CN106084093A - A kind of water soluble chelated resin transfer drive, water shutoff agent preparation and application process - Google Patents
A kind of water soluble chelated resin transfer drive, water shutoff agent preparation and application process Download PDFInfo
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- CN106084093A CN106084093A CN201610419348.3A CN201610419348A CN106084093A CN 106084093 A CN106084093 A CN 106084093A CN 201610419348 A CN201610419348 A CN 201610419348A CN 106084093 A CN106084093 A CN 106084093A
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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
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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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
- C08F8/00—Chemical modification by after-treatment
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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
- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—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
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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Abstract
A kind of water soluble chelated resin transfer drive, water shutoff agent preparation and application process are field of oilfield chemistry, and the shortcoming which overcoming other technology at present, for oil field transfer drive, the present situation in water blockoff field, is introduced into oil field transfer drive, water blockoff field；Water soluble chelated resin absorbs in the water of oil field and the mineral ion on formation skeleton surface, produces nano_scale particle, and with the increase of particle concentration in system, between microgranule, mutually absorption forms nanogel；Nano-resin gel adsorption, in the rock matrix surface of its flowed through regional stratum, reduces high permeability area territory, stratum permeability；On the other hand nano-resin gel slug is promoted comprehensively under water injection pressure drives, expand swept volume, thus water soluble chelated resin profile control agent has " block up, drive " dual function concurrently, the mineral constituent utilizing water soluble chelated resin to combine reservoir fluid self in the earth formation forms the characteristic of gel for oil field transfer drive, water blockoff, realize oil field " steady oil, control water ", improve recovery ratio.
Description
Technical field
The present invention relates to field of oilfield chemistry, especially a kind of water soluble chelated resin transfer drive, water shutoff agent preparation and application
Method.
Background technology
Profile control, transfer drive are waterflooding oil field middle and late stage " steady oil, control water ", improve the important means of recovery ratio.The most main
System to be applied is the polymeric systems such as polymer gel, Weak Gels, polymer microballoon, polymer Weak gel particle, and
Slope soil, cement, flyash, oil field sludge are the suspension profile control system that the inorganic particle class of main body adds some adjuvants.
Various underground crosslinked system based on polyacrylamide is originally the harshest at ground Gelation Conditions, injects in addition
In journey system component in formation pore for a long time migration cause absorption, dilute, shear, degraded etc., cause partial cross-linked body
System cannot cross-link；Polymerization species profile control agent adaptive temperature less than 90 DEG C, formation water salinity must not exceed the oil of 50000mg/L
Layer condition, applies limited at high temperature, high mineralization oil reservoir；System base fluid viscosity is high, poor for low-permeability oilfield injection, is not suitable for deep
Portion's transfer drive；Inorganic particle class suspension system, pre-crosslinking polymer, injection is poor, is only capable of entering near wellbore zone and improves water injection profile,
But poor selectivity, notes after the well profile modification even having and does not intake.
Summary of the invention
It is an object of the invention to provide that to have excellent temperature resistance, salt tolerance, one high temperature resistant, high salinity reservoirs water-soluble
Property chelating resin transfer drive, water shutoff agent preparation and application process, the shortcoming which overcoming at present other technology, it is an object of the invention to
It is achieved in that, for oil field transfer drive, the present situation in water blockoff field, water soluble chelated resin is introduced oil field transfer drive, water blockoff field；
Water soluble chelated resin " is gathered materials on the spot " to absorb and is combined in the water of oil field and the mineral ion on formation skeleton surface, produces nanoscale
Microgranule (mean particle dia 50nm), with the increase of particle concentration in system, between microgranule, mutually absorption forms nanogel；Nanotrees
Fat gel adsorption, in the rock matrix surface of its flowed through regional stratum, reduces high permeability area territory, stratum permeability；On the other hand receive
Rice resin gel slug is promoted comprehensively under water injection pressure drives, expansion swept volume, thus water soluble chelated resin profile control agent
Having " block up, drive " dual function concurrently, the mineral constituent utilizing water soluble chelated resin to combine reservoir fluid self in the earth formation is formed
Gel characteristic for oil field transfer drive, water blockoff, it is achieved oil field " steady oil, control water ", improve recovery ratio.
The water soluble chelated resin of the present invention is specifically made up of water soluble polymer skeleton and functional activity group, water-soluble
Property macromolecular scaffold be to be prepared by glycidyl methacrylate and the polymerization of two kinds of monomers of ethyleneglycol dimethyacrylate,
Water soluble polymer molecule of the skeleton amount is less than 15000, and the degree of cross linking is 18%；Its activity functional groups is by high to water solublity
Molecular skeleton ammonolysis and second chloric acidization obtain, and ammonolysis degree is more than 80%, and activity functional groups is carboxyl and amine carboxyl.
The present invention is in use, it can produce nano_scale particle, mean particle dia 50nm, satellite in conjunction with the mineral ion in water
The increase of particle concentration in system, between microgranule, mutually absorption forms gel nano-resin gel；Water soluble chelated resin is utilized to exist
Stratum combines mineral ion contained by oil-reservoir water self and forms the characteristic of gel, for oil field transfer drive, water blockoff, improve oil field and gather
Rate.
The preparation method is that: the first step, first will account for the methyl-prop that reaction system mass percent is 30%-50%
Olefin(e) acid ethylene oxidic ester and two kinds of monomers of ethyleneglycol dimethyacrylate are put in head tank and are mixed, wherein methacrylic acid contracting
Water glyceride and ethyleneglycol dimethyacrylate mass ratio are 10:3-10:1, and initiator azodiisobutyronitrile is added mixing
In monomer, its concentration is the 0.15%-0.35% of reaction system quality, then mixing raw material adds the reaction having excess water in advance
In still, excess water is tap water；Reacting 2 hours at a temperature of 40-50 DEG C, the prepared degree of cross linking is that 18% polymethylacrylic acid shrinks
Glyceride resin；
Second step, by the degree of cross linking be slowly add under 18% poly (glycidyl methacrylate) resin stirs in reactor dense
Degree is 25%-28% ammonia, and dosage is the 6%-8% of first step mixing raw materials quality, and room temperature ammonolysis reaction 24 hours prepares ammonolysis degree
Poly-methylamino glycerol resin more than 80%；
3rd step, in the ammonolysis degree poly-methylamino glycerol resin more than 80%, adding concentration is 30% sodium chloroacetate solution, its
Dosage is the 8%-10% of first step mixing raw materials quality, course of reaction dropping sodium carbonate liquor, keeps reaction system PH to 8-10,
React 5 hours at a temperature of 50-60 DEG C, prepared water-soluble poly methyl amine carboxyl glycerol resin, concentrated dehydration, pelletize, drying,
Obtain water soluble chelated resin transfer drive, water shutoff agent.
The performance indications of the present invention: outward appearance is white or canescence granule；Solid content is 85%；Bulk density is 1.05-
1.35g/cm3；Granularity 18-60 mesh >=80%；Dissolubility >=15g(temperature 20 DEG C)；Degree of gelation >=80%.
The index when present invention applies is, injects 0.6PV, and reservoir core plugging rate is all higher than 80%；Long cores post is uniformly sealed
Stifled；(water solublity chelates the closure resistance to erosion of nano-resin gel formation for experiment condition: temperature 120 DEG C, salinity 15.7 ten thousand ppm
Resin concentration 2%).
The nano-resin gel that the water soluble chelated resin of the present invention is formed is steady in a long-term under 400 DEG C of temperature conditionss,
Do not affected by formation water salinity simultaneously；Water soluble chelated resin good water solubility, base fluid viscosity is less than 100mpa.s.
Meaning of the present invention is, the nano-resin gel that the water soluble chelated resin of the present invention is formed is 400 DEG C of temperature
Under the conditions of steady in a long-term, do not affected by formation water salinity simultaneously, thus be there is excellent temperature resistance, salt tolerance, meet high temperature,
High salinity reservoirs transfer drive, the needs of water blockoff, it is adaptable to the envelope has channeling operation of steam injection development viscous crude field；Water solublity chelating tree
Fat good water solubility, base fluid viscosity be less than 100mpa.s, injection is good, it is adaptable to oil deposit deep part transfer drive, it is adaptable to LOW PERMEABILITY RESERVOIR and
Oil deposit deep part after many wheel transfer drives is taped the latent power transfer drive.During on-the-spot application, the water soluble chelated resin transfer drive of the present invention, water shutoff agent can be used
Transfer drive pump injects at well head, it is possible to water soluble chelated resin is made into concentrated solution dosing pump and injects water filling flow process by a certain percentage
System online injection.
Detailed description of the invention
Embodiment 1, the present invention are specifically made up of water soluble polymer skeleton and functional activity group, water soluble polymer bone
Frame is to be prepared by glycidyl methacrylate and two kinds of monomer polymerizations of ethyleneglycol dimethyacrylate, water solublity high score
Sub-molecule of the skeleton amount is less than 15000, and the degree of cross linking is 18%；Its activity functional groups is by water soluble polymer skeleton ammonia
Solving and second chloric acidization obtains, ammonolysis degree is more than 80%, and activity functional groups is carboxyl and amine carboxyl.
Embodiment 2, the present invention are in use, it can produce nano_scale particle, mean particle dia in conjunction with the mineral ion in water
50nm, with the increase of particle concentration in system, between microgranule, mutually absorption forms gel nano-resin gel；Utilize water solublity chela
Resin combines mineral ion contained by oil-reservoir water self in the earth formation and forms the characteristic of gel, for oil field transfer drive, water blockoff, improves
Oil recovery rate.
Embodiment 3, the preparation method is that: the first step, standby tap water 1200KG in reactor, by 600KG first
Base glycidyl acrylate monomer and 200KG ethyleneglycol dimethyacrylate raw material monomer are in in-tank mixing, by 4KG azo
Bis-isobutyronitrile complex is dissolved in mix monomer, starts blender, mixing raw material is added reactor, is to slowly warm up to 40-50 DEG C,
Reaction 2 hours at this temperature, the prepared degree of cross linking is 18% poly (glycidyl methacrylate) resin；
Second step, by the degree of cross linking be slowly add under 18% poly (glycidyl methacrylate) resin stirs in reactor dense
Degree is the ammonia 50KG of 25%, room temperature ammonolysis reaction 24 hours, to the ammonolysis degree poly-methylamino glycerol resin more than 80%；
3rd step, in the ammonolysis degree poly-methylamino glycerol resin more than 80%；Adding 70KG concentration is that 30% sodium chloroacetate is molten
Liquid, drips sodium carbonate liquor, keeps reaction system PH to 8-10, reacts 5 hours at a temperature of 50-60 DEG C, prepares water-soluble poly
Methyl amine carboxyl glycerol resin, concentrated dehydration, pelletize, drying, obtain water soluble chelated resin transfer drive, water shutoff agent.
Embodiment 4, the performance indications of the present invention: outward appearance is white or canescence granule；Solid content is 85%；Bulk density
For 1.05-1.35g/cm3；Granularity 18-60 mesh >=80%；Dissolubility >=15g(temperature 20 DEG C)；Degree of gelation >=80%.
Index when embodiment 5, the present invention apply is, injects 0.6PV, and reservoir core plugging rate is all higher than 80%；Long cores post obtains
To uniformly closure；The closure resistance to erosion of nano-resin gel formation, its temperature 120 DEG C, salinity 15.7 ten thousand ppm, water solublity chela
Resin concentration 2%；The present invention is steady in a long-term under 400 DEG C of temperature conditionss, is not affected by formation water salinity simultaneously；Water-soluble
Property chelating resin good water solubility, base fluid viscosity be less than 100mpa.s.
Claims (5)
1. a water soluble chelated resin transfer drive, water shutoff agent are made up of water soluble polymer skeleton and functional activity group, its
Feature is: water soluble polymer skeleton is by glycidyl methacrylate and two kinds of lists of ethyleneglycol dimethyacrylate
Body polymerization prepares, and water soluble polymer molecule of the skeleton amount is less than 15000, and the degree of cross linking is 18%；Its activity functional groups is to pass through
Obtaining water soluble polymer skeleton ammonolysis and second chloric acidization, ammonolysis degree is more than 80%, and activity functional groups is carboxyl and amine carboxylic
Base.
2. a kind of water soluble chelated resin transfer drive, the application process of water shutoff agent described in claim 1, is characterized in that: it can be in conjunction with
Mineral ion in water produces nano_scale particle, and mean particle dia 50nm, with the increase of particle concentration in system, between microgranule mutually
Absorption forms gel nano-resin gel；Water soluble chelated resin is utilized to combine mineral ion contained by oil-reservoir water self in the earth formation
Form the characteristic of gel, for oil field transfer drive, water blockoff, improve oil recovery rate.
3. a kind of water soluble chelated resin transfer drive, the preparation method of water shutoff agent described in claim 1, is characterized in that: the first step, first
First will account for glycidyl methacrylate and ethyleneglycol dimethyacrylate that reaction system mass percent is 30%-50%
Two kinds of monomers are put in head tank and are mixed, wherein glycidyl methacrylate and ethyleneglycol dimethyacrylate mass ratio
For 10:3-10:1, being added in mix monomer by initiator azodiisobutyronitrile, its concentration is the 0.15%-of reaction system quality
0.35%, then mixing raw material is added and has in the reactor of excess water in advance, excess water is tap water；At a temperature of 40-50 DEG C
Reacting 2 hours, the prepared degree of cross linking is 18% poly (glycidyl methacrylate) resin；
Second step, by the degree of cross linking be slowly add under 18% poly (glycidyl methacrylate) resin stirs in reactor dense
Degree is 25%-28% ammonia, and dosage is the 6%-8% of first step mixing raw materials quality, and room temperature ammonolysis reaction 24 hours prepares ammonolysis degree
Poly-methylamino glycerol resin more than 80%；
3rd step, in the ammonolysis degree poly-methylamino glycerol resin more than 80%, adding concentration is 30% sodium chloroacetate solution, its
Dosage is the 8%-10% of first step mixing raw materials quality, course of reaction dropping sodium carbonate liquor, keeps reaction system PH to 8-10,
React 5 hours at a temperature of 50-60 DEG C, prepared water-soluble poly methyl amine carboxyl glycerol resin, concentrated dehydration, pelletize, drying,
Obtain water soluble chelated resin transfer drive, water shutoff agent.
4. a kind of water soluble chelated resin transfer drive, the performance indications of water shutoff agent described in claim 1, is characterized in that: outward appearance is white
Color or canescence granule；Solid content is 85%；Bulk density is 1.05-1.35g/cm3；Granularity 18-60 mesh >=80%；In temperature 20
In the case of DEG C, dissolubility >=15g；Degree of gelation >=80%.
5. a kind of water soluble chelated resin transfer drive, water shutoff agent application process described in claim 2, is characterized in that: in temperature 120
DEG C, salinity 15.7 ten thousand ppm, in the case of water soluble chelated resin concentration 2%, inject 0.6PV, reservoir core plugging rate is all higher than
80%；Long cores post is uniformly blocked；The closure resistance to erosion of nano-resin gel formation；Under 400 DEG C of temperature conditionss the most surely
Fixed, do not affected by formation water salinity simultaneously；Aqueous solution base fluid viscosity is less than 100mpa.s.
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| CN201610419348.3A CN106084093A (en) | 2016-06-14 | 2016-06-14 | A kind of water soluble chelated resin transfer drive, water shutoff agent preparation and application process |
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| CN201610419348.3A CN106084093A (en) | 2016-06-14 | 2016-06-14 | A kind of water soluble chelated resin transfer drive, water shutoff agent preparation and application process |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050132931A1 (en) * | 2003-12-23 | 2005-06-23 | Samsung Electronics Co., Ltd. | Block copolymeric dispersant for pigment particle in aqueous system, and ink composition comprising the same |
| CN101235283A (en) * | 2008-03-04 | 2008-08-06 | 湖北大学 | Method for preparing amphiprotic polyacrylamide oil field compression fracture thickening agent |
| CN102603969A (en) * | 2011-10-17 | 2012-07-25 | 中国石油化工股份有限公司 | Cemented gel plugging agent and preparation method thereof |
-
2016
- 2016-06-14 CN CN201610419348.3A patent/CN106084093A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050132931A1 (en) * | 2003-12-23 | 2005-06-23 | Samsung Electronics Co., Ltd. | Block copolymeric dispersant for pigment particle in aqueous system, and ink composition comprising the same |
| CN101235283A (en) * | 2008-03-04 | 2008-08-06 | 湖北大学 | Method for preparing amphiprotic polyacrylamide oil field compression fracture thickening agent |
| CN102603969A (en) * | 2011-10-17 | 2012-07-25 | 中国石油化工股份有限公司 | Cemented gel plugging agent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 曾佑林等: ""一种新型亲水性胺基羧酸树脂的合成及其性能研究"", 《离子交换与吸附》 * |
| 王德中: "《环氧树脂生产与应用》", 30 June 2001 * |
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Inventor after: Zhang Zongxiao Inventor after: Zhang Yu Inventor after: Liu Qingsong Inventor after: Zhang Zhengwei Inventor after: Zhang Shang Inventor before: Zhang Zongxiao Inventor before: Zhang Yu Inventor before: Zhang Zhengwei Inventor before: Zhang Shang |
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