱凝胶调驱技术》", 31 December 2003, 石油工业出版社 * |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178098A (en) * | 2014-08-01 | 2014-12-03 | 克拉玛依市正诚有限公司 | High-strength gel profile control and plugging agent as well as preparation method and application method thereof |
| CN104403053A (en) * | 2014-11-14 | 2015-03-11 | 天津大港油田滨港集团博弘石油化工有限公司 | Polymer water-plugging precrosslinked oil displacement profile control agent for oil recovery and preparation method thereof |
| CN105860947A (en) * | 2016-04-19 | 2016-08-17 | 中国石油天然气股份有限公司 | Slowly-degradable high-temperature-resistant high-salinity profile control agent and preparation method thereof |
| CN105860947B (en) * | 2016-04-19 | 2018-10-16 | 中国石油天然气股份有限公司 | Slowly-degradable high-temperature-resistant high-salinity profile control agent and preparation method thereof |
| CN106675540A (en) * | 2016-11-21 | 2017-05-17 | 山东诺尔生物科技有限公司 | Temperature-resistant salt-resistant profile control plugging agent and preparation method thereof |
| CN107365573A (en) * | 2017-06-13 | 2017-11-21 | 中国石油天然气集团公司 | A kind of preparation method and application of middle low-temperature environment-friendly crosslinking agent |
| CN111087990A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | High-temperature-resistant gel plugging agent composition and preparation method and application thereof |
| CN109364418A (en) * | 2018-11-26 | 2019-02-22 | 山东科技大学 | A kind of plastigel material for preventing and treating spontaneous combustionof coal |
| CN113249103A (en) * | 2021-06-01 | 2021-08-13 | 中国石油大学(华东) | Seawater-based polyacrylamide high-temperature jelly profile control system |
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Application publication date: 20140402 |