CN105154054B - A kind of tertiary amine participates in crosslinking polymer oil displacement agent of synthesis and preparation method thereof - Google Patents
A kind of tertiary amine participates in crosslinking polymer oil displacement agent of synthesis and preparation method thereof Download PDFInfo
- Publication number
- CN105154054B CN105154054B CN201510484051.0A CN201510484051A CN105154054B CN 105154054 B CN105154054 B CN 105154054B CN 201510484051 A CN201510484051 A CN 201510484051A CN 105154054 B CN105154054 B CN 105154054B
- Authority
- CN
- China
- Prior art keywords
- solution
- oil displacement
- displacement agent
- preparation
- tertiary amine
- 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.)
- Active
Links
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
- C09K8/58—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Crosslinking polymer oil displacement agent of synthesis and preparation method thereof is participated in the invention discloses a kind of tertiary amine, its raw material constituent component mainly includes acrylamide, potassium peroxydisulfate, sodium hydrogensulfite and pentamethyl-diethylenetriamine；Its preparation method：Feed components are dissolved in the solution that each component is prepared in the deionized water no less than its 1.0 times of mass parts of formula ratio respectively；Acrylamide solution, pentamethyl-diethylenetriamine solution are added in reactor, nitrogen is passed through at stirring, 10~30 DEG C and removes the oxygen discharged in container, add potassium persulfate solution and solution of sodium bisulfite, question response system starts to polymerize, viscosity substantially increases, stopping is passed through nitrogen and stirring, and polymerisation is constant to temperature, that is, gluey oil displacement agent is prepared.The present invention has good performance, ageing resistance, temperature-resistant anti-salt performance.
Description
Technical field
The present invention relates to the technical field of high polymer material oil displacement agent, physical relationship is poly- to a kind of crosslinking of part branched moiety
Compound oil displacement agent and preparation method thereof.
Background technology
According to the difference of phase of development, oil exploitation is generally divided into three phases：Oil is exploited using oil reservoir energy
Primary oil recovery, the oil recovery efficiency in this stage typically only 15% or so；By injecting water, gas to oil reservoir, oil reservoir energy is supplemented
Measure so as to reach exploitation purpose for secondary oil recovery, tar productivity is 30~40%；Opened by new technologies such as physics, chemistry, biologies
The stage for adopting crude oil is tertiary oil recovery.In order to efficiently that residual oil in stratum is mined, need exploitation badly and be suitable for China spy
The tertiary oil recovery method of different geological conditions.The more ripe tertiary oil recovery technology of development mainly has four major classes：Chemical flooding, heating power
Drive, microorganism is driven and mixed phase is driven.Based on the understanding to reservoir geologic character and residual oil, chemical flooding turns into China majority oil field
Improve the important means of oil recovery.And the core of chemical flooding is the design synthesis and the design of oil displacement system of oil displacement agent.It is poly-
It is the mostly important technology of chemical flooding that compound, which drives, i.e., by adding polymer in water is injected, increases displacement phase viscosity, adjustment oil
Water mobility ratio, expand displacing phase swept volume, strengthen displacement efficiency, so as to improve oil displacement efficiency most possibly.Polymer flooding
Simple to operate, cost is relatively low, can be used in combination with profile-controlling and plugging agent, has certain permeability adjustment effect concurrently.
As artificial synthesized water soluble polymer, the compound of birdsing of the same feather flock together of the synthesis based on polyacrylamide and its derivative is
It is most widely used in chemical flooding at present, obtain the most prominent polymer oil-displacing agent of effect.Divided according to the structure of polyacrylamide,
Linear polyacrylamide and crosslinked polyacrylamide can be divided into again.
The polyacrylamide of cross-linking type can make profile-controlling and plugging agent use, because the swollen property of its good body can be carried out to high permeability formation
Profile control processing adjusts its permeability.But fully crosslinked polyacrylamide, because the degree of cross linking is high, hardness is big, and morphotropism is poor,
Migrated in hole difficult, it is impossible to play a part of oil displacement agent, therefore the use in tertiary oil recovery is restricted.Chinese patent
CN102731718A discloses a kind of crosslinking polyacrylamide reacted with aldehyde radical hydrogen, and its is easy for construction, and plastic is stable, device to hole
The profile control effect of gap is good, the extensive use in the note polymerizing technology of oil exploitation.Chinese patent CN1796484A disclose it is a kind of with
Acrylamide and acrylic acid are as host, and using bentonite or kaolin as reinforcing agent, N, N- methylene-bisacrylamides is hand over
Connection agent prepares the granular profile control agent of crosslinking copolymerization type.The linear polyacrylamide (HPAM) of partial hydrolysis uses master as oil displacement agent
If the increase swept volume that the viscosity based on its increase aqueous solution plays, improves the effect of mobility ratio.Chinese patent
CN00111320 reports have synthesized the polyacrylamide for the anionic that relative molecular mass is 2800-3600 ten thousand.It is in addition, Chinese
Patent CN102964519A discloses a kind of super high molecular weight amphiprotic polyacrylamide, and its relative molecular mass can reach
42800000.But under high temperature and high salt and the reservoir condition of serious heterogeneity, the polymer solution that HPAM is formed is to high permeability formation
Shut-off capacity is poor, is unfavorable in inhomogeneous formation effectively adjusting permeability, and HPAM agings are serious, and viscosity drastically declines,
To the bad adaptability of inhomogeneous formation, it is difficult to meet the requirement for improving recovery ratio.
The content of the invention
The deficiency of polymer oil-displacing agent is prepared for prior art, primary and foremost purpose of the invention, which is to provide one kind, has part
The tertiary amine of branched moiety cross-linked structure participates in the crosslinking polymer oil displacement agent of synthesis, to improve the heat and salt resistance of oil displacement agent
Energy and ageing resistace；Second object of the present invention is to provide the crosslinking polymer oil displacement agent that the tertiary amine participates in synthesis
Preparation method.
For the primary and foremost purpose of the present invention, tertiary amine provided by the invention participates in the crosslinking polymer oil displacement agent of synthesis,
Function monomer and crosslinking agent are used as using pentamethyl-diethylenetriamine (PMTDA), potassium sulfate-sodium hydrogensulfite is as primosome
System, PMTDA first pass through initiator and form branched structure, further couple termination and form part cross-linked structure, finally prepare portion
Divide the polymer oil-displacing agent being crosslinked and containing a large amount of branched structures.Its raw material constituent mainly includes in parts by weight：
For second object of the present invention, tertiary amine provided by the invention participates in synthesizing cross-linked type polymer oil-displacing agent
Preparation method, mainly comprise the technical steps that：
(1) preparation of solution, each component of raw material is dissolved in the deionization no less than its 1.0 times of mass parts of formula ratio respectively
In water, the solution of each component is prepared；
(2) polymerisation prepares oil displacement agent, and acrylamide solution, the pentamethyl-diethylenetriamine that step (1) is prepared add
Enter in reactor, after being passed through the oxygen that nitrogen is fully discharged in reactor and in reaction solution at stirring, 10~30 DEG C, added
Potassium sulfate solution and solution of sodium bisulfite initiated polymerization, question response, which polymerize to system viscosity, substantially to be increased, and stops being passed through
Nitrogen and stirring, system gel follow-up continuation of insurance warm 2-4 hours are treated, that is, gel oil displacement agent is prepared.
In order to facilitate the use of oil displacement agent, the present invention can participate in synthesizing cross-linked type polymer oil-displacing agent in above-mentioned tertiary amine
On the basis of preparation method, obtained gluey oil displacement agent is shredded, dried, crushed, sieved, to obtain the granular displacement of reservoir oil
Agent.
In the preparation method that tertiary amine of the present invention participates in synthesizing cross-linked type polymer oil-displacing agent, not only require logical
Enter the oxygen in nitrogen removing reactor, also require to remove the oxygen in reaction solution, therefore in reaction system viscosity substantially increase
All need to be passed through nitrogen before.The degree of logical nitrogen deoxygenation, it is related to the addition of potassium peroxydisulfate and sodium hydrogensulfite, discharge oxygen
Degree is high, adds the amount of potassium peroxydisulfate and sodium hydrogensulfite and can lack, and it is low to discharge the degree of oxygen, add potassium peroxydisulfate and
The amount of sodium hydrogensulfite can be larger, and appropriate cooperation then can initiated polymerization.
In the preparation method that tertiary amine of the present invention participates in synthesizing cross-linked type polymer oil-displacing agent, acrylamide is molten
Liquid, pentamethyl-diethylenetriamine solution preferably sequentially add reactor, be passed through under agitation nitrogen fully discharge in reactor and
Oxygen in reaction solution, sequentially adds potassium persulfate solution and solution of sodium bisulfite afterwards.
In the preparation method that tertiary amine of the present invention participates in synthesizing cross-linked type polymer oil-displacing agent, polymerisation
Initiation temperature is low, then reaction is carried out slower；Initiation temperature is too high, then reaction is carried out too fast, crosslinking can be brought imperfect, polymerization is anti-
Initiation temperature is answered typically to can be controlled in 10~30 DEG C of scopes.
In the preparation method that tertiary amine of the present invention participates in synthesizing cross-linked type polymer oil-displacing agent, each component is dissolved
The total amount of deionized water be generally 3~4 times of each raw material components total amount.Further, preferably take 100 parts of acrylamides
It is dissolved in wiring solution-forming in 150~360 parts of deionized water；0.025~0.108 part of pentamethyl-diethylenetriamine is dissolved in 10-50
Wiring solution-forming in the deionized water of part；0.03~0.05 part of potassium peroxydisulfate is dissolved in wiring solution-forming in 10~50 parts of deionized waters；
0.03~0.05 part of sodium hydrogensulfite is dissolved in wiring solution-forming in 10~50 parts of deionized waters.
Compared with prior art, the present invention has the advantages of following very prominent and technique effect：
1st, the crosslinking polymer oil displacement agent for preparing of the present invention has cross-linked polyacrylamide and linear polyacrylamide concurrently
Advantage.Wherein, branched structure assigns the good suspending power of its aqueous solution and higher viscosity, and suspension volume can reach 90%
More than, the viscosity that rheometer measures under 1000 μm of spacing may be up to 330.2mPaS, its cross-linked structure provide good elasticity and
Anti-shear ability, the modulus of elasticity that rheometer measures under 200 μm of spacing can reach 11.9Pa.
2nd, due in the structure of crosslinking polymer oil displacement agent that is prepared in the present invention there is branched chain structure, thus its
Suspension has good suspendability, and it is low to overcome traditional crosslinked polyacrylamide viscosity, the shortcomings of free settling.
3rd, crosslinking polymer oil displacement agent prepared by the present invention is compared with conventional linear acrylamide's oil displacement agent, in aging
During, its viscosity is one and first increases the process reduced again, has unique thickening behavior, and polymer suspension viscosity can
To be retained in a higher level within very long a period of time, the aging 90 days in 85 DEG C, 30000 salinity salt solution, its
Viscosity retention ratio is still up to 141%.
4th, crosslinking polymer oil displacement agent prepared by the present invention can migrate well in rock core, and two-tube rock core seepage flow is real
Test and show that it has efficient section corrective action.
Brief description of the drawings
Fig. 1 be HPAM under different salinity viscosity with shear rate change curve.
Fig. 2 be part branched moiety crosslinking polymer oil displacement agent of the present invention under different salinity viscosity with shear rate
Change curve.
Fig. 1 and Fig. 2 is respectively that HPAM and the product of embodiments of the invention 4 viscosity under different salinities become with shear rate
Change curve, it can be seen that with the increase of salinity, HPAM viscosity reduces successively；Partial cross-linked part branching type polyacrylamide
Amine oil displacement agent is in pure waterCurve is apparently higher than its curve in salt solution, but salinity increases to from 6666mg/L
50000mg/L, itsCurvilinear motion is little, and the increase mesohalobic to solution of its viscosity is insensitive.This is due to production of the present invention
The presence of the special partial cross-linked part branched structure of thing so that do not hydrolyze hyper-branched chain molecular structure and steric hindrance to sun
Ion attack electric double layer and high volence metal ion complexing carboxylic ions have stronger inhibitory action, therefore show good resistance to
Salt performance.
Fig. 3 is that the single tube seepage flow of branched moiety crosslinking polymer oil displacement agent in part of the present invention is tested.(fill out sand tube permeates
Rate：(1500±15)×10-3um2, solution salinity：19334mg/L, suspension concentration：0.15wt%)
Fig. 4 is the two-tube Seepage Experiment (permeability of part branched moiety crosslinking polymer oil displacement agent：1000/5000×
10-3um2, solution salinity：19334mg/L, suspension concentration：0.15wt%)
Fig. 3, Fig. 4 are respectively the single tube of the product of embodiment 2 and two-tube seepage flow performance test.From figure 3, it can be seen that fill out sand tube
In to play pressure very fast, and fluctuate obvious, the final pressure that balances reaches more than 1.2MPa, shows partial cross-linked part branching type polypropylene
Acid amides oil displacement agent Flooding Efficiency of being migrated in hole is good.Fig. 4 two-tube Seepage Experiment is respectively 5000 × 10 using permeability- 3um2With 1000 × 10-3um2Two parallel fill out sand tube research product selectivity profile control different size pore throats ability.Test shows,
When water drive balances, the ratio between shunt volume of hypertonic fill out sand tube and hypotonic fill out sand tube about 5:1, meet the ratio between the two permeability.But
After part crosslink part branching type POLYACRYLAMIDE FLOODING agent suspension is injected, the flow of hypertonic fill out sand tube tapers into and low
Ooze fill out sand tube flow and become big, produce uncommon reversal development.The reversal development of this shunt volume is referred to as " fluid diversion ".Driving
During replacing, the Liquid output of height osmos tube is up to 43.18%：56.82%, declaratives crosslink part branching type poly- third
Acrylamide oil displacement agent particle serves the effect for effectively adjusting heterogeneous fill out sand tube section, low-permeability back-up sand is in control maximum
The exploitation of degree, the swept volume of hypotonic pipe is greatly improved, improve oil displacement efficiency.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be that the present embodiment is served only for pair
The present invention is further described, it is impossible to is interpreted as limiting the scope of the invention, the person skilled in the art in the field can
To make some nonessential modifications and adaptations according to the content of the invention described above.
Following correlated performance test is carried out as follows to polymer oil-displacing agent sample made from following examples：
1. rheology testing
Steady state shearing is tested：Using the AR2000ex rotational rheometers of TA companies, using 40mm plate modes, sheet separation is
1000μm；Viscosity test pattern is arranged to 7.34s-1Shear rate under time sweep, average obtain steady-state viscosity, survey
It is 85 DEG C to try temperature.
Dynamic concussion test：Using identical rheometer and flat board, dynamic concussion test is 1Hz, stress 0.1Pa in frequency
Under the conditions of carry out time sweep, average obtain viscoelastic data, according to different test requests, sheet separation is arranged to 200 μ
M and 1000 μm, corresponding test temperature is respectively set to 25 DEG C and 85 DEG C.
Branched moiety cross-linked polymer oil-displacing agent in part used in rheology testing is 100-150 mesh, the concentration of suspension
For 0.5wt%, salt water salinity is 30000mg/L.
The salt solution used is tested as the simulation water according to Shengli Oil Field difference oil reservoir salinity and salt ionic concentration preparation, no
It is as shown in table 1 with saline formulation.
Table 1
| Salinity | H2O | NaCl | CaCl2 | MgCl2·6H2O | Na2SO4 |
| 6666mg/L | 1000mL | 6.191g | 0.2414g | 0.3514g | 0.0696g |
| 19334mg/L | 1000mL | 17.4578g | 1.1433g | 0.863g | 0 |
| 30000mg/L | 1000mL | 27.3067g | 1.11g | 3.833g | 0 |
| 50000mg/L | 1000mL | 42.758g | 2.825g | 8.917g | 0 |
2. suspendability is tested
The heteropolymer suspension that the partial cross-linked polymer oil-displacing agent of determination part branchization is formed in salt solution hangs
Floating body accumulates.
3. ageing properties are tested
The part branched moiety for determining the 0.5wt% concentration prepared by the present invention in salinity is 30000mg/L salt solution is handed over
The ageing properties of linked polymer oil displacement agent and linear polyacrylamide (HPAM) polymer solution at 85 DEG C.
4. single tube rock core Seepage Experiment
To make fill out sand tube, a length of 30cm, internal diameter 2.5cm by oneself, the permeability of fill out sand tube is experiment porous media used
(1500±15)×10-3um2, pore volume (pore volume) is 50 ± 0.5cm3.Whole Seepage Experiment is in digital temperature-controlled box
Middle progress, fluid injection rate are 0.5mL/min, and experimental temperature is 70 DEG C.
Experimental method：First into fill out sand tube inject salinity be 19334mg/L salt solution, record at regular intervals into
Mouth pressure.After pressure balance, change note 2000mg/L part branched moiety cross-linked polymer oil-displacing agent suspension, time recording
Pressure, sequent water flooding is carried out after pressure balance to balance.
5. two-tube rock core Seepage Experiment
Experiment is respectively (1000 ± 10) × 10 using the permeability of high permeability and low-permeability fill out sand tube-3μm2With
(5000±15)×10-3μm2, the total pore size volume of two parallel seepage flow pipes is 101.6 ± 0.5cm3.Noted in a manner of closing note point and adopting
Enter salt solution and part branched moiety cross-linked polymer oil-displacing agent suspension, injection rate 0.5mL/min, experimental temperature 70
℃。
Experimental method：After it is 19334mg/L salt solution to inject 1PV (pore volume) salinity, change note 1PV2000mg/L's
Part branched moiety cross-linked polymer oil-displacing agent suspension, carries out sequent water flooding afterwards.Time recording pressure becomes in experimentation
Change and the Liquid output of high and low permeability fill out sand tube, gathered by analyzing fractional flow curves and being crosslinked come comparative study part branched moiety
The transfer drive performance of compound oil displacement agent suspension.
Involved component number, percentage, it is mass parts in addition to special instruction in following embodiment
Number, mass percent.
Embodiment 1
(1) preparation of solution
100 parts of acrylamides are dissolved in wiring solution-forming in 180 parts of deionized water, 0.104 part of pentamethyl divinyl three
Amine is dissolved in wiring solution-forming in 40 parts of deionized water, and 0.05 part of potassium peroxydisulfate is dissolved in into wiring solution-forming in 50 parts of deionized waters,
0.03 part of sodium hydrogensulfite is dissolved in wiring solution-forming in 30 parts of deionized waters；
(2) polymerisation prepares oil displacement agent
By the acrylamide solution of step (1) preparation, pentamethyl-diethylenetriamine solution, sequentially add in reactor,
Stirring, nitrogen 15min led at 12 DEG C of temperature remove oxygen in reactor and in reaction solution, sequentially add potassium persulfate solution and
Solution of sodium bisulfite initiated polymerization, question response, which polymerize to system viscosity, substantially to be increased, and stopping is passed through nitrogen and stirring, treats
System gel follow-up continuation of insurance warm 2-4 hours, products therefrom is taken out, shredded, is dried, is crushed, screening.
The performance test results
The bullet measured under its 200 μm of spacing of partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent made from embodiment 1
Property modulus G '=3.48Pa；Viscosities il=the 330.2mPa.s measured under 1000 μm of spacing.Suspendability is excellent, concentration 0.5wt%
Solution left standstill 2 as a child suspension volume be more than 90%.
Embodiment 2
(1) preparation of solution
100 parts of acrylamides are dissolved in wiring solution-forming in 180 parts of deionized water, 0.025 part of pentamethyl divinyl three
Amine is dissolved in wiring solution-forming in 40 parts of deionized water, and 0.05 part of potassium peroxydisulfate is dissolved in into wiring solution-forming in 50 parts of deionized waters,
0.05 part of sodium hydrogensulfite is dissolved in wiring solution-forming in 50 parts of deionized waters；
(2) polymerisation prepares oil displacement agent
By the acrylamide solution of step (1) preparation, pentamethyl-diethylenetriamine solution, sequentially add in reactor,
Stirring, nitrogen 15min led at 12 DEG C of temperature remove oxygen in reactor and in reaction solution, sequentially add potassium persulfate solution and
Solution of sodium bisulfite initiated polymerization, question response, which polymerize to system viscosity, substantially to be increased, and stopping is passed through nitrogen and stirring, treats
System gel follow-up continuation of insurance warm 2-4 hours, products therefrom is taken out, shredded, is dried, is crushed, screening.
The performance test results
The bullet measured under its 200 μm of spacing of partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent made from embodiment 2
Property modulus G '=11.9Pa；Viscosities il=the 78.9mPa.s measured under 1000 μm of spacing.Concentration is 0.5wt% solution left standstill 2
As a child suspension volume was 80%.
Embodiment 3
(1) preparation of solution
100 parts of acrylamides are dissolved in wiring solution-forming in 180 parts of deionized water, 0.073 part of pentamethyl divinyl three
Amine is dissolved in wiring solution-forming in 40 parts of deionized water, and 0.05 part of potassium peroxydisulfate is dissolved in into wiring solution-forming in 50 parts of deionized waters,
0.04 part of sodium hydrogensulfite is dissolved in wiring solution-forming in 50 parts of deionized waters；
(2) polymerisation prepares oil displacement agent
By the acrylamide solution of step (1) preparation, pentamethyl-diethylenetriamine solution, sequentially add in reactor,
Stirring, nitrogen 15min led at 12 DEG C of temperature remove oxygen in reactor and in reaction solution, sequentially add potassium persulfate solution and
Solution of sodium bisulfite initiated polymerization, question response, which polymerize to system viscosity, substantially to be increased, and stopping is passed through nitrogen and stirring, treats
System gel follow-up continuation of insurance warm 2-4 hours, products therefrom is taken out, shredded, is dried, is crushed, screening.
The performance test results
The bullet measured under its 200 μm of spacing of partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent made from embodiment 3
Property modulus G '=5.23Pa；Viscosities il=the 266.9mPa.s measured under 1000 μm of spacing.Suspendability is excellent, concentration 0.5wt%
Solution left standstill 2 as a child suspension volume be more than 90%.
Embodiment 4
(1) preparation of solution
100 parts of acrylamides are dissolved in wiring solution-forming in 160 parts of deionized water, 0.054 part of pentamethyl divinyl three
Amine is dissolved in wiring solution-forming in 40 parts of deionized water, and 0.05 part of potassium peroxydisulfate is dissolved in into wiring solution-forming in 50 parts of deionized waters,
0.04 part of sodium hydrogensulfite is dissolved in wiring solution-forming in 40 parts of deionized waters；
(2) polymerisation prepares oil displacement agent
By the acrylamide solution of step (1) preparation, pentamethyl-diethylenetriamine solution, sequentially add in reactor,
Stirring, nitrogen 15min led at 12 DEG C of temperature remove oxygen in reactor and in reaction solution, sequentially add potassium persulfate solution and
Solution of sodium bisulfite initiated polymerization, question response, which polymerize to system viscosity, substantially to be increased, and stopping is passed through nitrogen and stirring, treats
System gel follow-up continuation of insurance warm 2-4 hours, products therefrom is taken out, shredded, is dried, is crushed, screening.
The performance test results
The bullet measured under its 200 μm of spacing of partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent made from embodiment 4
Property modulus G '=6.55Pa；Viscosities il=the 155.6mPa.s measured under 1000 μm of spacing.Suspendability is excellent, concentration 0.5wt%
Solution left standstill 2 as a child suspension volume more than 90%.
Embodiment 5
(1) preparation of solution
100 parts of acrylamides are dissolved in wiring solution-forming in 150 parts of deionized water, 0.042 part of pentamethyl divinyl three
Amine is dissolved in wiring solution-forming in 40 parts of deionized water, and 0.05 part of potassium peroxydisulfate is dissolved in into wiring solution-forming in 50 parts of deionized waters,
0.05 part of sodium hydrogensulfite is dissolved in wiring solution-forming in 40 parts of deionized waters；
(2) polymerisation prepares oil displacement agent
By the acrylamide solution of step (1) preparation, pentamethyl-diethylenetriamine solution, sequentially add in reactor,
Stirring, nitrogen 15min led at 12 DEG C of temperature remove oxygen in reactor and in reaction solution, sequentially add potassium persulfate solution and
Solution of sodium bisulfite initiated polymerization, question response, which polymerize to system viscosity, substantially to be increased, and stopping is passed through nitrogen and stirring, treats
System gel follow-up continuation of insurance warm 2-4 hours, products therefrom is taken out, shredded, is dried, is crushed, screening.
The performance test results
The bullet measured under its 200 μm of spacing of partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent made from embodiment 5
Property modulus G '=10.2Pa；Viscosities il=the 129.9mPa.s measured under 1000 μm of spacing.Concentration is 0.5wt% solution left standstill 2
As a child suspension volume was 90%.
Table 2 is the HPAM long-term ageing property tests of 0.5wt% strength solutions at 85 DEG C in 30000mg/L salt solution.
The 0.5wt% concentration in 30000mg/L salt solution for partial cross-linked partially branched polymer oil displacement agent of the invention of table 3
Long-term ageing property test of the solution at 85 DEG C.
Comparison sheet 2, table 3 are understood, although HPAM initial viscosities are very high, viscosity is anxious after aging under the conditions of high temperature and high salt
Play declines.And suspension shows in ageing process made of the partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent of the present invention
Reveal the trend entirely different with HPAM, at aging initial stage, its viscosity constantly increases, until viscosity just starts gradually to drop after 30 days
Low, viscosity is still up to 112.25mPa.s after aging 90 days, and viscosity retention ratio is up to 141.7%, and HPAM is glued after 90 days in aging
Degree is only 12.97mPa.s, and viscosity retention ratio is only 5.2%.As can be seen here, partial cross-linked part branching type poly- third of the invention
Long-term ageing property of the acrylamide oil displacement agent under the conditions of high temperature and high salt is far superior to the polyacrylamide of partial hydrolysis.Therefore,
The oil displacement agent of the present invention has longer service phase than HPAM in actual applications, is more beneficial for the application in tertiary oil recovery.
Table 2
Table 3
Claims (4)
1. a kind of tertiary amine participates in the crosslinking polymer oil displacement agent of synthesis, it is characterised in that raw material constituent component is in parts by weight
Mainly include：
2. the tertiary amine described in claim 1 participates in the preparation method of the crosslinking polymer oil displacement agent of synthesis, it is characterised in that
Mainly comprise the technical steps that：
(1) preparation of solution, each component of raw material is dissolved in the deionized water no less than its 1.0 times of mass parts of formula ratio respectively
In, prepare the solution of each component；
(2) polymerisation prepares oil displacement agent, and acrylamide solution, the pentamethyl-diethylenetriamine solution that step (1) is prepared add
Enter in reactor, after being passed through the oxygen that nitrogen is fully discharged in reactor and in reaction solution at stirring, 10~30 DEG C, added
Potassium sulfate solution and solution of sodium bisulfite initiated polymerization, question response, which polymerize to system viscosity, substantially to be increased, and stops being passed through
Nitrogen and stirring, system gel follow-up continuation of insurance warm 2-4 hours are treated, that is, gel oil displacement agent is prepared.
3. tertiary amine according to claim 2 participates in the preparation method of the crosslinking polymer oil displacement agent of synthesis, its feature
It is, obtained gluey oil displacement agent chopping, drying, crushing, screening is obtained into the oil displacement agent of powdery.
4. the tertiary amine according to Claims 2 or 3 participates in the preparation method of the crosslinking polymer oil displacement agent of synthesis, it is special
Sign is that acrylamide solution, pentamethyl-diethylenetriamine solution sequentially add reactor, are passed through nitrogen under agitation and fully arrange
Go out the oxygen in reactor and in reaction solution, sequentially add potassium persulfate solution and solution of sodium bisulfite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510484051.0A CN105154054B (en) | 2015-08-07 | 2015-08-07 | A kind of tertiary amine participates in crosslinking polymer oil displacement agent of synthesis and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510484051.0A CN105154054B (en) | 2015-08-07 | 2015-08-07 | A kind of tertiary amine participates in crosslinking polymer oil displacement agent of synthesis and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105154054A CN105154054A (en) | 2015-12-16 |
| CN105154054B true CN105154054B (en) | 2017-12-22 |
Family
ID=54795114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510484051.0A Active CN105154054B (en) | 2015-08-07 | 2015-08-07 | A kind of tertiary amine participates in crosslinking polymer oil displacement agent of synthesis and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105154054B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109207137A (en) * | 2017-07-07 | 2019-01-15 | 中国石油化工股份有限公司胜利油田分公司勘探开发研究院 | Polyacrylamide particle oil displacement agent and preparation method thereof |
| CN109266322B (en) * | 2018-09-10 | 2020-04-14 | 四川大学 | High-toughness polyacrylamide gel oil displacement agent and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6262169B1 (en) * | 1998-05-14 | 2001-07-17 | Eastman Chemical Company | Protonated amines for controlled crosslinking of latex polymers |
| CN101403457A (en) * | 2008-11-12 | 2009-04-08 | 申奇 | High-water absorption resin piping detection leak-blocking device, preparation method and application thereof |
| CN102382244A (en) * | 2011-08-17 | 2012-03-21 | 西南石油大学 | Gelation-delayed in-situ polymerized water shutoff gel for high-temperature reservoirs |
| CN102675535A (en) * | 2012-05-22 | 2012-09-19 | 西南石油大学 | Branched polyacrylamide and preparation method thereof |
| CN103193906A (en) * | 2013-04-01 | 2013-07-10 | 中国石油化工股份有限公司 | Preparation method of delayed-coagulation acrylamide single body profile control agent |
| CN104152123A (en) * | 2013-05-13 | 2014-11-19 | 中国石油化工股份有限公司 | Cationic chemical plugging agent and preparation method thereof |
| WO2015021694A1 (en) * | 2013-08-14 | 2015-02-19 | 中国石油化工股份有限公司 | Cationic copolymer and use thereof in leakage plugging agent |
-
2015
- 2015-08-07 CN CN201510484051.0A patent/CN105154054B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6262169B1 (en) * | 1998-05-14 | 2001-07-17 | Eastman Chemical Company | Protonated amines for controlled crosslinking of latex polymers |
| CN101403457A (en) * | 2008-11-12 | 2009-04-08 | 申奇 | High-water absorption resin piping detection leak-blocking device, preparation method and application thereof |
| CN102382244A (en) * | 2011-08-17 | 2012-03-21 | 西南石油大学 | Gelation-delayed in-situ polymerized water shutoff gel for high-temperature reservoirs |
| CN102675535A (en) * | 2012-05-22 | 2012-09-19 | 西南石油大学 | Branched polyacrylamide and preparation method thereof |
| CN103193906A (en) * | 2013-04-01 | 2013-07-10 | 中国石油化工股份有限公司 | Preparation method of delayed-coagulation acrylamide single body profile control agent |
| CN104152123A (en) * | 2013-05-13 | 2014-11-19 | 中国石油化工股份有限公司 | Cationic chemical plugging agent and preparation method thereof |
| WO2015021694A1 (en) * | 2013-08-14 | 2015-02-19 | 中国石油化工股份有限公司 | Cationic copolymer and use thereof in leakage plugging agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105154054A (en) | 2015-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11015109B2 (en) | Particulate profile control agent self-adaptive to size of formation pore throat and preparation method thereof | |
| CN101775275B (en) | Novel viscoelastic particle oil displacement agent and preparation method thereof | |
| CN104178102B (en) | Cross-linkable high-temperature-resistant residue-free multi-component copolymerization type fracturing fluid and preparation method thereof | |
| CN104087275B (en) | A kind of high-temperature-resistant high-salt tiny gels granular profile control agent and its preparation method and application | |
| CN101302266B (en) | Water-soluble micro-crosslinked copolymer, preparation and use thereof | |
| CN102952533B (en) | Composite cross-linked polymer weak gel oil displacement agent and preparation method thereof | |
| CN101798503A (en) | Novel polymeric oil-displacing agent for improving recovery ratio and application thereof | |
| Su et al. | Thermoviscosifying smart polymers for oil and gas production: state of the art | |
| CN109266322A (en) | A kind of polyacrylamide gel oil displacement agent and preparation method thereof with high tenacity | |
| CN106883357A (en) | A kind of pre-crosslinked gel delays swollen microballoon profile control agent and its production and use | |
| CN102558469B (en) | Cross-linking agent for profile control and oil displacement for high-temperature oil reservoir, as well as preparation method and application for same | |
| CN105153361B (en) | A kind of part branched moiety cross-linked polymer oil-displacing agent and preparation method thereof | |
| CN105153363A (en) | Partially-crosslinked and partially-branched copolymer oil displacement agent and preparation method thereof | |
| CN112898484B (en) | Oil-gas field plugging-regulating and flooding multifunctional medicament and preparation process thereof | |
| CN103923629A (en) | Plugging agent | |
| CN103555305A (en) | Hyperbranched slow-swelling profile control particles and preparation method thereof | |
| CN108659163B (en) | Double stimuli expanded gel particle and preparation method thereof for carbon dioxide drive process anti-gas channeling | |
| CN104371681A (en) | AA/AM/SSS underground cross-linked polymer gel plugging agent and preparation method thereof | |
| CN105085798B (en) | A kind of partial cross-linked partially branched polymer oil displacement agent of dual-network and preparation method thereof | |
| CN105154054B (en) | A kind of tertiary amine participates in crosslinking polymer oil displacement agent of synthesis and preparation method thereof | |
| CN105112034A (en) | High temperature resistant gel diverting agent and manufacturing method therefor and application thereof | |
| CN102391849B (en) | Imidazole polymer oil displacement agent and synthesizing method thereof | |
| CN106967406A (en) | A kind of oil displacement system and flooding method for heterogeneous reservoir | |
| CN111087998A (en) | Slow-expansion particles and preparation method thereof | |
| CN113136185A (en) | Organic water plugging gel for low-temperature hypersalinity oil reservoir |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |