CN107652400B - A kind of pH response type modified polyacrylamide oil displacement agent and preparation method thereof - Google Patents
A kind of pH response type modified polyacrylamide oil displacement agent and preparation method thereof Download PDFInfo
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- CN107652400B CN107652400B CN201710778132.0A CN201710778132A CN107652400B CN 107652400 B CN107652400 B CN 107652400B CN 201710778132 A CN201710778132 A CN 201710778132A CN 107652400 B CN107652400 B CN 107652400B
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- 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
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- 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
Abstract
The present invention provides a kind of pH response type modified polyacrylamide oil displacement agents and preparation method thereof.The raw material of the oil displacement agent forms are as follows: the acrylamide of 10wt%-85wt%, the sodium acrylate of 10wt%-40wt%, the poly- N of 5wt%-35wt%, N- diethyl amido ethylmethyl acrylate, the acrylic acid polyoxyethylene oxypropylene of 5wt%-15wt%, auxiliary agent, initiator and water.The present invention also provides the preparation methods of above-mentioned oil displacement agent.The viscosity of oil extraction Crude Oil can be effectively reduced in pH response type modified polyacrylamide oil displacement agent of the invention, while having good response to acid-base property, can effectively improve oil recovery factor.
Description
Technical field
The present invention relates to a kind of oil displacement agent more particularly to a kind of pH response type modified polyacrylamide oil displacement agent and its preparations
Method belongs to oil exploitation technology of reservoir sweep field.
Background technique
In recent years, the research and development of environmental response type oil displacement agent become hot spot that academia and industrial circle are paid close attention to it
One.Due to its unique, excellent performance and environmental response sexual function, in oilfield chemistry, material science, extraction and separation and catalysis
Etc. various fields be owned by potential, huge application prospect.With successively decreasing for the easy mine reserves of petroleum, at the crude oil after emulsification
Reason difficulty is continuously increased, and the exploitation for the adjustable oil displacement agent of behavior that emulsifies and be demulsified has become the focus of numerous scholar's researchs.
The chemical displacement of reservoir oil is most promising raising recovery efficiency technique, nowadays the active water drive class of common oil displacement agent
Oil displacement agent, micellar solution flooding class, microemulsion drive class oil displacement agent foam flooding class oil displacement agent.
Active water drive class oil displacement agent is most widely used, and recovery ratio can be improved and cost is relatively low, but applicable oil reservoir model
It encloses smaller, does not also have adjustable function.Whole features of the active water drive of the surfactant of micellar solution flooding class, and
Different salt and alcohol can be added to be modified, but higher cost.Microemulsion drives class oil displacement agent still in initial development stage, experiment
Method is not mature enough.Foam flooding class oil displacement agent is worst one of this few class surfactant stability, and existing scholar develops
The foam of novel stabilising, but lack the application and practice of practical aspect.
Summary of the invention
In order to solve the above-mentioned technical problem, the purpose of the present invention is to provide a kind of reduction exhaust emission, original can be improved
The oil displacement agent of oil recovery.
In order to achieve the above technical purposes, the present invention provides a kind of pH response type modified polyacrylamide oil displacement agent, with
Mass percent meter, the raw material composition of the pH response type modified polyacrylamide oil displacement agent are as follows: the acryloyl of 10wt%-85wt%
Amine, the sodium acrylate of 10wt%-40wt%, the poly- N of 5wt%-35wt%, N- diethyl amido ethylmethyl acrylate,
Structure is as shown in formula I, the acrylic acid polyoxyethylene oxypropylene of 5wt%-15wt%, structure as shown in formula II,
The initiator of 0.5wt%-3wt%, auxiliary agent and water, wherein (acrylamide, sodium acrylate, poly- N, N- diethyl amido ethyl first
Base acrylate and acrylic acid polyoxyethylene oxypropylene): auxiliary agent: the mass ratio of water is 3-5:0.5-1:5-7, pH response
The sum of mass percent of each raw material of type modified polyacrylamide oil displacement agent is 100%；
Wherein, a is the integer of 3-20, and b is the integer of 20-80, and c is the integer of 10-40.
In pH response type modified polyacrylamide oil displacement agent of the invention, it is preferable that by percentage to the quality, poly- N, N- bis-
The raw material composition of ethyl amido ethylmethyl acrylate include: the ethanol amine of 1wt%-3wt%, 1wt%-3wt% potassium naphthalene,
2- (N, N diethylin) ethyl methacrylate (DEA) of 40wt%-60wt%, 15wt%-25wt% triethylamine,
The acryloyl chloride of 15wt%-25wt%, wherein the quality hundred of each raw material in poly- N, N- diethyl amido ethylmethyl acrylate
Dividing the sum of ratio is 100%.
Above-mentioned poly- N, N- diethyl amido ethylmethyl acrylate are prepared according to the following steps:
Ethanol amine, potassium naphthalene are added in tetrahydrofuran, are completely dissolved at room temperature, alcoholates initiator is obtained；
DEA monomer is quickly adding into mixed solution, after reacting 4h-5h at room temperature, product is anti-with cold n-hexane
Multiple deposition and purification, it is spare；
Above-mentioned product is added into methylene chloride and triethylamine；
Acryloyl chloride is dissolved in methylene chloride, is added dropwise in solution；In 0 ± 3 DEG C of reaction 1-3h, it is placed at room temperature for
10h-16h；
Dichloromethane solution is washed out with distilled water, is extracted 2-3 times, the Precipitation in cold n-hexane, in vacuum tank
Middle drying for standby obtains poly- N, N- diethyl amido ethylmethyl acrylate.
In pH response type modified polyacrylamide oil displacement agent of the invention, it is preferable that by percentage to the quality, acrylic acid is poly-
The raw material composition of ethylene oxide propylene oxide include: the acrylic acid of 5wt%-15wt%, 5wt%-15wt% potassium hydroxide,
The ethylene oxide of 15wt%-45wt% and the propylene oxide of 40wt%-60wt%, wherein acrylic acid polyethylene oxide epoxy third
The sum of mass percent of each raw material of alkane is 100%.
Above-mentioned acrylic acid polyoxyethylene oxypropylene is prepared according to the following steps:
Acrylic acid and catalyst (KOH) are added in autoclave, are warming up to 115 ± 5 DEG C, is purged and is replaced with nitrogen
Three times, ethylene oxide is added, controlling gross pressure in reaction kettle is 0.2-0.4MPa, 140 ± 5 DEG C of reaction temperature, to reaction kettle
After interior pressure is fallen after rise, the reaction was continued 40-60min；Propylene oxide is added, control reacting kettle inner pressure is lower than 0.4MPa, continues anti-
Answer 60-90min；After temperature of reaction system is brought down below 80 DEG C, product is taken out, acrylic acid polyethylene oxide epoxy third is obtained
Alkane.
In pH response type modified polyacrylamide oil displacement agent of the invention, it is preferable that in formula I, a is the integer of 5-15；More
Preferably, a is 6 or 13.
In pH response type modified polyacrylamide oil displacement agent of the invention, it is preferable that in formula II, b is the integer of 40-80, c
For the integer of 20-40；It is highly preferred that b is 50 or 70, c 30.
In pH response type modified polyacrylamide oil displacement agent of the invention, it is preferable that the auxiliary agent of use is selected from dodecyl
One or more of sodium sulphate, dodecyl sodium sulfate, cetyl trimethylammonium bromide.
In pH response type modified polyacrylamide oil displacement agent of the invention, it is preferable that the initiator of use is selected from azo two
One or more of isobutyronitrile, peroxidating two acyl, persulfate.
In pH response type modified polyacrylamide oil displacement agent of the invention, it is preferable that the content of acrylamide is 20wt%-
The content of 75wt%, sodium acrylate are 15wt%-35wt%, and the content of poly- N, N- diethyl amido ethylmethyl acrylate are
10wt%-25wt%, the content of acrylic acid polyoxyethylene oxypropylene are 5wt%-10wt%.
In pH response type modified polyacrylamide oil displacement agent of the invention, it is preferable that (acrylamide, sodium acrylate, poly- N,
N- diethyl amido ethylmethyl acrylate and acrylic acid polyoxyethylene oxypropylene): auxiliary agent: the mass ratio of water is 4:
0.7:5.3。
The present invention also provides the preparation methods of above-mentioned pH response type modified polyacrylamide oil displacement agent, certainly by aqueous solution
Prepared by base process for copolymerization, the preparation method the following steps are included:
By acrylamide, sodium acrylate, poly- N, N- diethyl amido ethylmethyl acrylate, acrylic acid polyethylene oxide
Propylene oxide is mixed with auxiliary agent, water；
At 10 DEG C -15 DEG C, adjusting pH is 8.0-9.0, while being passed through nitrogen, and initiator is added, and after reacting 5h, obtains pH
Response type modified polyacrylamide oil displacement agent.
In the above preparation method, it is preferable that mass fraction is used to adjust pH for 10% sodium hydroxide solution.
In the above preparation method, the speed that is passed through of nitrogen is not required.
PH response type modified polyacrylamide oil displacement agent of the invention is suitable for oil extraction field, by effectively dispersing and
Emulsified crude oil significantly reduces viscosity of crude, reduces crude oil flow resistance in stratum and pit shaft, still has under the conditions of high temperature and high salt
There is significant viscosity reducing effect, can be improved oil production rate.
PH response type modified polyacrylamide oil displacement agent of the invention can effectively divide crude oil before adjusting pH value
The effects of dissipating, emulsifying significantly reduces viscosity of crude, reduces crude oil flow resistance in stratum and pit shaft；After adjusting pH value, by
A degree of microcosmic adjustment has been obtained in the structure and Assembling Behavior of oil displacement agent and can change the ability to function of itself and crude oil,
So that grease is easily isolated, to achieve the effect that fast emulsion breaking, this for reduce recovery process energy consumption, reduce exhaust emission,
It improves oil recovery factor and all has significance.
The viscosity of oil extraction Crude Oil can be effectively reduced in pH response type modified polyacrylamide oil displacement agent of the invention,
Viscosity break ratio can achieve 90% or more, have good sound much higher than the 60%-70% of traditional oil displacement agent, while to acid-base property
It answers, can effectively control dispersion and emulsified crude oil, advantageously reduce energy consumption in recovery process, reduce exhaust emission, improve crude oil
Harvest speed and recovery ratio.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
A kind of pH response type modified polyacrylamide oil displacement agent is present embodiments provided, is to be prepared according to the following steps
It arrives:
Various comonomers used by pH response type modified polyacrylamide oil displacement agent account for the percentage of gross mass are as follows: third
Acrylamide 68%, sodium acrylate 15%,；Function monomer 12% shown in formula III, function monomer 5% shown in formula IV.
Function monomer is specific the preparation method comprises the following steps: 2mmol ethanol amine, 2mmol potassium naphthalene are added to tetrahydrofuran in formula III
In, it is completely dissolved at room temperature, obtains alcoholates initiator；The pure drying DEA monomer of 30mmol is quickly adding into mixing
In solution, after reacting 5h at room temperature, product is purified with cold n-hexane repeated precipitation, spare；By the methylene chloride of 60mL and
The triethylamine of 14mmol is added in round-bottomed flask, in the above-mentioned product that 4mmol is added；12mmol acryloyl chloride is dissolved in dichloro
In methane, it is added dropwise in solution；In 0 DEG C of reaction 2h, then it is being placed at room temperature for 12h；With distilled water by dichloromethane solution
It washes out, extraction 2-3 times, then the Precipitation in cold n-hexane, the drying for standby in vacuum tank.
Function monomer is specific the preparation method comprises the following steps: 20g acrylic acid and 10gKOH catalyst are added to reaction under high pressure in formula IV
In kettle, 115 ± 5 DEG C are warming up to, three times with the displacement of nitrogen purging, adds 50g ethylene oxide, controlling gross pressure in reaction kettle is
140 ± 5 DEG C of 0.2-0.4MPa, reaction temperature, after reacting kettle inner pressure falling, the reaction was continued 60min；100g epoxy third is added
Alkane, control reacting kettle inner pressure are lower than 0.4MPa, the reaction was continued 60min；After temperature of reaction system is brought down below 80 DEG C, take out
Product.
Synthesis pH 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 to be added in reaction kettle, stirring is allowed to be completely dissolved material, then drops temperature of reaction system
To 10 DEG C, adjusting reaction system pH is 8.0, while being passed through nitrogen with the oxygen in sufficiently removal system.It is added under nitrogen protection
Initiator after the reaction was continued 5h, obtains gel intermediate product, by intermediate product cutting, it is dry, crush, obtain oil displacement agent.
Embodiment 2
A kind of pH response type modified polyacrylamide oil displacement agent is present embodiments provided, through the following steps that being prepared into
It arrives:
Various comonomers used by pH response type modified polyacrylamide oil displacement agent account for the percentage of gross mass are as follows: third
Acrylamide 65%, sodium acrylate 15%, function monomer 10% shown in Formula V, function monomer 10% shown in Formula IV.
Function monomer is specific the preparation method comprises the following steps: 4mmol ethanol amine, 4mmol potassium naphthalene are added to tetrahydrofuran in Formula V
In, it is completely dissolved a few minutes at room temperature, obtains alcoholates initiator；The pure drying DEA monomer of 60mmol is rapidly added
Into mixed solution, after reacting 5h at room temperature, product is purified with cold n-hexane repeated precipitation, spare；By the dichloro of 60mL
The triethylamine of methane and 14mmol are added in round-bottomed flask, in the above-mentioned product that 4mmol is added；12mmol acryloyl chloride is molten
In methylene chloride, it is added dropwise in solution；In 0 DEG C of reaction 2h, then it is being placed at room temperature for 12h；With distilled water by dichloromethane
Alkane solution washes out, extraction 2-3 times, then the Precipitation in cold n-hexane, the drying for standby in vacuum tank.
Function monomer is specific the preparation method comprises the following steps: 20g acrylic acid and 10gKOH catalyst are added to reaction under high pressure in Formula IV
In kettle, 115 ± 5 DEG C are warming up to, three times with the displacement of nitrogen purging, adds 50g ethylene oxide, controlling gross pressure in reaction kettle is
140 ± 5 DEG C of 0.2-0.4MPa, reaction temperature, after reacting kettle inner pressure falling, the reaction was continued 60min；100g epoxy third is added
Alkane, control reacting kettle inner pressure is lower than 0.4MPa, the reaction was continued 60min, after temperature of reaction system is brought down below 80 DEG C, takes out
Product.
PH response type modified polyacrylamide oil displacement agent is synthesized to prepare by aqueous free radical micellar co-polymerization method.It presses
Various comonomers, auxiliary agent and water are added in reaction kettle according to feed ratio, stirring is allowed to be completely dissolved, then by reaction system temperature
Degree is down to 10 DEG C, and adjusting reaction system pH is 8.0, while being passed through nitrogen with the oxygen in sufficiently removal system, under nitrogen protection
Initiator is added, obtains gel intermediate product after the reaction was continued 5h, by intermediate product cutting, it is dry, crush, obtain the displacement of reservoir oil
Agent.
Embodiment 3
A kind of pH response type modified polyacrylamide oil displacement agent is present embodiments provided, through the following steps that being prepared into
It arrives:
Various comonomers used by pH response type modified polyacrylamide oil displacement agent account for the percentage of gross mass are as follows: third
Acrylamide 55%, acrylic acid 15%, function monomer 20% shown in Formula VII, function monomer 10% shown in Formula VIII.
Function monomer is specific the preparation method comprises the following steps: 2mmol ethanol amine, 2mmol potassium naphthalene are added to tetrahydrofuran in Formula VII
In, it is completely dissolved at room temperature, obtains alcoholates initiator；The pure drying DEA monomer of 30mmol is quickly adding into mixing
In solution, after reacting 5h at room temperature, product is purified with cold n-hexane repeated precipitation, spare；By the methylene chloride of 60mL and
The triethylamine of 14mmol is added in round-bottomed flask, in the above-mentioned product that 4mmol is added；12mmol acryloyl chloride is dissolved in dichloro
In methane, it is added dropwise in solution；In 0 DEG C of reaction 2h, then it is being placed at room temperature for 12h；With distilled water by dichloromethane solution
It washes out, extraction 2-3 times, then the Precipitation in cold n-hexane.The drying for standby in vacuum tank.
Function monomer is specific the preparation method comprises the following steps: that 20g acrylic acid and 10g KOH catalyst are added to high pressure is anti-in Formula VIII
It answers in kettle, is warming up to 115 ± 5 DEG C, three times with the displacement of nitrogen purging, add 70g ethylene oxide, control gross pressure in reaction kettle
For 140 ± 5 DEG C of 0.2-0.4MPa, reaction temperature, after reacting kettle inner pressure falling, the reaction was continued 60min；160g epoxy is added
Propane, control reacting kettle inner pressure are lower than 0.4MPa, the reaction was continued 60min；After temperature of reaction system is brought down below 80 DEG C, take
Product out.
PH response type modified polyacrylamide oil displacement agent is synthesized to prepare by aqueous free radical micellar co-polymerization method.It presses
Various comonomers, auxiliary agent and water are added in reaction kettle according to feed ratio, stirring is allowed to be completely dissolved, then by reaction system temperature
Degree is down to 10 DEG C, and adjusting reaction system pH is 8.0, while being passed through nitrogen with the oxygen in sufficiently removal system.Under nitrogen protection
Initiator is added, obtains gel intermediate product after the reaction was continued 5h, by intermediate product cutting, it is dry, crush, obtain the displacement of reservoir oil
Agent.
Embodiment 4
A kind of pH response type modified polyacrylamide oil displacement agent is present embodiments provided, through the following steps that being prepared into
It arrives:
Various comonomers used by pH response type modified polyacrylamide oil displacement agent account for the percentage of gross mass are as follows: third
Acrylamide 50%, sodium acrylate 20%, function monomer 20% shown in Formula IX, function monomer 10% shown in Formula X.
Function monomer is specific the preparation method comprises the following steps: 4mmol ethanol amine, 4mmol potassium naphthalene are added to tetrahydrofuran in Formula IX
In, it is completely dissolved at room temperature, obtains alcoholates initiator；The pure drying DEA monomer of 60mmol is quickly adding into mixing
In solution, after anionic polymerisation reacts 5h at room temperature, product is purified with cold n-hexane repeated precipitation, spare；It will
The methylene chloride of 60mL and the triethylamine of 14mmol are added in round-bottomed flask, in the above-mentioned product that 4mmol is added；By 12mmol
Acryloyl chloride is dissolved in methylene chloride, is added dropwise in solution；In 0 DEG C of reaction 2h, then it is being placed at room temperature for 12h.With distillation
Water washes out dichloromethane solution, extraction 2-3 times, then the Precipitation in cold n-hexane.The drying for standby in vacuum tank.
Function monomer is specific the preparation method comprises the following steps: 20g acrylic acid and 10gKOH catalyst are added to autoclave in Formula X
In, 115 ± 5 DEG C are warming up to, three times with the displacement of nitrogen purging, adds 70g ethylene oxide, controlling gross pressure in reaction kettle is
140 ± 5 DEG C of 0.2-0.4MPa, reaction temperature, after reacting kettle inner pressure falling, the reaction was continued 60min.160g epoxy third is added
Alkane, control reacting kettle inner pressure are lower than 0.4MPa, the reaction was continued 60min.After temperature of reaction system is brought down below 80 DEG C, take out
Product.
PH response type modified polyacrylamide oil displacement agent is synthesized to prepare by aqueous free radical micellar co-polymerization method.It presses
Various comonomers, auxiliary agent and water are added in reaction kettle according to feed ratio, stirring is allowed to be completely dissolved, then by reaction system temperature
Degree is down to 10 DEG C, and adjusting reaction system pH is 8.0, while being passed through nitrogen with the oxygen in sufficiently removal system；Under nitrogen protection
Initiator is added, obtains gel intermediate product after the reaction was continued 5h, by intermediate product cutting, it is dry, crush, obtain oil displacement agent
Product.
Embodiment 5
The reduction rate of crude oil viscosity continuous mode of the pH response type modified polyacrylamide oil displacement agent of embodiment 1-4 is as follows.
It chooses dehydration degassed crude and is used as test oil sample, viscosity of crude 380mPa.s at 45 DEG C.The distillation of displacement of reservoir oil agent solution
Water is prepared.
(1) by viscous crude to be measured in the water bath with thermostatic control of target detection temperature 45 C constant temperature 1h, weigh 200g and (be accurate to
0.1g) viscous crude oil sample is added the viscous crude activator solution for the aimed concn that 200g (being accurate to 0.1g) prepares, is put into beaker
In 45 DEG C of water bath with thermostatic control, agitating paddle is placed in a beaker the heart by constant temperature 1h, and away from bottom (2-3) mm at, adjust revolving speed be
400r/min stirs 3min under constant temperature.
(2) the viscous crude lotion prepared with rotary viscosity design determining rapidly.At 45 DEG C, the selection 0-4 rotor of NDJ type,
Brookfield type chooses 61-64 rotor, contains sample cylinder diameter and is not less than 60mm, tests revolving speed 60r/min.
(3) every 2s, single reading is recorded, is recorded 50 times.Choose average value.
(4) reducing thick oil viscosity rate is calculated by formula (a).
In formula:
F- reducing thick oil viscosity rate, %；
μ0The viscosity of crude oil sample, mPa.s under test temperature；
μ-addition sample solution rear thick fat liquor viscosity, mPa.s.
Each sample does two Duplicate Samples, and taking arithmetic mean of instantaneous value is measurement result.Each measured value and arithmetic mean of instantaneous value it
Difference is not more than 1.0%.
The reduction rate of crude oil viscosity measurement result of the pH response type modified polyacrylamide oil displacement agent of embodiment 1-4 synthesis is shown in Table 1.
The pH response type modified polyacrylamide oil displacement agent reduction rate of crude oil viscosity measurement result of 1 embodiment 1-4 of table synthesis
| Embodiment | System viscosity (mPa.s) after oil sample viscosity reduction | Viscosity break ratio (%) |
| Embodiment 1 | 28 | 92.63 |
| Embodiment 2 | 32 | 91.57 |
| Embodiment 3 | 39 | 89.73 |
| Embodiment 4 | 35 | 90.79 |
Embodiment 6
The syneresis rate continuous mode of the pH response type modified polyacrylamide oil displacement agent of embodiment 1-4 synthesis is as follows.
It chooses dehydration degassed crude and is used as test oil sample, viscosity of crude 380mPa.s at 45 DEG C.The distillation of displacement of reservoir oil agent solution
Water is prepared, and is adjusted with pH value of the bronsted lowry acids and bases bronsted lowry to solution.
Have in plug graduated cylinder in 10mL and prepared oil displacement agent is added, it, will according to the volume ratio of crude oil and displacement of reservoir oil agent solution 1:1
Crude oil is added in tool plug graduated cylinder, is put into 45 DEG C of electrothermostats and is preheated 1h, vibrates tool with hand mode after taking-up
Plug graduated cylinder 200 times, then be put into 45 DEG C of insulating boxs, oscillation 200 times is taken out every 5min, until 30min, finally
It puts it into 45 DEG C of insulating boxs and stands 1h, record the volume change of water-oil phase.According to experimental record as a result, syneresis rate can be used
To indicate emulsion stability:
Syneresis rate=VWater layer/V0
Wherein, VWater layer- indicate that the volume of water is precipitated in emulsion,
V0The total volume of water in-expression emulsion.
By being calculated as a result, syneresis rate height indicates that emulsion stabilization is poor, syneresis rate is low to indicate the steady of emulsion
It is qualitative preferable.
The syneresis rate measurement result of the pH response type modified polyacrylamide oil displacement agent of embodiment 1-4 synthesis is shown in Table 2.
The pH response type modified polyacrylamide oil displacement agent syneresis rate measurement result of 2 embodiment 1-4 of table synthesis
Above embodiments explanation, pH response type modified polyacrylamide oil displacement agent of the invention can be effectively reduced crude oil and open
The viscosity of Crude Oil is adopted, while there is good response to acid-base property.
Claims (12)
1. a kind of pH response type modified polyacrylamide oil displacement agent, which is characterized in that by percentage to the quality, which changes
Property POLYACRYLAMIDE FLOODING agent raw material composition are as follows: the acrylamide of 10wt%-85wt%, the acrylic acid of 10wt%-40wt%
Sodium, the poly- N of 5wt%-35wt%, N- diethyl amido ethylmethyl acrylate, structure is as shown in formula I, 5wt%-
The acrylic acid polyoxyethylene oxypropylene of 15wt%, structure is as shown in formula II, the initiator of 0.5wt%-3wt%, auxiliary agent
And water；
Wherein, (acrylamide, sodium acrylate, poly- N, N- diethyl amido ethylmethyl acrylate and acrylic acid polycyclic oxygen second
Alkane propylene oxide): auxiliary agent: the mass ratio of water is 3-5:0.5-1:5-7, each original of pH response type modified polyacrylamide oil displacement agent
The sum of mass percent of material is 100%；
Wherein, a is the integer of 3-20, and b is the integer of 20-80, and c is the integer of 10-40.
2. pH response type modified polyacrylamide oil displacement agent according to claim 1, which is characterized in that with mass percent
Meter, the poly- N, N- diethyl amido ethylmethyl acrylate raw material composition include: 1wt%-3wt% ethanol amine,
2- (N, N diethylin) ethyl methacrylate, 15wt%-25wt% of the potassium naphthalene of 1wt%-3wt%, 40wt%-60wt%
Triethylamine, 15wt%-25wt% acryloyl chloride, wherein each original in poly- N, N- diethyl amido ethylmethyl acrylate
The sum of mass percent of material is 100%.
3. pH response type modified polyacrylamide oil displacement agent according to claim 1, which is characterized in that with mass percent
Meter, the raw material composition of the acrylic acid polyoxyethylene oxypropylene include: acrylic acid, the 5wt%- of 5wt%-15wt%
The propylene oxide of the potassium hydroxide of 15wt%, the ethylene oxide of 15wt%-45wt% and 40wt%-60wt%, wherein acrylic acid
The sum of mass percent of each raw material of polyoxyethylene oxypropylene is 100%.
4. pH response type modified polyacrylamide oil displacement agent according to claim 1, which is characterized in that in formula I, a 5-
15 integer.
5. pH response type modified polyacrylamide oil displacement agent according to claim 1, which is characterized in that in formula I, a be 6 or
13。
6. pH response type modified polyacrylamide oil displacement agent according to claim 1, which is characterized in that in formula II, b is
The integer of 40-80, c are the integer of 20-40.
7. pH response type modified polyacrylamide oil displacement agent according to claim 6, which is characterized in that in formula II, b 50
Or 70, c 30.
8. pH response type modified polyacrylamide oil displacement agent according to claim 1, which is characterized in that the auxiliary agent is selected from
One or more of lauryl sodium sulfate, dodecyl sodium sulfate, cetyl trimethylammonium bromide.
9. pH response type modified polyacrylamide oil displacement agent according to claim 1, which is characterized in that the initiator choosing
From one or more of azodiisobutyronitrile, peroxidating two acyl, persulfate.
10. pH response type modified polyacrylamide oil displacement agent according to claim 1, which is characterized in that the acryloyl
The content of amine is 20wt%-75wt%, and the content of the sodium acrylate is 15wt%-35wt%, the poly- N, N- diethylamide
The content of base ethylmethyl acrylate is 10wt%-25wt%, and the content of the acrylic acid polyoxyethylene oxypropylene is
5wt%-10wt%；
(acrylamide, sodium acrylate, poly- N, N- diethyl amido ethylmethyl acrylate and acrylic acid polyethylene oxide epoxy
Propane): auxiliary agent: the mass ratio of water is 4:0.7:5.3.
11. the preparation method of the described in any item pH response type modified polyacrylamide oil displacement agents of claim 1-10, feature
Be, the preparation method the following steps are included:
By acrylamide, sodium acrylate, poly- N, N- diethyl amido ethylmethyl acrylate, acrylic acid polyethylene oxide epoxy
Propane is mixed with auxiliary agent, water；
At 10 DEG C -15 DEG C, adjusting pH is 8.0-9.0, while being passed through nitrogen, and initiator is added, and after reacting 5h, obtains the pH
Response type modified polyacrylamide oil displacement agent.
12. preparation method according to claim 11, which is characterized in that use mass fraction molten for 10% sodium hydroxide
Liquid adjusts pH.
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| CN110669489B (en) * | 2019-10-14 | 2021-10-22 | 中国石油化工股份有限公司 | Low-power depolymerization emulsification viscosity reducer for cold production of thick oil and preparation method thereof |
| CN116064006B (en) * | 2021-11-01 | 2024-02-23 | 中国石油化工股份有限公司 | PH response type well wall stabilizing material and preparation method and application thereof |
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| CN1903974A (en) * | 2005-07-26 | 2007-01-31 | 中国科学院理化技术研究所 | Nano-water soluble microgel oil displacing material and its preparation method |
| CN101328251A (en) * | 2008-06-27 | 2008-12-24 | 苏州大学 | Biodegradable temperature/pH dual responsiveness aquagel |
| EP2348089A1 (en) * | 2010-01-26 | 2011-07-27 | S.P.C.M. Sa | Water-soluble polymers for oil recovery |
| CN102453254A (en) * | 2010-10-18 | 2012-05-16 | 中国石油化工股份有限公司 | Acrylic acid ester compound and polymer, preparation method and application thereof |
| CN103242498A (en) * | 2013-05-08 | 2013-08-14 | 中国科学院化学研究所 | Amphiphilic block inner quaternary ammonium salt as well as preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903974A (en) * | 2005-07-26 | 2007-01-31 | 中国科学院理化技术研究所 | Nano-water soluble microgel oil displacing material and its preparation method |
| CN101328251A (en) * | 2008-06-27 | 2008-12-24 | 苏州大学 | Biodegradable temperature/pH dual responsiveness aquagel |
| EP2348089A1 (en) * | 2010-01-26 | 2011-07-27 | S.P.C.M. Sa | Water-soluble polymers for oil recovery |
| CN102453254A (en) * | 2010-10-18 | 2012-05-16 | 中国石油化工股份有限公司 | Acrylic acid ester compound and polymer, preparation method and application thereof |
| CN103242498A (en) * | 2013-05-08 | 2013-08-14 | 中国科学院化学研究所 | Amphiphilic block inner quaternary ammonium salt as well as preparation method and application thereof |
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