CN106589224A - Hydrophobically associating polymer for oil displacement in high temperature and salinity reservoir and synthetic method - Google Patents
Hydrophobically associating polymer for oil displacement in high temperature and salinity reservoir and synthetic method Download PDFInfo
- Publication number
- CN106589224A CN106589224A CN201510681509.1A CN201510681509A CN106589224A CN 106589224 A CN106589224 A CN 106589224A CN 201510681509 A CN201510681509 A CN 201510681509A CN 106589224 A CN106589224 A CN 106589224A
- Authority
- CN
- China
- Prior art keywords
- high temperature
- hydrophobic
- oil
- associated polymer
- monomer
- 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.)
- Pending
Links
- 0 **(*)NC(C(*)=*)=O Chemical compound **(*)NC(C(*)=*)=O 0.000 description 2
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a hydrophobically associating water-soluble polymer and a synthetic method, which aim to solve the current problems of poor viscosity and low stability of the polymer for oil displacement at high temperature and salinity reservoir by adopting the Hydrophobically associating polymer for oil displacement at high temperature and salinity reservoir which is obtained by a mixture polymerized by a free radical micellar aqueous solution. The mixture comprises by mass: a. 100 parts of acrylamide; b. 0 to 60 parts of anionic monomer; c. 0.1 to 15 parts of hydrophobic monomer; d. 0 to 15 parts of surfactant; e. 200 to 2000 parts of the technical scheme of water. The hydrophobically associating polymer for oil displacement in high temperature and salinity reservoir and a synthetic method have the advantage of better solving the technical problem, which can be used in oil displacement agent for high temperature and salinity reservoir.
Description
Technical field
The present invention relates to high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer and its synthetic method, mainly solve mesh
The front displacement of reservoir oil problem of the low stability difference of polymer viscosity, can use as high temperature and high salt oil deposit oil displacement agent.
Background technology
Improve at present oil recovery factor become one of countries in the world onshore petroleum industry sustainable development it is urgent
Strategic task.In the method for improving the tertiary oil recovery (EOR) of oil recovery factor, polymer displacement of reservoir oil tech is accounted for
Critical role.Partially hydrolyzed polyacrylamide (PHPA) (HPAM) is polymerizations most used in polymer displacement of reservoir oil tech
Succeed and use in the oil fields such as thing, grand celebration, triumph, the Liaohe River in China.But HPAM actually should
There are many shortcomings with：Temperature tolerance is poor, when temperature is more than 70 DEG C, acylamino- (- CONH2) facile hydrolysiss, make
Obtain polymer solution viscosity to drastically reduce；Salt tolerance is bad, and carboxyl is very sensitive to salt, especially runs into high price
Easily precipitate during ion, containing Ca2+、Mg2+、Al3+Often there is phase point in the high stratum of plasma concentration
From；The high polymer dissolution velocity of relative molecular mass is slow, and easily shear degradation, main reason is that
HPAM has the flexible linear chain structure sensitive to salinity and temperature and shear action, so HPAM specifically divides
Minor structure determines that it is applied to middle low temperature, less salt oil reservoir.Therefore, the heat-resistant salt-resistant water-soluble polymer displacement of reservoir oil is helped
The research and development of agent have become the problem that each oil field of recent domestic and chemist are competitively studied.It is hydrophobic
Associative water-soluble salt-tolerance has become one of new focus of current polymer material science research, and it is
Refer to the class water-soluble polymer with a small amount of hydrophobic group on polymer hydrophilicity macromolecular chain.It is only due to its
Special amphiphilic structure makes that its aqueous solution characteristic is far from each other with general water-soluble polymer solution, and it is in higher temperature
Under finite concentration inorganic salt solution in still have good viscosifying action, be primarily due to its aqueous solution due to intermolecular
The association of hydrophobic group and form unstable Invertible Spaces network structure, defined by this association non-
Often big supramolecular structure, this structure is little by time effects, and the ability for resisting temperature damage is strong, in saline solution
In, the addition of small molecule electrolyte strengthens heat resistance and salt tolerance, and solution viscosity increases, and shows significantly anti-
Salt performance.
Numerous studies, wherein Southwest Petroleum Institute, Chengdu science and technology are carried out in terms of hydrophobic associated polymer in the country
University, petrochina exploration and development academy, University of Petroleum, Northcentral University etc. achieve preferably progress and into
Really.
The high-molecular hydrophobic associated polymer of Ou Yangjian etc. (CN1317501) synthesis, in 75 DEG C of total mineralisings
Degree 12000mg/L, wherein Ca2+And Mg2+For 300mg/L, sample concentration is 1500mg/L, using Bu Shi
Viscometer, shear rate is 36.7s-1Viscosity is 15.6～12.4mPa.s；Feng Ru Lignum Rhamnellae (CN1793189A)
Synthesized containing acrylamide, three kinds of structure lists of sodium acrylate and pi-allyl-alkyl phenyl ether using micelle copolymerization method
The hydrophobic associated polymer of unit, although have preferable Efficient Adhesive Promotion, but the conjunction of pi-allyl-alkyl phenyl ether monomer
Into complex；Zhong Chuanrong etc. (CN101293944A, CN 101148582A) has synthesized thick containing vinyl
PAH is used as the hydrophobic associated polymer of hydrophobic monomer, and the polymerization process time is longer, only have rated at 45 DEG C
Efficient Adhesive Promotion of the polymer in fresh water and saline, salt resistance effect assessment NaCl concentration<100000mg/L、
CaC12Concentration<The situation of 1000mg/L；Kong Ying etc. (CN1528734, CN1528797) has synthesized fluorine-containing
The water-soluble hydrophobic associated type polymer of super high molecular weight of carbon-based group, have rated it in triumph saline (total salinity
6000mg/L, calcium ions and magnesium ions 500mg/L) tackifying under the conditions of 70 DEG C, the wherein hydrophobic list of fluorinated acrylate
Body it is expensive；Jiang Liding (synthesis of new family's hydrophobic association polyacrylamide and its rheological characteristic of aqueous solution
Can, Master's thesis in 2007) adopt surface active monomer NaAMC14S and the homogeneous combined polymerization of AM aqueous solutions
Method be successfully prepared the copolymer NaAMC with hydrophobic block structure14S/AM, overcomes micelle and is total to
Some shortcomings that polymerization is brought using conventional surfactants, copolymer NaAMC14S/AM's is hydrophobic micro- embedding
The length of section can be controlled by adjusting the consumption of additional electrolyte, but research work biases toward theory, does not have
Evaluation result under the conditions of actual oil field mineral reserve.
The content of the invention
One of the technical problem to be solved is that the polymer of prior art glues in high temperature and high salt oil deposit
The low problem of degree, there is provided a kind of high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer, the hydrophobic associated polymer
With good water solublity, with good temperature-resistant anti-salt and anti-shear performance.
It is described thin that the two of the technical problem to be solved are to provide a kind of one of solution above-mentioned technical problem
The preparation method of water association polymer.
It is described thin that the three of the technical problem to be solved are to provide a kind of one of solution above-mentioned technical problem
Water association polymer is in high temperature and high salt oil deposit as the application of oil displacement agent.
In order to solve one of above-mentioned technical problem, technical scheme is as follows：The high temperature and high salt oil deposit displacement of reservoir oil is used
Hydrophobic associated polymer, is obtained by the mixture Jing micellar free radical copolymerizations represented including following masses part：
A) 100 parts of acrylamide；
B) 0～60 part of anionic monomer；
C) 0.1～15 part of hydrophobic monomer；
D) 0～15 part of surfactant；
E) 200～2000 parts of water.
In above-mentioned technical proposal, the radical polymerization anionic monomer preferably is selected from 2- acrylamido -2- methyl-props
At least one in sulfonic acid, acrylic acid, methacrylic acid, vinylbenzenesulfonic acid, vinyl sulfonic acid.
In above-mentioned skill book scheme, the hydrophobic monomer preferably be selected from anion hydrophobic monomer, cation hydrophobic monomer or
At least one in nonionic hydrophobic monomer.
In above-mentioned technical proposal, the anion hydrophobic monomer preferably has the formula shown in formula I；It is described
Cation hydrophobic monomer preferably has the formula shown in formula II；The nonionic hydrophobic monomer has formula III
Shown formula；
Wherein, R0For H or methyl, R1For C1～C22Alkyl chain, R2For C1～C22Alkyl, R3With
R4It is independently selected from C1～C4Alkyl, A be-COOH ,-SO3Na、-SO3H、-CONH2、
-CONHRSO3H、-CONHRSO3At least one in Na；X is halogen, more preferably chlorine；R is
C1～C22Alkylidene, R5For H or methyl, R6For C1～C22Alkyl.
In above-mentioned technical proposal, the surfactant preferably is selected from anionic surfactant, cationic surface
At least one in activating agent.
In above-mentioned technical proposal, the anionic surfactant preferably is selected from C8-16Alkyl sodium sulfate, C8-16
At least one in sodium alkyl benzene sulfonate；The cationic surface active agent preferably is selected from C8-16Alkyl bromide (chlorine)
Change at least one in ammonium.
In above-mentioned technical proposal, the surfactant preferably is selected from least in nonionic surfactant
Kind；Further preferably from C8～C22 alkylphenol polyoxyethylene (EO=4～30), C8～C22 fatty alcohol polyoxies
At least one in vinyl Ether (EO=4～30)；Present invention discover that when the surfactant preferably is selected from alkyl phenol
During at least one in polyoxyethylene ether (EO=4～30), fatty alcohol-polyoxyethylene ether (EO=4～30), this
Class surfactant not only facilitates the dissolving of hydrophobic monomer and hydrophobic associated polymer, has an effect on hydrophobic association and gathers
The synthetic reaction process of compound, is favorably improved the viscosifying action of the hydrophobic associated polymer for obtaining, with preferable
Synergistic function.
To solve the two of above-mentioned technical problem, technical scheme is as follows：A kind of above-mentioned technical proposal is arbitrary
The preparation method of described hydrophobic associated polymer, comprises the following steps：
A () adds the desired amount of water, acrylamide, anionic monomer, hydrophobic monomer, surface in polymeric kettle
Activating agent, stirs to form solution；
B () adjusts the pH value of solution to 7～10, radical polymerization initiator is added, in 10～30 DEG C of temperature
Cause 0.5～1 hour；
C () is polymerized 2～8 hours at a temperature of 40～60 DEG C, obtain aqueous gel hydrophobic associated polymer：
D () 80～95 DEG C of crushed after being dried, obtain high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer.
In above-mentioned technical proposal, the radical initiator is preferably redox initiator.
In above-mentioned technical proposal, the radical initiator consumption preferably account for the total weight of monomer 0.003～
0.5%.
In above-mentioned technical proposal, the radical initiator preferably is selected from Ammonium persulfate. or alkali metal persulphate extremely
Lack a kind of oxidant and in alkali metal sulfite, alkali metal bisulfite or alkali metal thiosulfate
At least one reducing agent composition.
In order to solve the three of above-mentioned technical problem, the technical solution used in the present invention is：A kind of above-mentioned technical proposal
Arbitrary described high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer is in high temperature and high salt oil deposit as oil displacement agent
Application.
In above-mentioned technical proposal, described application process those skilled in the art can be according to polymer in prior art
The method of drive is used, and has no particular/special requirement, for example but be not limited to by the high temperature and high salt oil deposit displacement of reservoir oil use
Hydrophobic associated polymer injects in reservoir formation contacted with underground crude oil in form of an aqueous solutions, and underground crude oil is driven
For out.
Using technical scheme, the hydrophobic associated polymer of preparation, molecular weight 200～20,000,000 it
Between, at 85 DEG C, in saline of the total salinity more than 80000mg/L, the hydrophobic associated polymer of 1500ppm
Viscosity be more than 100mPas, with preferable technique effect.The polymer have good temperature-resistant anti-salt,
Anti-shearing and heat aging performance, can use as high temperature and high salt oil deposit oil displacement agent.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
650g deionized waters are initially charged in polymeric kettle, 100g acrylamides, 54g 2- acrylamido is added
- 2- methyl propane sulfonic acids, 1.5g 2- acrylamido cetyl carboxylic acid sodium, 10g OPEOs
(EO=16), stir to being completely dissolved, it is 9 to adjust pH value with NaOH, and starts to be passed through high pure nitrogen,
Temperature in the kettle is down to into 15 DEG C after 30min, the aqueous solution of sodium bisulfite 15.5g of 0.1wt% is then sequentially added
With the persulfate aqueous solution 15.5g of 0.1wt% as initiator, continue to be sealed after logical nitrogen 30min.1
Reaction temperature is gradually increased to into 45 DEG C after hour, reaction obtains aqueous gel polymerizate after 3 hours,
The forced air drying 1.5h at 90 DEG C is cut after glue, is smashed to sieve with pulverizer and is obtained the hydrophobic associated polymer of dry state,
Sample analysis.
It is 90.9% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test Rong solution Shi Jian≤90min, press
GB/T12005.10-92 Molecular Weight for Polyacrylamide determines (viscosimetry) and determines intrinsic viscosity, and presses
[η]=3.73 × 10-4Mw0.66It is 6,320,000 to calculate molecular weight.Apparent viscosity is in 85 DEG C, saline total salinity
Under 80000mg/L～180000mg/L, 1500mg/L polymer concentration solution, using Haake torque rheometer, together
Heart cylinder shear rate 7.34s-1Under apparent viscosity the results are shown in Table 1.90 DEG C of viscosity retention ratios after aging 30 days
Respectively 112%.
【Embodiment 2】
650g deionized waters are initially charged in polymeric kettle, 100g acrylamides, 54g 2- acrylamido is added
- 2- methyl propane sulfonic acids, 1.5g 2- acrylamido cetyl carboxylic acid sodium, 10g dodecylbenzene sodium sulfonate, stir
Mix to being completely dissolved, it is 9 to adjust pH value with NaOH, and starts to be passed through high pure nitrogen, by kettle after 30min
Interior temperature is down to 15 DEG C, then sequentially adds the aqueous solution of sodium bisulfite 15.5g and 0.1wt% of 0.1wt%
Persulfate aqueous solution 15.5g continues to be sealed after logical nitrogen 30min as initiator.Will reaction after 1 hour
Temperature is gradually increased to 45 DEG C, and reaction obtains aqueous gel polymerizate after 3 hours, cuts after glue at 90 DEG C
Lower forced air drying 1.5h, is smashed to sieve with pulverizer and obtains the hydrophobic associated polymer of dry state, sample analysis.
It is 90.9% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test Rong solution Shi Jian≤90min, press
GB/T12005.10-92 Molecular Weight for Polyacrylamide determines (viscosimetry) and determines intrinsic viscosity, and by [η]=3.73
×10-4It is 6,320,000 that Mw0.66 calculates molecular weight.Apparent viscosity is in 85 DEG C, saline total salinity
Under 80000mg/L～180000mg/L, 1500mg/L polymer concentration solution, using Haake torque rheometer, together
Heart cylinder shear rate 7.34s-1Under apparent viscosity the results are shown in Table 1.90 DEG C of viscosity retention ratios after aging 30 days
Respectively 112%.
【Embodiment 3】
650g deionized waters are initially charged in polymeric kettle, 100g acrylamides, 54g 2- acrylamido is added
- 2- methyl propane sulfonic acids, 1.5g 2- acrylamido cetyl carboxylic acid sodium, 10g sodium lauryl sulphates, stirring
To being completely dissolved, it is 9 to adjust pH value with NaOH, and starts to be passed through high pure nitrogen, by kettle after 30min
Temperature is down to 15 DEG C, then sequentially adds the mistake of the aqueous solution of sodium bisulfite 15.5g and 0.1wt% of 0.1wt%
Potassium sulfate solution 15.5g continues to be sealed after logical nitrogen 30min as initiator.Will reaction temperature after 1 hour
Degree is gradually increased to 45 DEG C, and reaction obtains aqueous gel polymerizate after 3 hours, cuts after glue at 90 DEG C
Forced air drying 1.5h, is smashed to sieve with pulverizer and obtains the hydrophobic associated polymer of dry state, sample analysis.
It is 90.9% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test Rong solution Shi Jian≤90min, press
GB/T12005.10-92 Molecular Weight for Polyacrylamide determines (viscosimetry) and determines intrinsic viscosity, and by [η]=3.73
×10-4It is 10,320,000 that Mw0.66 calculates molecular weight.Apparent viscosity is in 85 DEG C, saline total salinity
Under 80000mg/L～180000mg/L, 1500mg/L polymer concentration solution, using Haake torque rheometer, together
Heart cylinder shear rate 7.34s-1Under apparent viscosity the results are shown in Table 1.90 DEG C of viscosity retention ratios after aging 30 days
Respectively 122%.
【Embodiment 4】
650g deionized waters are initially charged in a kettle., add 100g acrylamides, 60g acrylic acid, 15g 2-
Acrylamido dodecyl sodium sulfonate, XXg Brij 56s (EO=4) are stirred to completely molten
Solution, it is 9 to adjust pH value with NaOH, and starts to be passed through high pure nitrogen, is down to temperature in the kettle after 30min
15 DEG C, then sequentially add the potassium peroxydisulfate water of the aqueous solution of sodium bisulfite 17.5g and 0.1wt% of 0.1wt%
Solution 17.5g continues to be sealed after logical nitrogen 30min as initiator.Reaction temperature is gradually risen after 1 hour
To 45 DEG C, reaction obtains gel polymerizate after 3 hours, cuts after glue the forced air drying 1.5h at 90 DEG C,
Smashed to sieve with pulverizer and obtain hydrophobically associating polymers, sample analysis.
It is 89.8% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test Rong solution Shi Jian≤90min, press
GB/T12005.10-92 Molecular Weight for Polyacrylamide determines (viscosimetry) and determines intrinsic viscosity, and presses
[η]=3.73 × 10-4Mw0.66It is 7,580,000 to calculate molecular weight.Apparent viscosity is in 85 DEG C, saline total salinity
Under 80000mg/L～180000mg/L, 1500mg/L polymer concentration solution, using Haake torque rheometer, together
Heart cylinder shear rate 7.34s-1Under apparent viscosity the results are shown in Table 1.90 DEG C of viscosity retention ratios after aging 30 days
Respectively 124%.
【Embodiment 5】
650g deionized waters are initially charged in a kettle., add 100g acrylamides, 55.5g methacrylic acids
5g 2- acrylamido myristyl sodium phosphates, 10g dodecyl phenol polyethenoxy ethers (EO=30), stirring
To being completely dissolved, it is 9 to adjust pH value with NaOH, and starts to be passed through high pure nitrogen, by kettle after 30min
Temperature is down to 15 DEG C, then sequentially adds the mistake of the aqueous solution of sodium bisulfite 10g and 0.1wt% of 0.1wt%
Potassium sulfate solution 10g continues to be sealed after logical nitrogen 30min as initiator.By reaction temperature after 1 hour
45 DEG C are gradually increased to, reaction obtains gel polymerizate after 3 hours, cuts the forced air drying at 90 DEG C after glue
1.5h, smashed to sieve with pulverizer and obtain hydrophobic associated polymer, sample analysis.
It is 90.1% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test Rong solution Shi Jian≤90min, press
GB/T12005.10-92 Molecular Weight for Polyacrylamide determines (viscosimetry) and determines intrinsic viscosity, and presses
[η]=3.73 × 10-4Mw0.66It is 7,260,000 to calculate molecular weight.Apparent viscosity is in 85 DEG C, saline total salinity
Under 80000mg/L～180000mg/L, 1500mg/L polymer concentration solution, using Haake torque rheometer, together
Heart cylinder shear rate 7.34s-1Under apparent viscosity the results are shown in Table 1.90 DEG C of viscosity retention ratios after aging 30 days
Respectively 116%.
【Embodiment 6】
Be initially charged 650g deionized waters in a kettle., add 100g acrylamides, 40g vinylbenzenesulfonic acids,
12g solution properties, 15g Brij 35s (EO=10), stir
Mix to being completely dissolved, it is 9 to adjust pH value with NaOH, and starts to be passed through high pure nitrogen, by kettle after 30min
Interior temperature is down to 15 DEG C, then sequentially adds the aqueous solution of sodium bisulfite 15.2g and 0.1wt% of 0.1wt%
Persulfate aqueous solution 15.2g continues to be sealed after logical nitrogen 30min as initiator.Will reaction after 1 hour
Temperature is gradually increased to 45 DEG C, and reaction obtains gel polymerizate after 3 hours, cuts the air blast at 90 DEG C after glue
1.5h is dried, is smashed to sieve with pulverizer and is obtained hydrophobic associated polymer, sample analysis.
It is 88.9% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test Rong solution Shi Jian≤90min, press
GB/T12005.10-92 Molecular Weight for Polyacrylamide determines (viscosimetry) and determines intrinsic viscosity, and presses
[η]=3.73 × 10-4Mw0.66It is 8,950,000 to calculate molecular weight.Apparent viscosity is in 85 DEG C, saline total salinity
Under 80000mg/L～180000mg/L, 1500mg/L polymer concentration solution, using Haake torque rheometer, together
Heart cylinder shear rate 7.34s-1Under apparent viscosity the results are shown in Table 1.90 DEG C of viscosity retention ratios after aging 30 days
Respectively 121%.
【Embodiment 7】
Be initially charged 650g deionized waters in a kettle., add 100g acrylamides, 30g vinyl sulfonic acids,
9g hexadecyldimethyl benzyl ammonium allyl ammonium chlorides, 9g hexadecyltrimethylammonium chlorides, XXg docosyls
Polyoxyethylenated alcohol (EO=18), stirs to being completely dissolved, and it is 9 to adjust pH value with NaOH, and is started
High pure nitrogen is passed through, temperature in the kettle is down to into 15 DEG C after 30min, then sequentially add the sulfurous acid of 0.1wt%
The persulfate aqueous solution 13.9g of hydrogen sodium water solution 13.9g and 0.1wt% continues logical nitrogen as initiator
Seal after 30min.Reaction temperature is gradually increased to into 45 DEG C after 1 hour, reaction obtains gel and gathers after 3 hours
Product is closed, the forced air drying 1.5h at 90 DEG C is cut after glue, is smashed to sieve with pulverizer and is obtained hydrophobic association polymerization
Thing, sample analysis.
It is 89.7% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test Rong solution Shi Jian≤90min, press
GB/T12005.10-92 Molecular Weight for Polyacrylamide determines (viscosimetry) and determines intrinsic viscosity, and presses
[η]=3.73 × 10-4Mw0.66It is 6,770,000 to calculate molecular weight.Apparent viscosity is in 85 DEG C, saline total salinity
Under 80000mg/L～180000mg/L, 1500mg/L polymer concentration solution, using Haake torque rheometer, together
Heart cylinder shear rate 7.34s-1Under apparent viscosity the results are shown in Table 1.90 DEG C of viscosity retention ratios after aging 30 days
Respectively 114%.
【Embodiment 8】
650g deionized waters are initially charged in a kettle., add 100g acrylamides (AM), 20g vinyls
Benzenesulfonic acid (VBS), 6g cetyl acrylamides, 7g myristyl phenol polyethenoxy ethers (EO=8) are stirred
Mix to being completely dissolved, it is 9 to adjust pH value with NaOH, and starts to be passed through high pure nitrogen, by kettle after 30min
Interior temperature is down to 15 DEG C, then sequentially adds the aqueous solution of sodium bisulfite 12.3g and 0.1wt% of 0.1wt%
Persulfate aqueous solution 12.3g continues to be sealed after logical nitrogen 30min as initiator.Will reaction after 1 hour
Temperature is gradually increased to 45 DEG C, and reaction obtains gel polymerizate after 3 hours, cuts the air blast at 90 DEG C after glue
1.5h is dried, is smashed to sieve with pulverizer and is obtained hydrophobic associated polymer, sample analysis.
It is 91.2% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test Rong solution Shi Jian≤90min, press
GB/T12005.10-92 Molecular Weight for Polyacrylamide determines (viscosimetry) and determines intrinsic viscosity, and presses
[η]=3.73 × 10-4Mw0.66It is 9,150,000 to calculate molecular weight.Apparent viscosity is in 85 DEG C, saline total salinity
Under 80000mg/L～180000mg/L, 1500mg/L polymer concentration solution, using Haake torque rheometer, together
Heart cylinder shear rate 7.34s-1Under apparent viscosity the results are shown in Table 1.90 DEG C of viscosity retention ratios after aging 30 days
Respectively 117%.
【Comparative example 1】
650g deionized waters are initially charged in polymeric kettle, 100g acrylamides, 54g 2- acrylamido is added
- 2- methyl propane sulfonic acids, 1.5g 2- acrylamido cetyl carboxylic acid sodium, stir to being completely dissolved, and use NaOH
It is 9 to adjust pH value, and starts to be passed through high pure nitrogen, temperature in the kettle is down to into 15 DEG C after 30min, Ran Houyi
The persulfate aqueous solution 15.5g of the aqueous solution of sodium bisulfite 15.5g and 0.1wt% of secondary addition 0.1wt% makees
For initiator, continue to be sealed after logical nitrogen 30min.Reaction temperature is gradually increased to into 45 DEG C after 1 hour, reaction
Aqueous gel polymerizate is obtained after 3 hours, the forced air drying 1.5h at 90 DEG C is cut after glue, with crushing
Machine is smashed to sieve and obtains the hydrophobic associated polymer of dry state, sample analysis.
It is 91.2% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test Rong solution Shi Jian≤90min, press
GB/T12005.10-92 Molecular Weight for Polyacrylamide determines (viscosimetry) and determines intrinsic viscosity, and presses
[η]=3.73 × 10-4Mw0.66It is 15,680,000 to calculate molecular weight.Apparent viscosity is in 85 DEG C, saline total salinity
Under 80000mg/L～180000mg/L, 1500mg/L polymer concentration solution, using Haake torque rheometer, together
Heart cylinder shear rate 7.34s-1Under apparent viscosity the results are shown in Table 1.90 DEG C of viscosity retention ratios after aging 30 days
Respectively 49%.
【Comparative example 2】
650g deionized waters are initially charged in polymeric kettle, 100g acrylamides, 54g 2- acrylamido is added
- 2- methyl propane sulfonic acids, 1.5g 2- acrylamido cetyl carboxylic acid sodium, stir to being completely dissolved, and use NaOH
It is 9 to adjust pH value, and starts to be passed through high pure nitrogen, temperature in the kettle is down to into 15 DEG C after 30min, Ran Houyi
The persulfate aqueous solution 15.5g of the aqueous solution of sodium bisulfite 15.5g and 0.1wt% of secondary addition 0.1wt% makees
For initiator, continue to be sealed after logical nitrogen 30min.Reaction temperature is gradually increased to into 45 DEG C after 1 hour, reaction
Aqueous gel polymerizate is obtained after 3 hours, the forced air drying 1.5h at 90 DEG C is cut after glue, with crushing
Machine is smashed to sieve and obtains the hydrophobic associated polymer of dry state, sample analysis.
It is 91.2% by GB/T12005.2-89 polyacrylamide determination of solid content method test solid content, presses
GB/T12005.8-89 powdered polypropylene amide measuring of dissolution velocity method test Rong solution Shi Jian≤90min, press
GB/T12005.10-92 Molecular Weight for Polyacrylamide determines (viscosimetry) and determines intrinsic viscosity, and presses
[η]=3.73 × 10-4Mw0.66It is 15,680,000 to calculate molecular weight.Apparent viscosity is in 85 DEG C, saline total salinity
Under 80000mg/L～180000mg/L, 1500mg/L polymer concentrations, 96.5mg/L octyl phenol Polyethylene oxide
The composite solution of ether (EO=16) concentration, using Haake torque rheometer, concentric drums shear rate 7.34s-1Under
Apparent viscosity the results are shown in Table 1.90 DEG C of viscosity retention ratios after aging 30 days are respectively 49%.
1 85 DEG C of table, the polymer viscosity under different salinities
Claims (10)
1. high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer, by the mixture represented including following masses part
Jing micellar free radical copolymerizations and obtain：
A) 100 parts of acrylamide；
B) 0～60 part of anionic monomer；
C) 0.1～15 part of hydrophobic monomer；
D) 0～15 part of surfactant；
E) 200～2000 parts of water.
2. high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer according to claim 1, its feature exists
2- acrylamide-2-methylpro panesulfonic acids, acrylic acid, methacrylic acid, second are selected from the anionic monomer
At least one in alkenyl benzene sulfonic acid, vinyl sulfonic acid.
3. high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer according to claim 1, its feature exists
It is selected from anion hydrophobic monomer, cation hydrophobic monomer or nonionic hydrophobic monomer extremely in the hydrophobic monomer
Few one kind.
4. high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer according to claim 3, its feature exists
There is the formula shown in formula I in the anion hydrophobic monomer, the cation hydrophobic monomer has formula II
Shown formula, the nonionic hydrophobic monomer has the formula shown in formula III；
Wherein, R0For H or methyl, R1For C1～C22Alkyl chain, R2For C1～C22Alkyl, R3And R4
It is independently selected from C1～C4Alkyl, A be-COOH ,-SO3Na、-SO3H、-CONH2、-CONHRSO3H、
-CONHRSO3At least one in Na；X is halogen, and R is C1～C22Alkylidene, R5For H or first
Base, R6For C1～C22Alkyl.
5. high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer according to claim 1, its feature exists
Anionic surfactant, cationic surfactant or non-ionic surface are selected from the surfactant
At least one in activating agent.
6. high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer according to claim 5, its feature exists
C is selected from the anionic surfactant8-16Alkyl sodium sulfate, C8-16In sodium alkyl benzene sulfonate at least
It is a kind of；The cationic surface active agent is selected from C8-16Alkyl bromide (chlorine) changes at least one in ammonium；Institute
Nonionic surfactant is stated selected from alkylphenol polyoxyethylene (EO=4～30), fatty alcohol-polyoxyethylene ether
At least one in (EO=4～30).
7. the preparation side of the arbitrary described high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer of claim 1～6
Method, comprises the following steps：
A () adds the desired amount of water, acrylamide, anionic monomer, hydrophobic monomer, surface in polymeric kettle
Activating agent, stirs to form solution；
B () adjusts the pH value of solution to 7～10, radical polymerization initiator is added, in 10～30 DEG C of temperature
Cause 0.5～1 hour；
C () is polymerized 2～8 hours at a temperature of 40～60 DEG C, obtain aqueous gel hydrophobic associated polymer：
D () 80～95 DEG C of crushed after being dried, obtain high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer.
8. the preparation method of high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer according to claim 7,
It is characterized in that the radical initiator for redox initiator, its consumption for total monomer weight 0.003～
0.5%.
9. the preparation method of high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer according to claim 8,
It is characterized in that the radical initiator by selected from the oxidation of at least one of Ammonium persulfate. or alkali metal persulphate
Agent and at least one in alkali metal sulfite, alkali metal bisulfite or alkali metal thiosulfate
Reducing agent is constituted.
10. the high temperature and high salt oil deposit displacement of reservoir oil hydrophobic associated polymer described in claim 1～6 is in high temperature and high salt
As the application of oil displacement agent in oil reservoir.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510681509.1A CN106589224A (en) | 2015-10-20 | 2015-10-20 | Hydrophobically associating polymer for oil displacement in high temperature and salinity reservoir and synthetic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510681509.1A CN106589224A (en) | 2015-10-20 | 2015-10-20 | Hydrophobically associating polymer for oil displacement in high temperature and salinity reservoir and synthetic method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106589224A true CN106589224A (en) | 2017-04-26 |
Family
ID=58554678
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510681509.1A Pending CN106589224A (en) | 2015-10-20 | 2015-10-20 | Hydrophobically associating polymer for oil displacement in high temperature and salinity reservoir and synthetic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106589224A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955592A (en) * | 2017-11-24 | 2018-04-24 | 山东大学 | A kind of heavy crude thinner of demulsification certainly and preparation method and application |
| CN109135710A (en) * | 2018-10-09 | 2019-01-04 | 西南石油大学 | The identical association polymer compound oil displacement agent of monomer charge and single hop plug flooding method |
| CN109181672A (en) * | 2018-10-09 | 2019-01-11 | 西南石油大学 | The identical association polymer compound oil displacement agent of monomer charge and alternately injection flooding method |
| CN115947891A (en) * | 2023-03-15 | 2023-04-11 | 成都劳恩普斯科技有限公司 | Temperature-resistant salt-resistant instant polyacrylamide, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280038A (en) * | 2008-05-27 | 2008-10-08 | 湖北省化学研究院 | High molecular weight anionic polymer fluid dispersion, preparation and application thereof |
| CN104892823A (en) * | 2015-05-13 | 2015-09-09 | 中国石油天然气股份有限公司 | Medium-low molecular weight rigid tackifying polymer and preparation method and application thereof |
-
2015
- 2015-10-20 CN CN201510681509.1A patent/CN106589224A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280038A (en) * | 2008-05-27 | 2008-10-08 | 湖北省化学研究院 | High molecular weight anionic polymer fluid dispersion, preparation and application thereof |
| CN104892823A (en) * | 2015-05-13 | 2015-09-09 | 中国石油天然气股份有限公司 | Medium-low molecular weight rigid tackifying polymer and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 中国石油勘探开发研究院: "《中国石油勘探开发研究院五十年理论技术文集 1958-2008 开发篇•工程篇》", 31 October 2008 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955592A (en) * | 2017-11-24 | 2018-04-24 | 山东大学 | A kind of heavy crude thinner of demulsification certainly and preparation method and application |
| CN109135710A (en) * | 2018-10-09 | 2019-01-04 | 西南石油大学 | The identical association polymer compound oil displacement agent of monomer charge and single hop plug flooding method |
| CN109181672A (en) * | 2018-10-09 | 2019-01-11 | 西南石油大学 | The identical association polymer compound oil displacement agent of monomer charge and alternately injection flooding method |
| CN109181672B (en) * | 2018-10-09 | 2021-09-28 | 西南石油大学 | Monomer charge-identical association polymer composite oil displacement agent and alternate injection oil displacement method |
| CN115947891A (en) * | 2023-03-15 | 2023-04-11 | 成都劳恩普斯科技有限公司 | Temperature-resistant salt-resistant instant polyacrylamide, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104448128B (en) | Polymer mobility control agent suitable for high-temperature and high-salinity harsh reservoir and preparation method of polymer mobility control agent | |
| CN104448127B (en) | Polymer mobility control agent suitable for special high salinity reservoirs and preparation method thereof | |
| Sarsenbekuly et al. | Study of salt tolerance and temperature resistance of a hydrophobically modified polyacrylamide based novel functional polymer for EOR | |
| CN106243266B (en) | A kind of tackifier for drilling fluid and preparation method thereof, application | |
| US4702319A (en) | Enhanced oil recovery with hydrophobically associating polymers containing sulfonate functionality | |
| CN102464976B (en) | Oil-displacing composition and preparation method thereof | |
| CN103421137B (en) | The preparation method of high temperature resistance polyacrylamide for oil displacement | |
| US4709759A (en) | Enhanced oil recovery with hydrophobically associating polymers containing N-vinyl-pyrrolidone functionality | |
| CN104449636B (en) | Oil displacement agent of recovery ratio and preparation method thereof is improved suitable for high temperature and high salt harshness oil reservoir | |
| CN103666433B (en) | Oil-displacing agent composition used for improving recovery ratio of high-temperature reservoir and preparation method of composition | |
| CN104448125A (en) | Amphoteric hydrophobically-associating polymer and preparation method thereof | |
| CN106589224A (en) | Hydrophobically associating polymer for oil displacement in high temperature and salinity reservoir and synthetic method | |
| CN105505364A (en) | Oil displacing agent for increasing oil recovery in high temperature high salt mid-low permeability oil reservoir, preparation method and applications thereof | |
| CN106397694B (en) | A kind of micro- block hydrophobic associated polymer of high salt tolerance combed and preparation method thereof | |
| CN107759738B (en) | Water-soluble thermal tackifying copolymer, preparation method and application | |
| CN106589227B (en) | High-temperature high-salinity oil reservoir polyacrylamide oil displacement agent and preparation method thereof | |
| CN105567208A (en) | Oil-displacement composition with improved injectivity, and preparation method and application thereof | |
| CN108314999A (en) | The method for efficiently improving oil recovery factor | |
| CN103160269A (en) | Water base guanidine gum fracturing fluid and preparation method thereof | |
| CN115572347A (en) | High-temperature-resistant high-salt-resistant tackifying and shearing-improving agent for water-based drilling fluid and preparation method and application thereof | |
| CN103788295B (en) | A kind of two-step method prepares the method for acrylamide based copolymer | |
| CN106590591A (en) | Oil displacement agent composition used for oil recovery, and preparation method thereof | |
| CN102464975A (en) | Composition for increasing recovery ratio of high-temperature and high-salt oil reservoir and preparation method thereof | |
| CN106317308A (en) | Acrylamide copolymer, preparation method and application thereof | |
| CN106589232B (en) | Hydrophobic association acrylamide copolymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170426 |
|
| RJ01 | Rejection of invention patent application after publication |