CN105154054A - Cross-linked polymer flooding agent adopting triamine participating in synthesis and preparation method of cross-linked polymer flooding agent - Google Patents

Cross-linked polymer flooding agent adopting triamine participating in synthesis and preparation method of cross-linked polymer flooding agent Download PDF

Info

Publication number
CN105154054A
CN105154054A CN201510484051.0A CN201510484051A CN105154054A CN 105154054 A CN105154054 A CN 105154054A CN 201510484051 A CN201510484051 A CN 201510484051A CN 105154054 A CN105154054 A CN 105154054A
Authority
CN
China
Prior art keywords
solution
parts
dissolved
forming
displacing agent
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.)
Granted
Application number
CN201510484051.0A
Other languages
Chinese (zh)
Other versions
CN105154054B (en
Inventor
曹绪龙
黄光速
宋新旺
吴锦荣
苏智青
姜祖明
李江波
刘汉超
王超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan University
Exploration and Development Research Institute of Sinopec Henan Oilfield Branch Co
Original Assignee
Sichuan University
Exploration and Development Research Institute of Sinopec Henan Oilfield Branch Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sichuan University, Exploration and Development Research Institute of Sinopec Henan Oilfield Branch Co filed Critical Sichuan University
Priority to CN201510484051.0A priority Critical patent/CN105154054B/en
Publication of CN105154054A publication Critical patent/CN105154054A/en
Application granted granted Critical
Publication of CN105154054B publication Critical patent/CN105154054B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a cross-linked polymer flooding agent adopting triamine participating in synthesis and a preparation method of the cross-linked polymer flooding agent. Raw material components of the cross-linked polymer flooding agent mainly comprise acrylamide, potassium persulfate, sodium bisulfite and pentamethyldiethylenetriamine. The preparation method of the cross-linked polymer flooding agent comprises the following steps: each raw material component is dissolved in deionized water no less than 1.0 time in parts by mass of the formula ratio of the component, and the solution of the component is prepared; an acrylamide solution and an pentamethyldiethylenetriamine solution are added to a reactor, nitrogen is introduced during stirring at 10-30 DEG C to remove oxygen in the reactor, an potassium persulfate solution and a sodium bisulfite solution are added, nitrogen introducing and stirring are stopped when a reaction system starts polymerization and the viscosity is improved greatly, the polymerization reaction is performed until the temperature is constant, and the colloidal flooding agent is prepared. The cross-linked polymer flooding agent has good usability, ageing resistance, temperature resistance and salt tolerance.

Description

A kind of tertiary amine participates in crosslinking polymer oil-displacing agent of synthesis and preparation method thereof
Technical field
The present invention relates to the technical field of macromolecular material oil-displacing agent, physical relationship is to a kind of part branched moiety cross-linked polymer oil-displacing agent and preparation method thereof.
Background technology
According to the difference of phase of development, oil production is generally divided into three phases: the primary oil recovery utilizing oil reservoir energy recover petroleum, and the oil-production efficiency of this one-phase generally only has about 15%; By injecting water, gas to oil reservoir, supplement oil reservoir energy thus reach exploitation object for secondary oil recovery, tar productivity is 30 ~ 40%; Be tertiary oil recovery by the stage of the new technology crude oil extractions such as physics, chemistry, biology.In order to exploit out by irreducible oil in stratum efficiently, need the tertiary oil recovery method that exploitation is suitable for China's special geologic condition badly.Develop comparatively ripe tertiary oil recovery technology and mainly contain four large classes: chemical flooding, heating power drive, microorganism drives and mixed phase drives.Based on the understanding to reservoir geologic character and irreducible oil, chemical flooding becomes the important means that oil recovery is improved in the most oil field of China.And the core of chemical flooding is the design and synthesis of oil-displacing agent and the design of flooding system.Polymer flooding is the of paramount importance technology of chemical flooding, namely by adding polymkeric substance at injection water, increases sweeping phase viscosity, and adjustment oil and water mobility ratio, expands sweeping phase swept volume, strengthens displacement efficiency, thus improves oil displacement efficiency most possibly.Polymer flooding is simple to operate, and cost is lower, can be combined with profile-controlling and plugging agent, has certain rate of permeation regulating effect concurrently.
As the water-soluble polymer of synthetic, be most widely used general in current chemical flooding based on the synthesis base polymer of polyacrylamide and derivative thereof, the polymer oil-displacing agent that Results is the most outstanding.Divide according to the structure of polyacrylamide, linear polyacrylamide and crosslinked polyacrylamide can be divided into again.
The polyacrylamide of cross-linking type can be made profile-controlling and plugging agent and use, because the swollen property of its good body can carry out profile control process to high permeability formation regulate its rate of permeation.But, completely crosslinked polyacrylamide due to degree of crosslinking high, hardness is large, and deformability is poor, and in hole, migration is difficult, and can not play the effect of oil-displacing agent, the use therefore in tertiary oil recovery is restricted.Chinese patent CN102731718A discloses a kind of with the crosslinking polyacrylamide of aldehyde radical H-H reaction, its easy construction, and plastic is stablized, good to the profile control effect of hole, widespread use in the note polymerizing technology of oil production.Chinese patent CN1796484A discloses a kind of using acrylamide and vinylformic acid as host, and using wilkinite or kaolin as toughener, N,N methylene bis acrylamide is the granular profile control agent that crosslinking copolymerization type prepared by linking agent.The linear polyacrylamide (HPAM) of partial hydrolysis uses mainly based on the increase swept volume that the viscosity of its increase aqueous solution plays as oil-displacing agent, improves the effect of mobility ratio.Chinese patent CN00111320 report has synthesized the polyacrylamide that relative molecular mass is the anionic of 2800-3600 ten thousand.In addition, Chinese patent CN102964519A discloses a kind of ultra-high molecular weight amphiprotic polyacrylamide, and its relative molecular mass can reach 4,280 ten thousand.But under the reservoir condition of high temperature and high salt and serious heterogeneity, the shut-off capacity of polymers soln to high permeability formation that HPAM is formed is poor, be unfavorable for effectively regulating rate of permeation in inhomogeneous formation, and HPAM is seriously aging, viscosity sharply declines, to the bad adaptability of inhomogeneous formation, be difficult to meet the requirement improving recovery ratio.
Summary of the invention
The deficiency of polymer oil-displacing agent is prepared for prior art, primary and foremost purpose of the present invention is to provide the crosslinking polymer oil-displacing agent that a kind of tertiary amine with part branched moiety crosslinking structure participates in synthesis, to improve temperature resistant antisalt performance and the ageing resistance of oil-displacing agent; Second object of the present invention is to provide the preparation method that described tertiary amine participates in the crosslinking polymer oil-displacing agent of synthesis.
For primary and foremost purpose of the present invention, tertiary amine provided by the invention participates in the crosslinking polymer oil-displacing agent of synthesis, adopt pentamethyl-diethylenetriamine (PMTDA) as function monomer and linking agent, potassium sulfate-sodium bisulfite is as initiator system, PMTDA first forms branched structure by initiator, further coupling stops forming section crosslinking structure, finally prepares partial cross-linked and containing a large amount of branched structure polymer oil-displacing agent.Its raw material moiety mainly comprises with parts by weight:
For second object of the present invention, tertiary amine provided by the invention participates in the preparation method of synthesizing cross-linked type polymer oil-displacing agent, mainly comprises following processing step:
(1) preparation of solution, is dissolved in each component of raw material respectively in the deionized water being no less than its formula ratio 1.0 times of mass parts, prepares the solution of each component;
(2) polyreaction prepares oil-displacing agent, acrylamide soln step (1) prepared, pentamethyl-diethylenetriamine add in reactor, stirring, pass into oxygen that nitrogen fully discharges in reactor and in reaction solution at 10 ~ 30 DEG C after, add potassium persulfate solution and sodium sulfite solution initiated polymerization, question response is polymerized to system viscosity obviously to be increased, stop passing into nitrogen and stirring, treat the follow-up continuation of insurance temperature 2-4 hour of system gel, namely prepare gel oil-displacing agent.
The conveniently use of oil-displacing agent, the present invention can on the preparation method basis that above-mentioned tertiary amine participates in synthesizing cross-linked type polymer oil-displacing agent, is carried out by obtained gluey oil-displacing agent shredding, dries, pulverizes, sieves, to obtain granular oil-displacing agent.
Participate in the preparation method of synthesizing cross-linked type polymer oil-displacing agent at tertiary amine of the present invention, not only require to pass into the oxygen in nitrogen removing reactor, also require the oxygen in removing reaction solution, therefore all needed to pass into nitrogen before reaction system viscosity obviously increases.The degree of logical nitrogen deoxygenation, relevant to the add-on of Potassium Persulphate and sodium bisulfite, the degree of discharging oxygen is high, the amount adding Potassium Persulphate and sodium bisulfite can be lacked, the degree of discharging oxygen is low, the amount adding Potassium Persulphate and sodium bisulfite can be larger, and suitable cooperation then can both initiated polymerization.
Participate in the preparation method of synthesizing cross-linked type polymer oil-displacing agent at tertiary amine of the present invention, acrylamide soln, pentamethyl-diethylenetriamine solution preferably add reactor successively, under agitation passing into nitrogen fully discharges in reactor and oxygen in reaction solution, adds potassium persulfate solution and sodium sulfite solution successively more afterwards.
Participate at tertiary amine of the present invention in the preparation method of synthesizing cross-linked type polymer oil-displacing agent, the kick off temperature of polyreaction is low, then reaction is carried out slower; Kick off temperature is too high, then reaction is carried out too fast, and can bring crosslinked imperfect, polyreaction kick off temperature generally can be controlled in 10 ~ 30 DEG C of scopes.
Participate in the preparation method of synthesizing cross-linked type polymer oil-displacing agent at tertiary amine of the present invention, the total amount of dissolving the deionized water of each component is generally 3 ~ 4 times of each feed composition total amount.Further, preferably take 100 parts of acrylamides to be dissolved in wiring solution-forming in the deionized water of 150 ~ 360 parts; The pentamethyl-diethylenetriamine of 0.025 ~ 0.108 part is dissolved in wiring solution-forming in the deionized water of 10-50 part; 0.03 ~ 0.05 part of Potassium Persulphate is dissolved in wiring solution-forming in 10 ~ 50 parts of deionized waters; 0.03 ~ 0.05 part of sodium bisulfite is dissolved in wiring solution-forming in 10 ~ 50 parts of deionized waters.
Compared with prior art, the present invention has following very outstanding advantage and technique effect:
1, the crosslinking polymer oil-displacing agent that prepared by the present invention has the advantage of cross-linked polyacrylamide and linear polyacrylamide concurrently.Wherein, branched structure gives the good suspending power of its aqueous solution and higher viscosity, suspension volume can reach more than 90%, the viscosity that under 1000 μm of spacing, rheometer records can up to 330.2mPaS, its crosslinking structure provides good elasticity and anti-shear ability, and the Young's modulus that under 200 μm of spacing, rheometer records can reach 11.9Pa.
2, there is branched chain structure due in the structure of crosslinking polymer oil-displacing agent prepared in the present invention, thus its suspension has good suspension property, overcomes traditional crosslinked polyacrylamide viscosity low, the shortcomings such as free settling.
3, the crosslinking polymer oil-displacing agent prepared of the present invention is compared with linear acrylamide's oil-displacing agent in the past, in weathering process, its viscosity is one and first increases the process reduced again, there is unique thickening behavior, and polymer suspension fluid viscosity can be retained in a higher level within very long for some time, in 85 DEG C, in 30000 salinity salt solution aging 90 days, its viscosity retention ratio was still up to 141%.
4, the crosslinking polymer oil-displacing agent that prepared by the present invention can be migrated well in rock core, and two-tube rock core Seepage Experiment shows that it has efficient section Accommodation.
Accompanying drawing explanation
Fig. 1 be HPAM under different salinity viscosity with the change curve of shearing rate.
Fig. 2 be part branched moiety crosslinking polymer oil-displacing agent of the present invention under different salinity viscosity with the change curve of shearing rate.
Fig. 1 and Fig. 2 is respectively HPAM and embodiments of the invention 4 product viscosity under different salinity, with shear rate change curve, can be found out, along with the increase of salinity, HPAM viscosity reduces successively; Partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent is in pure water curve is apparently higher than its curve in salt solution, but salinity is increased to 50000mg/L from 6666mg/L, its curvilinear motion is little, and its viscosity is insensitive to the mesohalobic increase of solution.This is the existence due to the special partial cross-linked part branched structure of product of the present invention, make not to be hydrolyzed the molecular structure of hyper-branched chain and sterically hinderedly all have stronger restraining effect to positively charged ion attack electrostatic double layer and high volence metal ion complexing carboxylic ions, therefore showing good salt resistant character.
Fig. 3 is the single tube seepage flow test of part branched moiety crosslinking polymer oil-displacing agent of the present invention.(fill out sand tube rate of permeation: (1500 ± 15) × 10 -3um 2, solution salinity: 19334mg/L, suspension concentration: 0.15wt%)
Fig. 4 is the two-tube Seepage Experiment (rate of permeation: 1000/5000 × 10 of part branched moiety crosslinking polymer oil-displacing agent -3um 2, solution salinity: 19334mg/L, suspension concentration: 0.15wt%)
Fig. 3, Fig. 4 are respectively the single tube of embodiment 2 product and two-tube seepage flow performance test.As can be seen from Figure 3, play pressure very fast in fill out sand tube, and fluctuation obviously, final equilibrium pressure reaches more than 1.2MPa, shows that partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent Flooding Efficiency of migrating in hole is good.The two-tube Seepage Experiment of Fig. 4 adopts rate of permeation to be respectively 5000 × 10 -3um 2with 1000 × 10 -3um 2the ability of the different size pore throats of two parallel fill out sand tube research product selectivity profile controls.Test shows, during water drive balance, height oozes fill out sand tube and is about 5:1 with the ratio of the fractional flow of hypotonic fill out sand tube, meets the ratio of the two rate of permeation.But when after injection part crosslink part branching type POLYACRYLAMIDE FLOODING agent suspension, the flow that height oozes fill out sand tube diminishes gradually and hypotonic fill out sand tube flow becomes large, produces uncommon reversal development.The reversal development of this fractional flow is called " fluid diversion ".In displacement process, the Liquid output of height permeation tube is up to 43.18%:56.82%, declaratives crosslink part branching type POLYACRYLAMIDE FLOODING agent particle serves the effect of effectively adjustment heterogeneous body fill out sand tube section, low permeability fill out sand tube is farthest developed, greatly improve the swept volume of hypotonic pipe, improve oil displacement efficiency.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that the present embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
The polymer oil-displacing agent sample obtained to following examples has carried out following correlated performance test as follows:
1. rheology testing
Steady state shearing is tested: the AR2000ex rotational rheometer using TA company, and adopt 40mm plate mode, sheet separation is 1000 μm; Viscosity test pattern is set to 7.34s -1shearing rate under time scan, acquisition steady-state viscosity of averaging, probe temperature is 85 DEG C.
Dynamic concussion test: adopt identical rheometer and flat board, dynamic concussion test is 1Hz in frequency, stress is carry out time scan under 0.1Pa condition, to average acquisition viscoelastic data, according to different test requests, sheet separation is set to 200 μm and 1000 μm, and corresponding probe temperature is set to 25 DEG C and 85 DEG C respectively.
Rheology testing part branched moiety used cross-linked polymer oil-displacing agent is 100-150 order, and the concentration of suspension is 0.5wt%, and salt water salinity is 30000mg/L.
The salt solution that experiment adopts is the Simulated Water according to the different oil reservoir salinity of Shengli Oil Field and salt ionic concentration preparation, and different saline formulation is as shown in table 1.
Table 1
Salinity H 2O NaCl CaCl 2 MgCl 2·6H 2O Na 2SO 4
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. suspension property test
The suspension volume of the heteropolymer suspension that the partial cross-linked polymer oil-displacing agent of determination part point branching is formed in salt solution.
3. aging resistance test
Be determined at part branched moiety cross-linked polymer oil-displacing agent and the aging resistance of linear polyacrylamide (HPAM) polymers soln at 85 DEG C that salinity is the 0.5wt% concentration that in 30000mg/L salt solution prepared by the present invention.
4. single tube rock core Seepage Experiment
Test porous medium used for self-control fill out sand tube, long is 30cm, and internal diameter is 2.5cm, and the rate of permeation of fill out sand tube is (1500 ± 15) × 10 -3um 2, volume of voids (porevolume) is 50 ± 0.5cm 3.Whole Seepage Experiment carries out in digital temperature-controlled box, and fluid injection speed is 0.5mL/min, and experimental temperature is 70 DEG C.
Experimental technique: first inject the salt solution that salinity is 19334mg/L in fill out sand tube, record intake pressure at regular intervals.When after pressure equilibrium, change the part branched moiety cross-linked polymer oil-displacing agent suspension of note 2000mg/L, time recording pressure, after pressure equilibrium, carry out sequent water flooding to balance.
5. two-tube rock core Seepage Experiment
Test adopts the rate of permeation of high permeability and low permeability fill out sand tube to be respectively (1000 ± 10) × 10 -3μm 2(5000 ± 15) × 10 -3μm 2, the total pore size volume of two parallel seepage flow pipes is 101.6 ± 0.5cm 3.The mode of adopting to close note point injects salt solution and part branched moiety cross-linked polymer oil-displacing agent suspension, and injection speed is 0.5mL/min, and experimental temperature is 70 DEG C.
Experimental technique: after injection 1PV (volume of voids) salinity is 19334mg/L salt solution, changes the part branched moiety cross-linked polymer oil-displacing agent suspension of note 1PV2000mg/L, carry out sequent water flooding afterwards.The Liquid output of time recording pressure change and high and low rate of permeation fill out sand tube in experimentation, carrys out the transfer drive performance of comparative study part branched moiety cross-linked polymer oil-displacing agent suspension by analyzing fractional flow curves.
In following embodiment, involved component number, per-cent, except special instruction, be mass fraction, mass percent.
Embodiment 1
(1) preparation of solution
100 parts of acrylamides are dissolved in wiring solution-forming in the deionized water of 180 parts, the pentamethyl-diethylenetriamine of 0.104 part is dissolved in wiring solution-forming in the deionized water of 40 parts, 0.05 part of Potassium Persulphate is dissolved in wiring solution-forming in 50 parts of deionized waters, and 0.03 part of sodium bisulfite is dissolved in wiring solution-forming in 30 parts of deionized waters;
(2) polyreaction prepares oil-displacing agent
Acrylamide soln, pentamethyl-diethylenetriamine solution that step (1) is prepared, add in reactor successively, at stirring, temperature 12 DEG C, logical nitrogen 15min removes the oxygen in reactor and in reaction solution, add potassium persulfate solution and sodium sulfite solution initiated polymerization more successively, question response is polymerized to system viscosity obviously to be increased, stop passing into nitrogen and stirring, treat the follow-up continuation of insurance temperature 2-4 hour of system gel, products therefrom is taken out, chopping, dry, pulverize, sieve.
The performance test results
Elastic modulus G '=the 3.48Pa recorded under its 200 μm of spacing of partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent that embodiment 1 is obtained; Viscosities il=the 330.2mPa.s recorded under 1000 μm of spacing.Suspension property is excellent, and the solution left standstill 2 of concentration 0.5wt% as a child suspension volume is greater than 90%.
Embodiment 2
(1) preparation of solution
100 parts of acrylamides are dissolved in wiring solution-forming in the deionized water of 180 parts, the pentamethyl-diethylenetriamine of 0.025 part is dissolved in wiring solution-forming in the deionized water of 40 parts, 0.05 part of Potassium Persulphate is dissolved in wiring solution-forming in 50 parts of deionized waters, and 0.05 part of sodium bisulfite is dissolved in wiring solution-forming in 50 parts of deionized waters;
(2) polyreaction prepares oil-displacing agent
Acrylamide soln, pentamethyl-diethylenetriamine solution that step (1) is prepared, add in reactor successively, at stirring, temperature 12 DEG C, logical nitrogen 15min removes the oxygen in reactor and in reaction solution, add potassium persulfate solution and sodium sulfite solution initiated polymerization more successively, question response is polymerized to system viscosity obviously to be increased, stop passing into nitrogen and stirring, treat the follow-up continuation of insurance temperature 2-4 hour of system gel, products therefrom is taken out, chopping, dry, pulverize, sieve.
The performance test results
Elastic modulus G '=the 11.9Pa recorded under its 200 μm of spacing of partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent that embodiment 2 is obtained; Viscosities il=the 78.9mPa.s recorded under 1000 μm of spacing.Concentration be 0.5wt% solution left standstill 2 as a child suspension volume be 80%.
Embodiment 3
(1) preparation of solution
100 parts of acrylamides are dissolved in wiring solution-forming in the deionized water of 180 parts, the pentamethyl-diethylenetriamine of 0.073 part is dissolved in wiring solution-forming in the deionized water of 40 parts, 0.05 part of Potassium Persulphate is dissolved in wiring solution-forming in 50 parts of deionized waters, and 0.04 part of sodium bisulfite is dissolved in wiring solution-forming in 50 parts of deionized waters;
(2) polyreaction prepares oil-displacing agent
Acrylamide soln, pentamethyl-diethylenetriamine solution that step (1) is prepared, add in reactor successively, at stirring, temperature 12 DEG C, logical nitrogen 15min removes the oxygen in reactor and in reaction solution, add potassium persulfate solution and sodium sulfite solution initiated polymerization more successively, question response is polymerized to system viscosity obviously to be increased, stop passing into nitrogen and stirring, treat the follow-up continuation of insurance temperature 2-4 hour of system gel, products therefrom is taken out, chopping, dry, pulverize, sieve.
The performance test results
Elastic modulus G '=the 5.23Pa recorded under its 200 μm of spacing of partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent that embodiment 3 is obtained; Viscosities il=the 266.9mPa.s recorded under 1000 μm of spacing.Suspension property is excellent, and the solution left standstill 2 of concentration 0.5wt% as a child suspension volume is greater than 90%.
Embodiment 4
(1) preparation of solution
100 parts of acrylamides are dissolved in wiring solution-forming in the deionized water of 160 parts, the pentamethyl-diethylenetriamine of 0.054 part is dissolved in wiring solution-forming in the deionized water of 40 parts, 0.05 part of Potassium Persulphate is dissolved in wiring solution-forming in 50 parts of deionized waters, and 0.04 part of sodium bisulfite is dissolved in wiring solution-forming in 40 parts of deionized waters;
(2) polyreaction prepares oil-displacing agent
Acrylamide soln, pentamethyl-diethylenetriamine solution that step (1) is prepared, add in reactor successively, at stirring, temperature 12 DEG C, logical nitrogen 15min removes the oxygen in reactor and in reaction solution, add potassium persulfate solution and sodium sulfite solution initiated polymerization more successively, question response is polymerized to system viscosity obviously to be increased, stop passing into nitrogen and stirring, treat the follow-up continuation of insurance temperature 2-4 hour of system gel, products therefrom is taken out, chopping, dry, pulverize, sieve.
The performance test results
Elastic modulus G '=the 6.55Pa recorded under its 200 μm of spacing of partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent that embodiment 4 is obtained; Viscosities il=the 155.6mPa.s recorded under 1000 μm of spacing.Suspension property is excellent, the solution left standstill 2 of concentration 0.5wt% 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 the deionized water of 150 parts, the pentamethyl-diethylenetriamine of 0.042 part is dissolved in wiring solution-forming in the deionized water of 40 parts, 0.05 part of Potassium Persulphate is dissolved in wiring solution-forming in 50 parts of deionized waters, and 0.05 part of sodium bisulfite is dissolved in wiring solution-forming in 40 parts of deionized waters;
(2) polyreaction prepares oil-displacing agent
Acrylamide soln, pentamethyl-diethylenetriamine solution that step (1) is prepared, add in reactor successively, at stirring, temperature 12 DEG C, logical nitrogen 15min removes the oxygen in reactor and in reaction solution, add potassium persulfate solution and sodium sulfite solution initiated polymerization more successively, question response is polymerized to system viscosity obviously to be increased, stop passing into nitrogen and stirring, treat the follow-up continuation of insurance temperature 2-4 hour of system gel, products therefrom is taken out, chopping, dry, pulverize, sieve.
The performance test results
Elastic modulus G '=the 10.2Pa recorded under its 200 μm of spacing of partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent that embodiment 5 is obtained; Viscosities il=the 129.9mPa.s recorded under 1000 μm of spacing.Concentration be 0.5wt% solution left standstill 2 as a child suspension volume be 90%.
Table 2 is HPAM 0.5wt% strength solution long-term ageing property test at 85 DEG C in 30000mg/L salt solution.
Table 3 is partial cross-linked partially branched polymer oil-displacing agent of the present invention 0.5wt% strength solution long-term ageing property test at 85 DEG C in 30000mg/L salt solution.
Comparison sheet 2, table 3 are known, although HPAM initial viscosity is very high, under high temperature and high salt condition, aging rear viscosity sharply declines.And the suspension that partial cross-linked part branching type POLYACRYLAMIDE FLOODING of the present invention agent is made shows the diverse trend with HPAM in weathering process, at the aging initial stage, its viscosity constantly increases, until viscosity just starts to reduce gradually after 30 days, after aging 90 days, viscosity is still up to 112.25mPa.s, viscosity retention ratio is up to 141.7%, and HPAM viscosity after aging 90 days is only 12.97mPa.s, and viscosity retention ratio is only 5.2%.As can be seen here, the long-term ageing property of partial cross-linked part branching type POLYACRYLAMIDE FLOODING agent of the present invention under high temperature and high salt condition is far superior to the polyacrylamide of partial hydrolysis.Therefore, oil-displacing agent of the present invention has the longer military service phase than HPAM in actual applications, is more conducive to the application in tertiary oil recovery.
Table 2
Table 3

Claims (10)

1. tertiary amine participates in a crosslinking polymer oil-displacing agent for synthesis, it is characterized in that raw material composition component mainly comprises with parts by weight:
2. tertiary amine according to claim 1 participates in the preparation method of the crosslinking polymer oil-displacing agent of synthesis, it is characterized in that mainly comprising following processing step:
(1) preparation of solution, is dissolved in each component of raw material respectively in the deionized water being no less than its formula ratio 1.0 times of mass parts, prepares the solution of each component;
(2) polyreaction prepares oil-displacing agent, acrylamide soln step (1) prepared, pentamethyl-diethylenetriamine solution add in reactor, stirring, pass into oxygen that nitrogen fully discharges in reactor and in reaction solution at 10 ~ 30 DEG C after, add potassium persulfate solution and sodium sulfite solution initiated polymerization, question response is polymerized to system viscosity obviously to be increased, stop passing into nitrogen and stirring, treat the follow-up continuation of insurance temperature 2-4 hour of system gel, namely prepare gel oil-displacing agent.
3. the preparation method of the crosslinking polymer oil-displacing agent of tertiary amine participation synthesis according to claim 2, is characterized in that, by obtained gluey oil-displacing agent chopping, oven dry, pulverizing, sieves the oil-displacing agent obtaining powdery.
4. the tertiary amine according to Claims 2 or 3 participates in the preparation method of the crosslinking polymer oil-displacing agent of synthesis, it is characterized in that, acrylamide soln, pentamethyl-diethylenetriamine solution add reactor successively, under agitation passing into nitrogen fully discharges in reactor and oxygen in reaction solution, then adds potassium persulfate solution and sodium sulfite solution successively.
5. the tertiary amine according to Claims 2 or 3 participates in the preparation method of the crosslinking polymer oil-displacing agent of synthesis, and it is characterized in that, the total amount of dissolving the deionized water of each component is 3 ~ 4 times of each feed composition total amount.
6. tertiary amine according to claim 4 participates in the preparation method of the crosslinking polymer oil-displacing agent of synthesis, and it is characterized in that, the total amount of dissolving the deionized water of each component is 3 ~ 4 times of each feed composition total amount.
7. the tertiary amine according to Claims 2 or 3 participates in the preparation method of the crosslinking polymer oil-displacing agent of synthesis, it is characterized in that: 100 parts of acrylamides are dissolved in wiring solution-forming in the deionized water of 150 ~ 360 parts; The pentamethyl-diethylenetriamine of 0.025 ~ 0.108 part is dissolved in wiring solution-forming in the deionized water of 10-50 part; 0.03 ~ 0.05 part of Potassium Persulphate is dissolved in wiring solution-forming in 10 ~ 50 parts of deionized waters; 0.03 ~ 0.05 part of sodium bisulfite is dissolved in wiring solution-forming in 10 ~ 50 parts of deionized waters.
8. tertiary amine according to claim 4 participates in the preparation method of the crosslinking polymer oil-displacing agent of synthesis, it is characterized in that: 100 parts of acrylamides are dissolved in wiring solution-forming in the deionized water of 150 ~ 360 parts; The pentamethyl-diethylenetriamine of 0.025 ~ 0.108 part is dissolved in wiring solution-forming in the deionized water of 10-50 part; 0.03 ~ 0.05 part of Potassium Persulphate is dissolved in wiring solution-forming in 10 ~ 50 parts of deionized waters; 0.03 ~ 0.05 part of sodium bisulfite is dissolved in wiring solution-forming in 10 ~ 50 parts of deionized waters.
9. tertiary amine according to claim 5 participates in the preparation method of the crosslinking polymer oil-displacing agent of synthesis, it is characterized in that: 100 parts of acrylamides are dissolved in wiring solution-forming in the deionized water of 150 ~ 360 parts; The pentamethyl-diethylenetriamine of 0.025 ~ 0.108 part is dissolved in wiring solution-forming in the deionized water of 10-50 part; 0.03 ~ 0.05 part of Potassium Persulphate is dissolved in wiring solution-forming in 10 ~ 50 parts of deionized waters; 0.03 ~ 0.05 part of sodium bisulfite is dissolved in wiring solution-forming in 10 ~ 50 parts of deionized waters.
10. tertiary amine according to claim 6 participates in the preparation method of the crosslinking polymer oil-displacing agent of synthesis, it is characterized in that: 100 parts of acrylamides are dissolved in wiring solution-forming in the deionized water of 150 ~ 360 parts; The pentamethyl-diethylenetriamine of 0.025 ~ 0.108 part is dissolved in wiring solution-forming in the deionized water of 10-50 part; 0.03 ~ 0.05 part of Potassium Persulphate is dissolved in wiring solution-forming in 10 ~ 50 parts of deionized waters; 0.03 ~ 0.05 part of sodium bisulfite is dissolved in wiring solution-forming in 10 ~ 50 parts of deionized waters.
CN201510484051.0A 2015-08-07 2015-08-07 A kind of tertiary amine participates in crosslinking polymer oil displacement agent of synthesis and preparation method thereof Active CN105154054B (en)

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 true CN105154054A (en) 2015-12-16
CN105154054B 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)

Cited By (2)

* Cited by examiner, † Cited by third party
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
CN109266322A (en) * 2018-09-10 2019-01-25 四川大学 A kind of polyacrylamide gel oil displacement agent and preparation method thereof with high tenacity

Citations (7)

* Cited by examiner, † Cited by third party
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

Patent Citations (7)

* Cited by examiner, † Cited by third party
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

Cited By (2)

* Cited by examiner, † Cited by third party
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
CN109266322A (en) * 2018-09-10 2019-01-25 四川大学 A kind of polyacrylamide gel oil displacement agent and preparation method thereof with high tenacity

Also Published As

Publication number Publication date
CN105154054B (en) 2017-12-22

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
CN104017135B (en) Method for preparing microbial polysaccharide modified copolymer gel plugging agent
CN101798503B (en) Novel polymeric oil-displacing agent for improving recovery ratio and application thereof
CN103555305B (en) Hyperbranched slow-swelling profile control particles and preparation method thereof
CN103320112B (en) A kind of anti-shearing dendritic polymers oil-displacing agent and synthetic method thereof
Su et al. Thermoviscosifying smart polymers for oil and gas production: state of the art
CN105153363A (en) Partially-crosslinked and partially-branched copolymer oil displacement agent and preparation method thereof
CN105367708B (en) A kind of profile control agent and its manufacture method and a kind of quadripolymer and its manufacture method
CN109266322A (en) A kind of polyacrylamide gel oil displacement agent and preparation method thereof with high tenacity
CN104371681A (en) AA/AM/SSS underground cross-linked polymer gel plugging agent and preparation method thereof
CN105482033B (en) A kind of polymer microballoon and its preparation method and application
CN109369848A (en) A kind of functional form temperature-resistant anti-salt plugging agent and preparation method thereof
El-Hoshoudy et al. Investigation of Optimum Polymerization Conditions for Synthesis of Cross‐Linked Polyacrylamide‐Amphoteric Surfmer Nanocomposites for Polymer Flooding in Sandstone Reservoirs
CN105112034B (en) High-temperature-resistant gel diverting agent and preparation method and application thereof
CN104829784A (en) Dissoluble polymeric microsphere deep profile modifying and flooding agent and preparation method thereof
CN102898590A (en) Twin-tailed hydrophobically associating polymer oil-displacement agent containing beta-cyclodextrin and synthetic method thereof
CN103421137A (en) Preparation method of high temperature resistance polyacrylamide for oil displacement
CN108659163B (en) Double stimuli expanded gel particle and preparation method thereof for carbon dioxide drive process anti-gas channeling
Chen Polyacrylamide and its derivatives for oil recovery
CN105153361B (en) A kind of part branched moiety cross-linked polymer oil-displacing agent and preparation method thereof
CN105085798A (en) Double-network polymer oil-displacing agent with crosslinked part and branched part and preparing method of polymer oil-displacing agent
CN102391849B (en) Imidazole polymer oil displacement agent and synthesizing method thereof
CN106520107A (en) Acryloyl morpholine polymer oil-displacing agent and preparation method thereof
CN105154054A (en) Cross-linked polymer flooding agent adopting triamine participating in synthesis and preparation method of cross-linked polymer flooding agent

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