CN107828400A - Salt response type modified polyacrylamide oil displacement agent and preparation method thereof - Google Patents
Salt response type modified polyacrylamide oil displacement agent and preparation method thereof Download PDFInfo
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- CN107828400A CN107828400A CN201710947567.3A CN201710947567A CN107828400A CN 107828400 A CN107828400 A CN 107828400A CN 201710947567 A CN201710947567 A CN 201710947567A CN 107828400 A CN107828400 A CN 107828400A
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- oil displacement
- modified polyacrylamide
- displacement agent
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- 238000006073 displacement reaction Methods 0.000 title claims abstract description 82
- 150000003839 salts Chemical class 0.000 title claims abstract description 54
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 73
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 46
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 propylene oxide ethylene sodium sulfate Chemical compound 0.000 claims abstract description 21
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 16
- 229920000570 polyether Polymers 0.000 claims abstract description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 239000000178 monomer Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 150000005846 sugar alcohols Polymers 0.000 claims description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 238000010926 purge Methods 0.000 claims description 10
- 230000033228 biological regulation Effects 0.000 claims description 7
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- USNWAMPROKAEIT-UHFFFAOYSA-N [Na].C(C=C)(=O)O Chemical compound [Na].C(C=C)(=O)O USNWAMPROKAEIT-UHFFFAOYSA-N 0.000 claims 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 claims 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- TZYWNLMUPXRXAF-UHFFFAOYSA-L disodium ethene sulfate Chemical compound S(=O)(=O)([O-])[O-].[Na+].C=C.[Na+] TZYWNLMUPXRXAF-UHFFFAOYSA-L 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 70
- 239000010779 crude oil Substances 0.000 abstract description 21
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- 229940047670 sodium acrylate Drugs 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- YNDGLMYLSGEDHX-UHFFFAOYSA-N 1,2,4,3-trioxathiane 3,3-dioxide Chemical compound O=S1(=O)OCCOO1 YNDGLMYLSGEDHX-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011814 protection agent Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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
The invention provides a salt response type modified polyacrylamide oil displacement agent and a preparation method thereof. The salt response type modified polyacrylamide oil displacement agent comprises the following raw materials: acrylamide, sodium acrylate, acrylic acid polyether polyol, acrylic acid polyethylene oxide propylene oxide ethylene sodium sulfate, an auxiliary agent, an initiator and water. The invention also provides a preparation method of the oil displacement agent. The oil displacement agent can effectively reduce the viscosity of crude oil for exploitation of crude oil, and has good ionic response strength.
Description
Technical field
The present invention relates to a kind of oil displacement agent, more particularly to a kind of salt response type modified polyacrylamide oil displacement agent and its preparation
Method, belong to technical field of petroleum extraction.
Background technology
Stimuli responsive type oil displacement agent refers to, when extraneous or environmental condition changes, itself to occur physically or chemically to become
A kind of oil displacement agent of change.This kind of oil displacement agent is possessed huge due to its unique performance in various fields such as oilfield chemistry, oil exploitations
Big application prospect.With the reduction of petroleum reserves, the continuous increase of exploitation difficulty, the oil displacement agent with performance-adjustable causes
The very big concern of researcher.
Nowadays the active water drive class oil displacement agent of common chemical oil displacement agent, micellar solution flooding class, microemulsion drive the class displacement of reservoir oil
Agent foam flooding class oil displacement agent.Wherein, active water drive class oil displacement agent is most widely used, can improve recovery ratio and cost is relatively low,
But applicable oil reservoir scope is smaller, poor to environment-responsive, does not also possess adjustable function.Live on the surface of micellar solution flooding class
Whole features of the property active water drive of agent, and different salt can be added and alcohol is modified, but cost is higher.Microemulsion drives
Class oil displacement agent is not mature enough still in initial development stage, experimental method.The stability of foam flooding class oil displacement agent is worst, and lacks
The application and practice of few actual aspect.
For the above situation, there is provided it is a kind of that there is good response to environment, and the displacement of reservoir oil of recovery ratio can be effectively improved
Agent becomes this area urgent problem to be solved.
The content of the invention
In order to solve the above-mentioned technical problem, it is an object of the invention to provide one kind can effectively reduce oil extraction original
The viscosity of oil, while there is the oil displacement agent of good Ion response intensity.
, should the invention provides a kind of salt response type modified polyacrylamide oil displacement agent in order to realize above-mentioned technical purpose
The raw material composition of salt response type modified polyacrylamide oil displacement agent includes：Acrylamide, PAA, acrylic polyether polyalcohol
With acrylic acid polyoxyethylene oxypropylene oxyethylene sulfate, auxiliary agent, initiator and water, wherein, acrylamide accounts for four kinds of monomers
40%-90%, the PAA of gross mass account for the 20%-40% of four kinds of monomer gross mass, acrylic polyether polyalcohol accounts for four kinds
1%-10%, the acrylic acid polyoxyethylene oxypropylene oxyethylene sulfate of monomer gross mass account for the 1%- of four kinds of monomer gross mass
15%, the gross mass of four kinds of monomers：Auxiliary agent：Initiator：The mass ratio of water is 3-5：0.3-0.7：0.05-0.2：5-7, four kinds of lists
Body is：Acrylamide, PAA, acrylic polyether polyalcohol, acrylic acid polyoxyethylene oxypropylene oxyethylene sulfate；Should
The mass percent sum of each raw material of salt response type modified polyacrylamide oil displacement agent is 100%, wherein, acrylic polyether is polynary
The structural formula of alcohol shown in formula I, the structural formula of acrylic acid polyoxyethylene oxypropylene oxyethylene sulfate as shown in Formula II,
A is 1-20 integer, and b is 30-100 integer, and c is 20-60 integer.
In above-mentioned salt response type modified polyacrylamide oil displacement agent, it is preferable that a is 5-15 integer, and b is 35-90's
Integer, c are 20-50 integer.
In above-mentioned salt response type modified polyacrylamide oil displacement agent, it is preferable that a is 7 or 14, b are 40 or 80, c 40.
In above-mentioned salt response type modified polyacrylamide oil displacement agent, it is preferable that acrylamide accounts for four kinds of monomer gross mass
50%-80%, that PAA accounts for the 25%-35% of four kinds of monomer gross mass, acrylic polyether polyalcohol accounts for four kinds of monomers is total
2%-7%, the acrylic acid polyoxyethylene oxypropylene oxyethylene sulfate of quality account for the 5%-10% of four kinds of monomer gross mass.
In above-mentioned salt response type modified polyacrylamide oil displacement agent, it is preferable that acrylic polyether polyalcohol is according to following
It is prepared by step：
10g-30g acrylic acid and 5g-15g KOH are mixed, are warming up to 115 ± 5 DEG C, nitrogen purging displacement；
30g-120g oxirane is added, controls gross pressure to be treated for 0.2MPa-0.4MPa, 140 ± 5 DEG C of reaction temperature
After reacting kettle inner pressure falls back to 0.05MPa-0.15MPa, 60min is reacted；
Add the 5g-15g lauryl alcohol that enters, control pressure is less than 0.4MPa, continues to react 60min, cools the temperature to less than 80
DEG C, obtain acrylic polyether polyalcohol.
In above-mentioned salt response type modified polyacrylamide oil displacement agent, it is preferable that acrylic acid polyoxyethylene oxypropylene
Oxyethylene sulfate is prepared according to following steps：
10g-30g acrylic acid and 5g-15g KOH are mixed, are warming up to 115 ± 5 DEG C, is purged and replaced with nitrogen；
30g-120g oxirane is added, controls anti-gross pressure as 0.2MPa-0.4MPa, 140 ± 5 DEG C of reaction temperature,
After pressure falls after rise in question response kettle, 60min is reacted；
50g-80g expoxy propane is added, control pressure is less than 0.4MPa, continues to react 60min, adds 30g-50g's
Oxyethylene sulfate, 60min is reacted, cools the temperature to less than 80 DEG C, obtains acrylic acid polyoxyethylene oxypropylene oxyethylene sulfate
Sodium.
In above-mentioned salt response type modified polyacrylamide oil displacement agent, it is preferable that the auxiliary agent of use includes dodecyl sulphur
Sour sodium, dodecyl sodium sulfate, cetyl trimethylammonium bromide, alkylpolyoxyethylene sodium sulphate and dodecyl gather
One or more of combinations in oxygen vinethene sodium phosphate.
In above-mentioned salt response type modified polyacrylamide oil displacement agent, it is preferable that it is different that the initiator of use includes azo two
One or more combination in butyronitrile, peroxidating two acyl and persulfate.
Present invention also offers the preparation method of above-mentioned salt response type modified polyacrylamide oil displacement agent, by the aqueous solution from
Prepared by base process for copolymerization, the preparation method comprises the following steps：
Again at room temperature, by acrylamide, PAA, acrylic polyether polyalcohol, acrylic acid PEO epoxy third
Alkane oxyethylene sulfate, auxiliary agent and water mixing, are stirred (being allowed to be completely dissolved)；
Temperature is down to 15 DEG C -25 DEG C, and pH is to 8.0-10.0 for regulation, while is passed through nitrogen, adds trigger under nitrogen protection
Agent, 4h is reacted, obtains gel intermediate product；
Intermediate product is cut, dried, is crushed to the mesh of 60 mesh -100, obtains the salt response type modified polyacrylamide displacement of reservoir oil
Agent.
The above-mentioned salt response type modified polyacrylamide oil displacement agent of the present invention is applied to oil extraction.By effectively scattered and
Emulsified crude oil, significantly reduces viscosity of crude, reduces crude oil flow resistance in stratum and pit shaft, has under low-salt conditions notable
Viscosity reducing effect, it is possible to increase oil production rate.
The salt response type modified polyacrylamide oil displacement agent of the present invention has good response to salt ion, passes through change
Salt ionic concentration, its ability to function with crude oil can be changed, when salt ionic concentration is relatively low, emulsifying capacity is stronger, is more easy to disperse
Crude oil, and in high salt ionic concentration, demulsification ability is stronger, reaches water-oil separating, so as to regulate and control emulsification and demulsification.Regulation from
Before sub- intensity, there is good emulsion dispersion property, viscosity of crude can be significantly reduced, reduce crude oil flow resistance；Adjust from
After sub- intensity, because oil displacement agent is in different ionic strength environment, with Assembling Behavior micro-variations occur for its structure, so as to
Change its ability to function with crude oil so that profit is easily isolated, so as to reach the effect of fast emulsion breaking.This is exploited for reducing
Cost, raising oil recovery factor are respectively provided with significance.
Embodiment
In order to which technical characteristic, purpose and the beneficial effect of the present invention is more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Embodiment 1
A kind of salt response type modified polyacrylamide oil displacement agent is present embodiments provided, it is prepared into according to following steps
Arrive：
Various comonomers account for comonomer gross mass used by synthesis salt response type modified polyacrylamide oil displacement agent
Percentage be：Acrylamide 60%, PAA 30%, the function monomer 3% shown in formula III, the function list shown in formula IV
Body 7%.
The specific preparation method of function monomer is in formula III：Acrylic acid 20g and catalyst KOH are added to reaction under high pressure
In kettle, 115 ± 5 DEG C are warming up to, with the displacement of nitrogen purging three times, oxirane 50g is added, controls the gross pressure in reactor to be
140 ± 5 DEG C of 0.2-0.4MPa, reaction temperature, after pressure falls after rise in question response kettle, continue to react 60min.Lauryl alcohol 10g is added,
Control reacting kettle inner pressure is less than 0.4MPa, continues to react 60min, cools the temperature to less than 80 DEG C, takes out product.
The specific preparation method of function monomer is in formula IV：Acrylic acid 20g and catalyst KOH are added to autoclave
In, 115 ± 5 DEG C are warming up to, with the displacement of nitrogen purging three times, oxirane 50g is added, controls the gross pressure in reactor to be
140 ± 5 DEG C of 0.2-0.4MPa, reaction temperature, after pressure falls after rise in question response kettle, continue to react 60min；Add expoxy propane
60g, control reacting kettle inner pressure are less than 0.4MPa, continue to react 60min；Then oxyethylene sulfate 35g is added, is reacted
60min, after temperature of reaction system is brought down below into 80 DEG C, take out product.
Synthesis salt response type modified polyacrylamide oil displacement agent is prepared by aqueous free radical process for copolymerization.According to throwing
Than various comonomers, auxiliary agent and water are added in reactor, stirring is allowed to be completely dissolved material, and reaction temperature then is down into 20
DEG C, regulation reaction system pH is 9.0, while is passed through nitrogen with the oxygen in fully removal system.Add and trigger under nitrogen protection
Agent, continue to obtain gel intermediate product after reacting 4h.Intermediate product is cut, dried, is crushed to the mesh of 60 mesh -100, is driven
Finish product.
Embodiment 2
A kind of salt response type modified polyacrylamide oil displacement agent is present embodiments provided, it is prepared into according to following steps
Arrive：
Various comonomers account for comonomer gross mass used by synthesis salt response type modified polyacrylamide oil displacement agent
Percentage be：Acrylamide 65%, PAA 25%, the function monomer 4% shown in Formula V, the function monomer shown in Formula IV
6%.
The specific preparation method of function monomer is in Formula V：Acrylic acid 20g and catalyst KOH are added to autoclave
In, 115 ± 5 DEG C are warming up to, with the displacement of nitrogen purging three times, oxirane 50g is added, controls the gross pressure in reactor to be
140 ± 5 DEG C of 0.2-0.4MPa, reaction temperature, after pressure falls after rise in question response kettle, continue to react 60min.Lauryl alcohol 10g is added,
Control reacting kettle inner pressure is less than 0.4MPa, continues to react 60min.After temperature of reaction system is brought down below into 80 DEG C, production is taken out
Thing.
The specific preparation method of function monomer is in Formula IV：Acrylic acid 20g and catalyst KOH are added to autoclave
In, 115 ± 5 DEG C are warming up to, with the displacement of nitrogen purging three times, oxirane 100g is added, controls the gross pressure in reactor to be
140 ± 5 DEG C of 0.2-0.4MPa, reaction temperature, after pressure falls after rise in question response kettle, continue to react 60min.Add expoxy propane
60g, control reacting kettle inner pressure are less than 0.4MPa, continue to react 60min.Then oxyethylene sulfate 35g is added, is reacted
60min, after cooling the temperature to less than 80 DEG C, take out product.
Salt response type modified polyacrylamide oil displacement agent is synthesized to prepare by aqueous free radical micellar co-polymerization method.Press
Various comonomers, auxiliary agent and water are added in reactor according to rate of charge, stirring is allowed to be completely dissolved, then by reaction system temperature
Degree is down to 20 DEG C, and regulation pH is 9.0, while is passed through nitrogen with the oxygen in fully removal system.Add and trigger under nitrogen protection
Agent, continue to obtain gel intermediate product after reacting 4h.Intermediate product is cut, dried, is crushed to the mesh of 60 mesh -100, is driven
Finish product.
Embodiment 3
A kind of salt response type modified polyacrylamide oil displacement agent is present embodiments provided, it is prepared into according to following steps
Arrive：
Various comonomers account for comonomer gross mass used by synthesis salt response type modified polyacrylamide oil displacement agent
Percentage be：Acrylamide 50%, acrylic acid 35%, the function monomer 5% shown in Formula VII, the function list shown in Formula VIII
Body 10%.
The specific preparation method of function monomer is in Formula VII：Acrylic acid 20g and catalyst KOH are added to reaction under high pressure
In kettle, 115 ± 5 DEG C are warming up to, with the displacement of nitrogen purging three times, oxirane 100g is added, controls gross pressure in reactor
For 140 ± 5 DEG C of 0.2-0.4MPa, reaction temperature, after pressure falls after rise in question response kettle, continue to react 60min.Add lauryl alcohol
10g, control reacting kettle inner pressure are less than 0.4MPa, continue to react 60min.After temperature of reaction system is brought down below into 80 DEG C, take
Go out product.
The specific preparation method of function monomer is in Formula VIII：Acrylic acid 20g and catalyst KOH are added to autoclave
In, 115 ± 5 DEG C are warming up to, with the displacement of nitrogen purging three times, oxirane 50g is added, controls the gross pressure in reactor to be
140 ± 5 DEG C of 0.2~0.4MPa, reaction temperature, after pressure falls after rise in question response kettle, continue to react 60min.Add expoxy propane
60g, control reacting kettle inner pressure are less than 0.4MPa, continue to react 60min.Then oxyethylene sulfate 35g is added, is reacted
60min, after temperature of reaction system is brought down below into 80 DEG C, take out product.
Salt response type modified polyacrylamide oil displacement agent is synthesized to prepare by aqueous free radical micellar co-polymerization method.Press
Various comonomers, auxiliary agent and water are added in reactor according to rate of charge, stirring is allowed to be completely dissolved, then by reaction system temperature
Degree is down to 20 DEG C, and regulation reaction system pH is 9.0, while is passed through nitrogen with the oxygen in fully removal system.Under nitrogen protection
Initiator is added, continues to obtain gel intermediate product after reacting 4h.Intermediate product is cut, dry, crushed, obtains oil displacement agent
Product.
Embodiment 4
A kind of salt response type modified polyacrylamide oil displacement agent is present embodiments provided, it is prepared into according to following steps
Arrive：
Various comonomers account for comonomer gross mass used by synthesis salt response type modified polyacrylamide oil displacement agent
Percentage be：Acrylamide 56%, PAA 28%, the function monomer 5% shown in Formula IX, the function monomer shown in Formula X
11%.
The specific preparation method of function monomer is in Formula IX：Acrylic acid 20g and catalyst KOH are added to autoclave
In, 115 ± 5 DEG C are warming up to, with the displacement of nitrogen purging three times, oxirane 100g is added, controls the gross pressure in reactor to be
140 ± 5 DEG C of 0.2-0.4MPa, reaction temperature, after pressure falls after rise in question response kettle, continue to react 60min.Lauryl alcohol 10g is added,
Control reacting kettle inner pressure is less than 0.4MPa, continues to react 60min.After temperature of reaction system is brought down below into 80 DEG C, production is taken out
Thing.
The specific preparation method of function monomer is in Formula X：Acrylic acid 20g and catalyst KOH are added in autoclave,
115 ± 5 DEG C are warming up to, with the displacement of nitrogen purging three times, adds oxirane 100g, it is 0.2- to control gross pressure in reactor
140 ± 5 DEG C of 0.4MPa, reaction temperature, after pressure falls after rise in question response kettle, continue to react 60min.Add expoxy propane 60g, control
Reacting kettle inner pressure processed is less than 0.4MPa, continues to react 60min.Then oxyethylene sulfate 35g is added, reacts 60min, will be anti-
After answering system temperature to be brought down below 80 DEG C, product is taken out.
Salt response type modified polyacrylamide oil displacement agent is synthesized to prepare by aqueous free radical micellar co-polymerization method.Press
Various comonomers, auxiliary agent and water are added in reactor according to rate of charge, stirring is allowed to be completely dissolved, then by reaction system temperature
Degree is down to 20 DEG C, and regulation reaction system pH is 9.0, while is passed through nitrogen with the oxygen in fully removal system.Under nitrogen protection
Initiator is added, continues to obtain gel intermediate product after reacting 4h.Intermediate product is cut, dried, is crushed to 60 mesh -100
Mesh, obtain oil displacement agent product.
Embodiment 5
The reduction rate of crude oil viscosity continuous mode of the salt response type modified polyacrylamide oil displacement agent of embodiment 1-4 synthesis is as follows.
Selection dehydration degassed crude, which is used as, tests oil sample, viscosity of crude 310mPas at 45 DEG C.Displacement of reservoir oil agent solution distills
Water is prepared.
By crude oil to be measured in the water bath with thermostatic control of target detection temperature 45 C constant temperature 1h, weigh 200g crude oil samples in beaker
In, the crude oil activating agent solution for the aimed concn that 200g is prepared is added, is put into 45 DEG C of water bath with thermostatic control, constant temperature 1h, in 400r/
Under min rotating speeds, 3min is stirred.The emulsion of crude oil prepared with rotary viscosity design determining rapidly.Reduction rate of crude oil viscosity is counted as follows
Calculate.
In formula：F is reduction rate of crude oil viscosity, %；μ0For the viscosity of crude oil sample under test temperature, mPas；μ is addition sample
The viscosity of emulsion of crude oil, mPas after solution.
The reduction rate of crude oil viscosity measurement result of the salt response type modified polyacrylamide oil displacement agent of embodiment 1-4 synthesis is shown in Table 1.
Table 1
| Embodiment | System viscosity (mPas) after oil sample viscosity reduction | Viscosity break ratio (%) |
| Embodiment 1 | 33 | 89.35 |
| Embodiment 2 | 40 | 87.10 |
| Embodiment 3 | 30 | 90.32 |
| Embodiment 4 | 34 | 89.03 |
Embodiment 6
The syneresis rate continuous mode of the salt salt response type modified polyacrylamide oil displacement agent of embodiment 1-4 synthesis is as follows.
Selection dehydration degassed crude, which is used as, tests oil sample, viscosity of crude 310mPas at 45 DEG C.Displacement of reservoir oil agent solution distills
Water is prepared, and uses MgCl2Ion concentration in solution is adjusted.
The oil displacement system prepared is added in 10mL has plug graduated cylinder, according to crude oil and displacement of reservoir oil agent solution 1:1 volume ratio,
Crude oil is added in tool plug graduated cylinder, is put into 45 DEG C of electrothermostats and preheats 1h, vibrated after taking-up with hand mode
Tool plug graduated cylinder 200 times, then be put into 45 DEG C of insulating boxs, vibration 200 times is taken out every 5min, untill 30min, most
After put it into 45 DEG C of insulating boxs and stand 15min, record the Volume Changes of water-oil phase.According to experimental record result, can use
Syneresis rate represents emulsion stability：
Syneresis rate=VWater layer/V0
In formula：VWater layerRepresent that emulsion separates out the volume of water,
V0Represent the cumulative volume of emulsion reclaimed water.
By the result being calculated, syneresis rate is high to represent that emulsion stabilization is poor, and syneresis rate is low to represent the steady of emulsion
It is qualitative preferable.The syneresis rate measurement result of the salt response type modified polyacrylamide oil displacement agent of embodiment 1-4 synthesis is shown in Table 2.
Table 2
Above example illustrates that salt response type modified polyacrylamide oil displacement agent of the invention has good to salt ion
Response, by changing salt ionic concentration, its ability to function with crude oil can be changed, so as to regulate and control emulsification and demulsification.
Claims (10)
1. a kind of salt response type modified polyacrylamide oil displacement agent, it is characterised in that the salt response type modified polyacrylamide drives
The raw material composition of finish includes：Acrylamide, PAA, acrylic polyether polyalcohol, acrylic acid PEO epoxy third
Alkane oxyethylene sulfate, auxiliary agent, initiator and water, wherein, acrylamide accounts for the 40%-90% of four kinds of monomer gross mass, acrylic acid
Sodium accounts for the 20%-40% of four kinds of monomer gross mass, acrylic polyether polyalcohol accounts for the 1%-10% of four kinds of monomer gross mass, propylene
Sour polyoxyethylene oxypropylene oxyethylene sulfate accounts for the 1%-15% of four kinds of monomer gross mass, the gross mass of four kinds of monomers：Help
Agent：Initiator：The mass ratio of water is 3-5：0.3-0.7：0.05-0.2：5-7, four kinds of monomers are：Acrylamide, acrylic acid
Sodium, acrylic polyether polyalcohol, acrylic acid polyoxyethylene oxypropylene oxyethylene sulfate；The salt response type modified polypropene acyl
The mass percent sum of each raw material of amine oil displacement agent be 100%, wherein, the structural formula of acrylic polyether polyalcohol shown in formula I,
The structural formula of acrylic acid polyoxyethylene oxypropylene oxyethylene sulfate as shown in Formula II,
A is 1-20 integer, and b is 30-100 integer, and c is 20-60 integer.
2. salt response type modified polyacrylamide oil displacement agent according to claim 1, it is characterised in that a is the whole of 5-15
Number, b are 35-90 integer, and c is 20-50 integer.
3. salt response type modified polyacrylamide oil displacement agent according to claim 2, it is characterised in that a is 7 or 14, b are
40 or 80, c 40.
4. salt response type modified polyacrylamide oil displacement agent according to claim 1, it is characterised in that acrylamide accounts for four
50%-80%, the PAA of kind monomer gross mass account for the 25%-35% of four kinds of monomer gross mass, acrylic polyether polyalcohol
Account for the 2%-7% of four kinds of monomer gross mass, acrylic acid polyoxyethylene oxypropylene oxyethylene sulfate accounts for four kinds of monomer gross mass
5%-10%.
5. salt response type modified polyacrylamide oil displacement agent according to claim 1, it is characterised in that the acrylic acid gathers
Ethoxylated polyhydric alcohol is prepared according to following steps：
10g-30g acrylic acid and 5g-15g KOH are mixed, are warming up to 115 ± 5 DEG C, nitrogen purging displacement；
30g-120g oxirane is added, controls gross pressure as 0.2MPa-0.4MPa, 140 ± 5 DEG C of reaction temperature, question response
After pressure falls back to 0.05MPa-0.15MPa in kettle, 60min is reacted；
5g-15g lauryl alcohol is added, control pressure is less than 0.4MPa, continues to react 60min, cools the temperature to less than 80 DEG C, obtain
To the acrylic polyether polyalcohol.
6. salt response type modified polyacrylamide oil displacement agent according to claim 1, it is characterised in that the acrylic acid gathers
Ethylene oxide propylene oxide oxyethylene sulfate is prepared according to following steps：
10g-30g acrylic acid and 5g-15g KOH are mixed, are warming up to 115 ± 5 DEG C, is purged and replaced with nitrogen；
30g-120g oxirane is added, controls anti-gross pressure to be treated anti-for 0.2MPa-0.4MPa, 140 ± 5 DEG C of reaction temperature
Answer in kettle after pressure falling, reaction 60min；
50g-80g expoxy propane is added, control pressure is less than 0.4MPa, continues to react 60min, adds 30g-50g ethene
Sodium sulphate, 60min is reacted, cools the temperature to less than 80 DEG C, obtains the acrylic acid polyoxyethylene oxypropylene oxyethylene sulfate
Sodium.
7. salt response type modified polyacrylamide oil displacement agent according to claim 1, it is characterised in that the auxiliary agent includes
Lauryl sodium sulfate, dodecyl sodium sulfate, cetyl trimethylammonium bromide, alkylpolyoxyethylene sodium sulphate and
One or more of combinations in alkylpolyoxyethylene sodium phosphate.
8. salt response type modified polyacrylamide oil displacement agent according to claim 1, it is characterised in that the initiator bag
Include the one or more combination in azodiisobutyronitrile, peroxidating two acyl and persulfate.
9. the preparation method of the salt response type modified polyacrylamide oil displacement agent described in claim any one of 1-8, its feature exist
In the preparation method comprises the following steps：
At room temperature, by acrylamide, PAA, acrylic polyether polyalcohol, acrylic acid polyoxyethylene oxypropylene second
Alkene sodium sulphate, auxiliary agent and water mixing, stirring；
Temperature is down to 15 DEG C -25 DEG C, and pH is to 8.0-10.0 for regulation, while is passed through nitrogen, adds initiator under nitrogen protection, instead
4h is answered, obtains gel intermediate product；
Intermediate product is cut, dried, is crushed to the mesh of 60 mesh -100, obtains the salt response type modified polyacrylamide displacement of reservoir oil
Agent.
10. the application of the salt response type modified polyacrylamide oil displacement agent described in claim any one of 1-8, it is characterised in that
The salt response type modified polyacrylamide oil displacement agent is used in oil extraction.
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