CN107828402A - One kind improves deep-layer heavy crude CO2The chemical addition agent of gas drive process recovery ratio - Google Patents
One kind improves deep-layer heavy crude CO2The chemical addition agent of gas drive process recovery ratio Download PDFInfo
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- CN107828402A CN107828402A CN201710430272.9A CN201710430272A CN107828402A CN 107828402 A CN107828402 A CN 107828402A CN 201710430272 A CN201710430272 A CN 201710430272A CN 107828402 A CN107828402 A CN 107828402A
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- 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
- C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
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- 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
Abstract
The invention discloses one kind to improve deep-layer heavy crude CO2The chemical addition agent of gas drive process recovery ratio, is made up of solubilizer and thinner, and the weight ratio of solubilizer and thinner is 1~6:1；Wherein, the solubilizer is P-methoxybenzoic acid ester type compound；The thinner is long alkyl chain methacrylates styrene vinyl acetate co-polymer.The chemical addition agent of the present invention, it can both promote CO2It is miscible in viscous crude ability, reduce CO2Minimum miscibility pressure between viscous crude, form CO2Miscible-phase displacement, viscosity of thickened oil can be substantially reduced again, improve viscous crude mobile performance, so as to improve thick oil recovery ratio, with efficiency high, economy is strong, the advantages such as energy consumption is small, the high deep low permeability reservoir that the strata pressure that is particularly suitable for use in is high, viscosity of crude is high and permeability is low, has broad application prospects.
Description
Technical field
The present invention relates to one kind to improve deep-layer heavy crude CO2The chemical addition agent of gas drive process recovery ratio, can promote CO2It is miscible
In viscous crude ability, viscosity of thickened oil is reduced, belongs to oil field development technical field.
Background technology
Deep-layer heavy crude refers to reservoir buried depth amplitude big (900~1300m) heavy crude reservoir, compared with general shallow layer thick oil,
Deep-layer heavy crude, which removes, to be had outside the features such as viscosity is big, underground poor fluidity, also buried deep steam injection pressure height, steam injection heat waste with reservoir
Greatly, oil reservoir is thin, and oil reservoir sensitiveness is strong, loose cementation and the development scheme selection difficulty factor for being unfavorable for exploitation such as big, belongs to
Difficulty adopts viscous crude.Based on these factors, deep-layer heavy crude development problem is always the problem that annoying oil exploitation work, and crude oil glues
Thick, poor fluidity, the flowing near shaft bottom and the borehole wall is excessively poor, and many difficulties are brought to oil extraction operation.Practice result shows,
Conventional crude production technique such as notes CO2Drive, steam thermal recovery, chemical viscosity reduction, microorganism drive etc. are for exploiting deep-layer heavy crude effect simultaneously
It is undesirable.Therefore, the new the Technology of Heavy Oil Recovery of exploitation is ground, it is urgent problem to be solved to reduce thickened oil recovery difficulty.
At present in oil extraction field, CO is noted2Gas drive and chemical viscosity reduction are the preferable two kinds of technologies of prospect, and both act on
Principle is different.Wherein, CO is noted2Drive refers to CO2Stratum is injected after being compressed to certain pressure, in this process CO2Can it is miscible in
Crude oil, so that crude oil volumetric expansion, reduces oil density and viscosity, mixed phase effect is formed, improves crude oil fluidity.Note CO2
Drive because its power consumption is small, and CO can be fixed2Reduce greenhouse effects and receive much concern.Chemical viscosity reduction technology of reservoir sweep was recovering the oil
Thinner is injected to stratum in journey, it is to destroy the overlapping packed structures of plane between asphalitine supermolecule and colloid molecule that it, which is acted on,
Pitch micella spatial extent degree is reduced, makes the distribution of pitch micella more scattered, so as to reduce viscosity of thickened oil, enhancing viscous crude flowing
Property, improve thick oil recovery ratio.Conventional thinner can be divided into surfactant thinner and oil-soluble viscosity reduction in the market
Agent.Practice result shows, either CO2Gas drive or chemical viscosity reduction, one of which technology effect in thickened oil recovery is used alone
It is unsatisfactory.At present, both at home and abroad there is not yet relevant by CO2The report that two kinds of gas drive, chemical viscosity reduction technologies are combined.
The content of the invention
For above-mentioned prior art, the invention provides one kind to improve deep-layer heavy crude CO2The chemistry of gas drive process recovery ratio
Additive, it contains solubilizer and thinner, can promote CO2It is miscible thick suitable for deep layer in viscous crude ability, reduction viscosity of thickened oil
The exploitation of oil.
The present invention is achieved by the following technical solutions：
One kind improves deep-layer heavy crude CO2The chemical addition agent of gas drive process recovery ratio, is made up of solubilizer and thinner, increases
The weight of solvent and thinner ratio is 1~6:1；Wherein, the solubilizer is that can dissolve crude oil polar compound, pair of long-chain component
Methoxy benzoic acid ester type compound (can be commercially available, or conventional method is prepared) by conventional market, its contain ester group,
Phenyl ring and saturated alkyl chain, the polar compound in crude oil is can dissolve, and promote CO2Crude oil is dissolved in, promotes CO2- crude oil mixed phase
Development, form mixed phase and drive, expand crude oil, reduce the density and viscosity of crude oil, the mobility of increase crude oil in the earth formation；Its phase
To molecular mass 180.07~320.22, structural formula is as follows, and in structural formula, n is 2~12 integer；
The thinner is long alkyl chain methacrylates-styrene-vinyl acetate co-polymer, its polar group contained
Such as phenyl ring, ester group can effectively break the viscous crude studies on asphaltene macromolecular piled up overlapping with colloid planes of molecules,
So as to destroy the space net structure that asphaltene colloid is formed, the viscosity of viscous crude is effectively reduced；Its structural formula is as follows：
In formula ,-R represents saturated alkyl chain, and its C atomicity is 12~20；i:j:K=(5~10):(2~8):(1~3).
Long alkyl chain methacrylates-styrene-the vinyl acetate co-polymer, is to be prepared by the following method to obtain
's：Using methyl methacrylate, styrene and vinylacetate as raw material, three's mol ratio is (5~10):(2~8):(1~
3), using toluene as solvent, initiator azodiisobutyronitrile (dosage is the 5% of raw material gross weight), under nitrogen atmosphere, 65 are added
6~10h of reaction is stirred at reflux under the conditions of~75 DEG C, obtains terpolymer；80 DEG C ± 2 DEG C are warming up to, is slowly added to the concentrated sulfuric acid (matter
Measure concentration 98%) (concentrated sulfuric acid volume：Raw material gross weight=1:1, g：Ml), add and methyl methacrylate equimolar amounts
Saturated alkyl monohydric alcohol (its C atomicity be 12~20), 4~6h of ester exchange reaction is carried out under nitrogen scope, obtains crude product；Will be thick
Transferred product purifies into ethanol, produces long alkyl chain methacrylates-styrene-vinyl acetate co-polymer.
The raising deep-layer heavy crude CO of the present invention2The chemical addition agent of gas drive process recovery ratio, during concrete application, companion can be passed through
Note or preposition mode inject stratum, improve CO2The ability of viscous crude is dissolved in, viscosity of crude is reduced, so as to improve oil recovery factor.
When being injected in a manner of with note, its total usage amount is the CO that the displacement of reservoir oil uses2The 1%~10% of total amount；Noted in a manner of preposed attributives
Fashionable, its total usage amount is CO in preposed attributives layer2The 5%~30% of total amount.
The present invention is by CO2Two kinds of gas drive, chemical viscosity reduction technologies combine, using compound throughput development scheme, design and research and development
It is a kind of that there is promotion CO simultaneously2It is dissolved in viscous crude ability and effectively reduces the chemical system of viscosity of thickened oil, it can both increases
Enter CO2It is miscible in viscous crude ability, reduce CO2Minimum miscibility pressure between-viscous crude, form CO2Miscible-phase displacement, it can substantially reduce again thick
Oil viscosity, improve viscous crude mobile performance, so as to improve thick oil recovery ratio, there is efficiency high, economy is strong, and it is excellent that energy consumption is small etc.
Gesture.
The raising deep-layer heavy crude CO of the present invention2The chemical addition agent of gas drive process recovery ratio, have good solubilising and drop concurrently
Viscous characteristic, injection mode is simple, and stratum is applied widely, and the strata pressure that is particularly suitable for use in is high, viscosity of crude is high and permeability
Low high deep low permeability reservoir, has broad application prospects.
Brief description of the drawings
Fig. 1：The structural representation of the equipment therefor of embodiment 2, wherein, 1 is CO2Gas cylinder, 2 be additive tank, and 3 be crude oil
Tank, 4 be booster pump, and 5 be high pressure pump, and 6 be air accumulator, and 7 be High-pressure phase equilibria kettle, and 8 be pressure gauge, and 9 be pressure maintaining valve, and 10 are
Atmospheric valve, 11 be liquid-phase collection bottle, and 12 be gas phase receiving flask, and 13 be mass flowmenter.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Involved instrument, reagent, material etc. in following embodiments, it is existing in the prior art unless otherwise noted
Conventional instrument, reagent, material etc., can be obtained by regular commercial sources.Involved experimental method in following embodiments, inspection
Survey method etc., it is existing normal experiment method, detection method etc. in the prior art unless otherwise noted.
Embodiment 1 prepares chemical addition agent and determines its viscosity-reducing performance
Chemical addition agent, by solubilizer P-methoxybenzoic acid propyl ester and thinner lauryl methacrylate-styrene-
Vinyl acetate co-polymer forms, and both mass ratioes are 4:1.Solubilizer and thinner are added in beaker, stir 1h at room temperature
It is sufficiently mixed uniformly above, produce chemical addition agent.
The preparation method of the thinner lauryl methacrylate-styrene-vinyl acetate co-polymer is：Equipped with
Mechanical agitation, condenser pipe 150ml three-necked bottles in, add 80ml toluene as solvent, it is 10g then to sequentially add total amount, is rubbed
You are than being 10:8:1 methyl methacrylate, styrene and vinylacetate, and the initiator azo of raw material gross weight 5%
Bis-isobutyronitrile, lead to N2In displacement bottle after air, after reaction 8h is stirred at reflux under the conditions of 70 DEG C, terpolymer is obtained；Afterwards
At 80 DEG C, the concentrated sulfuric acids of 10ml 98% are slowly added to constant pressure funnel, are added and methyl methacrylate equimolar amounts
N-dodecanol, 80 DEG C, under nitrogen atmosphere carry out ester exchange reaction 5h, obtain lauryl methacrylate-styrene-acetic acid second
Enoate copolymer crude product.Crude product is transferred in ethanol and purified, produces net product.
Viscosity break ratio of the chemical additive system to viscous crude is prepared using rotation viscometer method measure, wherein viscous crude used is oily
Sample is the dune shape viscous crude of sieve 322, and its four component forms respectively asphalitine 23.6%, colloid 30.1%, saturation point 35.2, fragrance
Divide 11.1%.Before experiment, viscous crude sample about 80g or so is taken in 100mL beakers, using 100 DEG C of stirring 1h of oil bath pan constant temperature, is made
It is fully mixed.Take out, be placed in Temperature fall at room temperature.Sample is placed in oil bath pan, and is placed on rotation viscometer rotor
Underface, adjustment rotors normal highly protrude into viscous crude, and constant temperature is opened rotation viscometer and measured afterwards for a period of time.Due to
The characteristic of non-newtonian fluid, viscosity and all close phase such as rotating speed during measurement, rotor model and testing time of viscous crude sample
Close.The 3min of time of measuring selection in the present embodiment, rotor speed are set to 5r/min, every time record data after measurement.Investigate temperature
Degree and influence of the chemical addition agent addition to viscosity break ratio, wherein each transformation temperature is both needed to more than constant temperature 1h, and chemistry addition
Agent needs to be stirred continuously after adding makes it be sufficiently mixed uniformly rear re-test.Table 1 is viscosity and viscosity reduction before and after addition chemical addition agent
Rate with temperature test result, table 2 be at 100 DEG C viscosity break ratio with chemical addition agent addition test result.It can see from table,
The additive viscosity reducing effect of the present invention is obvious, and reduction rate of crude oil viscosity is reachable after 5% oil driving additive is added under the conditions of 100.14 DEG C
87.57%.
Viscosity and viscosity break ratio are with temperature test result before and after the addition oil driving additive of table 1
Viscosity break ratio is with chemical addition agent addition test result at 2 100 DEG C of table
Embodiment 2 tests chemical addition agent to promoting CO2It is dissolved in the performance of viscous crude
Equipment therefor is as shown in figure 1, chemical addition agent used is consistent with embodiment 1.Inspection apparatus air-tightness is needed before experiment,
CO is passed through in toward autoclave2, 2h is kept under 25MPa, if pressure oscillation is no more than 1%, it is believed that air-tightness is good.Experiment
When, 25g viscous crude is first weighed in equilibrium still, opens CO2Sampling valve and gas phase sampling valve, with 100~200ml/min CO2Gas
10min is purged, air in emptying kettle, closes all valves afterwards.Water bath with thermostatic control is opened, pressure is risen into 15MPa, stirring balance
More than 1h reaches vapor liquid equilibrium.Afterwards, crack liquid phase sampling valve, about 20mg liquid phase samples are taken out, and to the gas flow of release
Measured, during can by joystick maintain kettle in pressure it is constant.Need at least it be repeated twice per sub-sampling, it is random to reduce
Error.Chemical addition agent is injected in kettle by high pressure pump, needs to be corrected chemical addition agent volume before injection every time.Table
3 show CO after the different amount chemical addition agents of addition2The mass percent in viscous crude, from result it is obvious that with
The increase of chemical addition agent, CO2Meltage is substantially increased in viscous crude, but addition no longer changes substantially more than 5% meltage.
Table 3 adds CO after different amount chemical addition agents2The mass percent in viscous crude
Embodiment 3 prepares chemical addition agent and determines its performance
Chemical addition agent, by solubilizer P-methoxybenzoic acid propyl ester and thinner octadecyl methacrylate-styrene-
Vinyl acetate co-polymer forms, and both mass ratioes are 4:1.Solubilizer and thinner are added in beaker, stir 1h at room temperature
It is sufficiently mixed uniformly above, produce chemical addition agent.
The preparation method of the thinner octadecyl methacrylate-styrene-vinyl acetate co-polymer is：Equipped with
Mechanical agitation, condenser pipe 150ml three-necked bottles in, add 80ml toluene as solvent, it is 10g then to sequentially add total amount, is rubbed
You are than being 10:8:1 methyl methacrylate, styrene and vinylacetate, and the initiator azo of raw material gross weight 5%
Bis-isobutyronitrile, lead to N2In displacement bottle after air, after reaction 8h is stirred at reflux under the conditions of 70 DEG C, terpolymer is obtained；Afterwards
At 80 DEG C, the concentrated sulfuric acids of 10ml 98% are slowly added to constant pressure funnel, are added and methyl methacrylate equimolar amounts
Positive octadecyl alcolol, 80 DEG C, under nitrogen atmosphere carry out ester exchange reaction 5h, obtain octadecyl methacrylate-styrene-acetic acid second
Enoate copolymer crude product.Crude product is transferred in ethanol and purified, produces net product.
The method of its viscosity-reducing performance is determined with embodiment 1, is as a result shown, when chemical addition agent addition is 5% at 100 DEG C
Viscosity break ratio is 83.9%.
Chemical addition agent is tested to promoting CO2It is dissolved in the performance of viscous crude, method is with embodiment 2, as a result as shown in table 4,
With the increase of chemical addition agent, CO2Meltage is substantially increased in viscous crude.
Table 4 adds CO after different amount chemical addition agents2The mass percent in viscous crude
Embodiment 4 prepares chemical addition agent
Chemical addition agent, by the monooctyl ester of solubilizer P-methoxybenzoic acid third and thinner hexadecyl metrhacrylate-benzene second
Alkene-vinyl acetate co-polymer composition, both mass ratioes are 1:1.Solubilizer and thinner are added in beaker, stirred at room temperature
More than 1h makes it be sufficiently mixed uniformly, produces chemical addition agent.
The preparation method of the thinner hexadecyl metrhacrylate-styrene-vinyl acetate co-polymer is：Equipped with
Mechanical agitation, condenser pipe 150ml three-necked bottles in, add 80ml toluene as solvent, it is 10g then to sequentially add total amount, is rubbed
You are than being 5:2:3 methyl methacrylate, styrene and vinylacetate, and the initiator azo of raw material gross weight 5%
Bis-isobutyronitrile, lead to N2In displacement bottle after air, after reaction 8h is stirred at reflux under the conditions of 70 DEG C, terpolymer is obtained；Afterwards
At 80 DEG C, the concentrated sulfuric acids of 10ml 98% are slowly added to constant pressure funnel, are added and methyl methacrylate equimolar amounts
Positive hexadecanol, 80 DEG C, under nitrogen atmosphere carry out ester exchange reaction 5h, obtain hexadecyl metrhacrylate-styrene-acetic acid second
Enoate copolymer crude product.Crude product is transferred in ethanol and purified, produces net product.
Embodiment 5 prepares chemical addition agent
Chemical addition agent, by solubilizer P-methoxybenzoic acid butyl ester and thinner tetradecyl methylacrylate-styrene-
Vinyl acetate co-polymer forms, and both mass ratioes are 6:1.Solubilizer and thinner are added in beaker, stir 1h at room temperature
It is sufficiently mixed uniformly above, produce chemical addition agent.
The preparation method of the thinner tetradecyl methylacrylate-styrene-vinyl acetate co-polymer is：Equipped with
Mechanical agitation, condenser pipe 150ml three-necked bottles in, add 80ml toluene as solvent, it is 10g then to sequentially add total amount, is rubbed
You are than being 8:5:2 methyl methacrylate, styrene and vinylacetate, and the initiator azo of raw material gross weight 5%
Bis-isobutyronitrile, lead to N2In displacement bottle after air, after reaction 8h is stirred at reflux under the conditions of 70 DEG C, terpolymer is obtained；Afterwards
At 80 DEG C, the concentrated sulfuric acids of 10ml 98% are slowly added to constant pressure funnel, are added and methyl methacrylate equimolar amounts
Tetradecanol, 80 DEG C, under nitrogen atmosphere carry out ester exchange reaction 5h, obtain tetradecyl methylacrylate-styrene-acetic acid second
Enoate copolymer crude product.Crude product is transferred in ethanol and purified, produces net product.
Although above-mentioned the embodiment of the present invention is described in conjunction with the embodiments, not the present invention is protected
The limitation of scope, one of ordinary skill in the art should be understood that on the basis of technical scheme, those skilled in the art
Various modifications or deformation that creative work can make need not be paid still within protection scope of the present invention.
Claims (10)
1. one kind improves deep-layer heavy crude CO2The chemical addition agent of gas drive process recovery ratio, it is characterised in that：By solubilizer and viscosity reduction
Agent forms, and the weight ratio of solubilizer and thinner is 1~6:1；Wherein, the solubilizer is P-methoxybenzoic acid esters chemical combination
Thing, its structural formula is as follows, and in structural formula, n is 2~12 integer；
The thinner is long alkyl chain methacrylates-styrene-vinyl acetate co-polymer, and its structural formula is as follows：
In formula ,-R represents saturated alkyl chain, and its C atomicity is 12~20；i:j:K=(5~10):(2~8):(1~3).
2. raising deep-layer heavy crude CO according to claim 12The chemical addition agent of gas drive process recovery ratio, it is characterised in that：
The weight ratio of the solubilizer and thinner is 4:1.
3. raising deep-layer heavy crude CO according to claim 12The chemical addition agent of gas drive process recovery ratio, it is characterised in that：
The solubilizer is P-methoxybenzoic acid propyl ester.
4. raising deep-layer heavy crude CO according to claim 12The chemical addition agent of gas drive process recovery ratio, it is characterised in that：
The thinner is lauryl methacrylate-styrene-vinyl acetate co-polymer.
5. the raising deep-layer heavy crude CO according to claim 1 or 42The chemical addition agent of gas drive process recovery ratio, its feature exist
In：Long alkyl chain methacrylates-styrene-the vinyl acetate co-polymer, is prepared by the following method to obtain：With first
Base methyl acrylate, styrene and vinylacetate are raw material, and three's mol ratio is (5~10):(2~8):(1~3), with first
Benzene is solvent, add initiator azodiisobutyronitrile, under nitrogen atmosphere, be stirred at reflux under the conditions of 65~75 DEG C reaction 6~
10h, obtain terpolymer；80 DEG C ± 2 DEG C are warming up to, is slowly added to the concentrated sulfuric acid, is added and methyl methacrylate equimolar
The saturated alkyl monohydric alcohol of amount, the C atomicities of saturated alkyl monohydric alcohol are 12~20, and ester exchange reaction 4 is carried out under nitrogen scope
~6h, obtains crude product；Crude product is transferred in ethanol and purified, produces long alkyl chain methacrylates-styrene-vinylacetate
Copolymer.
6. raising deep-layer heavy crude CO according to claim 52The chemical addition agent of gas drive process recovery ratio, it is characterised in that：
The dosage of the azodiisobutyronitrile is the 5% of raw material gross weight.
7. raising deep-layer heavy crude CO according to claim 52The chemical addition agent of gas drive process recovery ratio, it is characterised in that：
The concentrated sulfuric acid be mass concentration 98% the concentrated sulfuric acid, concentrated sulfuric acid volume：Raw material gross weight=1:1, g：ml.
8. raising deep-layer heavy crude CO according to claim 52The chemical addition agent of gas drive process recovery ratio, it is characterised in that：
The preparation method of the thinner lauryl methacrylate-styrene-vinyl acetate co-polymer is：Stirred equipped with machinery
Mix, in the 150ml three-necked bottles of condenser pipe, add 80ml toluene as solvent, it is 10g then to sequentially add total amount, and mol ratio is
10:8:1 methyl methacrylate, styrene and vinylacetate, and the isobutyl of initiator azo two of raw material gross weight 5%
Nitrile, lead to N2In displacement bottle after air, after reaction 8h is stirred at reflux under the conditions of 70 DEG C, terpolymer is obtained；Afterwards at 80 DEG C
Under, the concentrated sulfuric acids of 10ml 98% are slowly added to constant pressure funnel, add positive ten with methyl methacrylate equimolar amounts
Glycol, 80 DEG C, ester exchange reaction 5h is carried out under nitrogen atmosphere, crude product is obtained, crude product is transferred in ethanol and purified, i.e.,
.
9. raising deep-layer heavy crude CO according to any one of claims 1 to 82The chemical addition agent of gas drive process recovery ratio is in depth
Layer viscous crude CO2Application in the harvesting of gas drive process, it is characterised in that：By injecting stratum with note or preposition mode.
10. application according to claim 9, it is characterised in that：When being injected in a manner of with note, the total use of chemical addition agent
Measure the CO used for the displacement of reservoir oil2The 1%~10% of total amount；When being injected in a manner of preposed attributives, the total usage amount of chemical addition agent is
CO in preposed attributives layer2The 5%~30% of total amount.
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