CN103897683A - Authigenic heat injection composition for underground catalytic oxidation of crude oil - Google Patents
Authigenic heat injection composition for underground catalytic oxidation of crude oil Download PDFInfo
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- CN103897683A CN103897683A CN201410086425.9A CN201410086425A CN103897683A CN 103897683 A CN103897683 A CN 103897683A CN 201410086425 A CN201410086425 A CN 201410086425A CN 103897683 A CN103897683 A CN 103897683A
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- water
- crude oil
- air
- injection composition
- catalytic oxidation
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- 239000000203 mixture Substances 0.000 title claims abstract description 110
- 238000002347 injection Methods 0.000 title claims abstract description 83
- 239000007924 injection Substances 0.000 title claims abstract description 83
- 239000010779 crude oil Substances 0.000 title claims abstract description 52
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 46
- 230000003647 oxidation Effects 0.000 title claims abstract description 43
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 35
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 27
- 239000012071 phase Substances 0.000 claims abstract description 24
- 239000007790 solid phase Substances 0.000 claims abstract description 22
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 37
- 239000003921 oil Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 18
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 17
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 17
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 17
- 239000012530 fluid Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical group 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- -1 Z 250 Chemical compound 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 239000000230 xanthan gum Substances 0.000 claims description 2
- 229940082509 xanthan gum Drugs 0.000 claims description 2
- 235000010493 xanthan gum Nutrition 0.000 claims description 2
- 239000003570 air Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000004939 coking Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract 1
- 230000001360 synchronised effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 26
- 238000005516 engineering process Methods 0.000 description 24
- 238000011084 recovery Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000002105 nanoparticle Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 11
- 230000001590 oxidative effect Effects 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000004088 simulation Methods 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000005465 channeling Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
Classifications
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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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Geochemistry & Mineralogy (AREA)
- Catalysts (AREA)
Abstract
The invention provides an authigenic heat injection composition for underground catalytic oxidation of crude oil. The injection composition is a three-phase stable disperse system composed of water phase (anionic surfactant), an auxiliary agent, solid phase (nano-catalyst) and gas phase (air); the injection composition comprises the following raw materials: 0.1-1% of anionic surfactant taken as water phase, 0.1-1% of auxiliary agent, 0.1-1% of nano-catalyst taken as solid phase, and the balance of water, wherein the sum of the mass percent of the water phase, the auxiliary agent, the solid phase and the water is 100%; the volume ratio of the adding amount of the air to the total amount of the water phase, the auxiliary agent, the solid phase and the water is (3-7): 1. After the injection composition is adopted, the sweep efficiency of the air can be improved, the synchronous carrying of the catalyst and the air can be realized, and the problem of separation of underground air and catalyst can be avoided; the composition contains the efficient nanometer oxide catalyst, and the crude oil can be catalyzed to have oxidation reaction under the mild conditions, and therefore the problem that the stratum is blocked by coking caused by severe oxidation reaction is effectively avoided.
Description
Technical field
The present invention relates to a kind of injection composition for crude oil underground catalytic oxidation Self-heating, belong to oil development technical field.
Background technology
In oilfield development process, crude oil viscosity lowering is one of Major Technology improving oil recovery.Viscous crude, super-heavy oil deposit and be difficult for exploitation because its surplus oil multilist reveals the feature that polarity is large, viscosity is large through the maturing field of long-period water drive etc., cost of winning also can rise, and at this moment just needs to adopt to fall glutinous technology and could realize cost-effectively and exploiting.At present existingly fall glutinous production technique and comprise: steam treatment fall glutinous, mix and rarely fall glutinous, reducing viscosity by emulsification and the technology such as glutinous fall in air injection.Increasingly sophisticated along with oil-field development object, glutinous high energy consumption, the expensive severe challenge of being faced with falls in steam treatment; Mix rare falling and stick due to a large amount of thin oil of needs consumption, reducing viscosity by emulsification faces the bottleneck problems such as output oil breakdown of emulsion difficulty, has greatly limited the industrial application of above-mentioned technology.Glutinous know-why falls in air injection: crude oil and air are in underground generation oxidizing reaction release of heat, thereby heating oil reservoir reduces viscosity of crude.Therefore, compared with steam injection technology, utilize the spontaneous heat drop of underground crude oil glutinous, significantly reduced the thermosteresis of ground and injection process, energy utilization efficiency is high, is that following crude oil viscosity lowering exploitation improves one of major technique developing direction of recovery ratio.
In prior art, expanding swept volume is that one of glutinous main difficult technical falls in air injection.Compare littlely with crude oil due to density of air, viscosity, cause injecting air channelling, onlap and fingering easily occur on stratum; Meanwhile, air and crude oil are in underground generation oxidizing reaction, and speed of reaction and temperature of reaction poor controllability, cause crude oil coking amount large, stop up duct, stratum, and restriction is injected air and involved in oil reservoir.
Air injection falls the glutinous major way that expands swept volume and is mainly divided into following several:
Prior art one:
Injection-production pattern is adjusted.Adopt the mode of adjusting injection-production pattern to improve air swept volume, not only with high costs, improve effect also not obvious.
Prior art two:
Injection-production program is adjusted.Injection-production program adjustment is only applicable to the special oil reservoir of part, and as adopted the method for a kind of segmentation air injection fireflood in Chinese patent CN201010154476, the method, for the larger oil reservoir of core intersection, can be improved onlap and gas channeling phenomenon to a certain extent.
Prior art three:
Injection system is optimized.Comparatively speaking, the method for optimizing injection system can improve swept volume more efficiently, and suitability is relatively strong, becomes the main path that improves air swept volume.Peaceful wound etc. (peaceful wound etc. Tang's 80 wellblock air foam flooding shaft pilot tests. Guangdong chemical industry, 2013,1:49-51) carry out air foam pilot test at Tang's two of 80 wellblocks well group, test-results shows, air foam has effectively reduced advancing by leaps and bounds of fracture orientation, has improved swept volume.But this technology has mainly realized the mobility that reduces sweeping phase, and does not embody the method that improves displaced phase mobility, thereby, the inapplicable heavy crude reservoir higher with viscosity of crude of this technology.The method of the controlled Self-heating of low temperature in a kind of viscous crude original position is provided in patent 103147732, the method has adopted catalyzer control crude oil and oxygen-containing gas speed of reaction, has both reduced the temperature threshold of reaction, has reduced energy consumption, again too fast the and green coke of anti-oxidation.But oxygen-containing gas and catalyzer substep inject, and the phenomenons such as has channeling, onlap, fingering easily occur institute's gas injection body, cause oxygen-containing gas and catalyst separating in well far away stratum, cause the injection efficiency of air and catalyzer low.Patent CN103396779 has proposed a kind of oil by injecting air buffering catalytic oxidation of thick milk sap catalyst system, in the process of air injection, alternately inject oxide catalyst, compared with direct injection air, its oxidising process is more gentle controlled, had reducing viscosity by emulsifying and oil soluble viscosity reduction etc. technology concurrently, but this technology have air and catalyzer equally in underground segregative problem, causes air and catalyzer injection efficiency low simultaneously.A kind of stratum catalytic oxidation thick oil thermal recovery method is provided in patent CN101539012, and the technology such as the method can be driven surfactant, flue gas flooding, thermal recovery and catalytic pyrolysis upgrading viscosity reduction is incorporated into one.Fail the defect of simultaneous implantation but have equally air and catalyzer, the sweep efficiency of air and catalyzer is low, and then causes recovery ratio lower.
In the prior art visible, there is no and can realize the technology that improves air sweep efficiency and can realize again air and catalyzer simultaneous implantation.
Summary of the invention
In view of the defect of above-mentioned prior art existence, the object of the invention is to propose a kind of injection composition for crude oil underground catalytic oxidation Self-heating, can either improve the sweep efficiency of air, can realize again required underground in-situ catalytic oxidation efficient solid nano catalyzer and air are synchronously carried to underground, avoid the problem of underground air, catalyst separating, can also effectively avoid vigorous oxidation reaction to cause the coking of crude oil and stop up stratum.
Object of the present invention is achieved by the following technical programs:
For an injection composition for crude oil underground catalytic oxidation Self-heating, be the three-phase stable dispersion that the anion surfactant by water and auxiliary agent, the nanocatalyst of solid phase and the air of gas phase forms, it comprises that following raw material forms:
Taking the mass percent sum of anion surfactant, auxiliary agent, solid phase nanocatalyst and the water of water as 100%, the content of anion surfactant is 0.1%-1%, the content of auxiliary agent is 0.1%-1%, and the content of nanocatalyst is 0.1%-1%, and its surplus is water;
The volume ratio of the total amount of air add-on and water, auxiliary agent, solid phase and water is (3-7): 1.
The overall accumulated amount of the liquid system during nanocatalyst and the water of anion surfactant that above-mentioned " total amount of water, auxiliary agent, solid phase and water " is the water that mixes in three-phase dispersion system raw material composition, auxiliary agent, solid phase forms.
The above-mentioned injection composition for crude oil underground catalytic oxidation Self-heating, preferred, described nanocatalyst is metal oxide particle, preferred, the particle diameter of described particle is 10nm-30nm.
The above-mentioned injection composition for crude oil underground catalytic oxidation Self-heating, preferably, described metal oxide comprises one or more the combination in oxide compound, the oxide compound of molybdenum and the oxide compound of manganese of oxide compound, copper of oxide compound, the nickel of oxide compound, the cobalt of oxide compound, the iron of oxide compound, the ruthenium of oxide compound, the chromium of aluminium.
The above-mentioned injection composition for crude oil underground catalytic oxidation Self-heating, preferably, described metal oxide comprises one or more the combination in aluminium sesquioxide, chromium sesquioxide, ruthenium tetroxide, ferric oxide, Z 250, iron protoxide, cobalt sesquioxide, nickel oxide, cupric oxide, molybdic oxide, manganese oxide, Manganse Dioxide and manganic oxide.
The above-mentioned injection composition for crude oil underground catalytic oxidation Self-heating, preferably, described anion surfactant comprises one or more the combination in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and polyoxyethylenated alcohol sodium sulfate, the fatty alcohol carbon number of described polyoxyethylenated alcohol sodium sulfate is 12-14, and Soxylat A 25-7 chain footing is 2-3.
The above-mentioned injection composition for crude oil underground catalytic oxidation Self-heating, preferred, described auxiliary agent is to have the water-soluble substances that increases glutinous effect.
The above-mentioned injection composition for crude oil underground catalytic oxidation Self-heating, preferred, described auxiliary agent comprises one or more the combination in xanthan gum, Xylo-Mucine and polyacrylamide.
The present invention also provides the preparation method of the above-mentioned injection composition for crude oil underground catalytic oxidation Self-heating, comprises the steps:
Nanocatalyst, anion surfactant and auxiliary agent are added to the water, obtain mixture water liquid;
By the ultrasonic dispersion at 20 DEG C-60 DEG C of this mixture water liquid, obtain finely dispersed nanocatalyst fluid;
By this nanocatalyst fluid and quantitative air mixed, obtain described injection composition.
In above-mentioned preparation method, preferred, the ultrasonic dispersion at 50 DEG C of described mixture water liquid, obtains finely dispersed nanocatalyst fluid.
The present invention also provides the above-mentioned injection composition for crude oil underground catalytic oxidation Self-heating falling the application that sticks displacement medicament as oil production.
Above-mentioned injection composition can be oxidized by (150 DEG C-250 DEG C) catalysis crude oil under comparatively gentle condition, and while using said composition, needing first provide start-up temperature by electrically heated or steam treatment etc.
Injection composition of the present invention can improve the sweep efficiency of air; Can realize again efficient solid nano catalyzer required underground in-situ catalytic oxidation and air being synchronously carried to underground, avoid the problem of underground air, catalyst separating; In said composition, also contain efficient nano oxide catalyst, there is oxidizing reaction in catalysis crude oil, effectively avoid vigorous oxidation to react the coking causing and stop up stratum under comparatively gentle condition.
Injection composition for crude oil underground catalytic oxidation Self-heating provided by the invention has following beneficial effect compared with falling sticking method with existing air injection:
1) by regulating air and the ratio of water and the content of auxiliary agent in this system, can realize the mobility control to three-phase composition, thereby improve the mobility ratio of air and crude oil, improve the sweep efficiency that injects composition;
2) said composition is oxidized required efficient nanocatalyst taking water (containing anion surfactant and auxiliary agent) as carrier by underground catalytic and air is synchronously carried to underground, effectively improved underground, the contact efficiency of air, catalyzer and crude oil;
3) the nano oxidized catalyzer containing in said composition, because it has the characteristic of high-specific surface area, therefore catalytic efficiency is high, can make crude oil, under middle cold condition, oxidizing reaction occur, and can effectively avoid high temperature oxidation to react the coking causing and stop up stratum.
Embodiment
Below just the specific embodiment of the present invention is described in further detail, so that technical solution of the present invention is easier to understand, grasp.
Embodiment 1
The present embodiment provides a kind of injection composition for crude oil underground catalytic oxidation Self-heating, said composition is the three-phase stable dispersion being made up of the sodium lauryl sulphate of water and Xylo-Mucine, the aluminium sesquioxide particle of solid phase and the air of gas phase, comprises following raw material composition:
By percentage to the quality, the content of sodium lauryl sulphate is 0.1% of mixture water liquid (nanocatalyst and water by the anion surfactant of water, auxiliary agent, solid phase form) gross weight, the content of Xylo-Mucine is 0.1% of mixture water liquid gross weight, particle diameter is that the content of the aluminium sesquioxide particle of 20nm is 0.1% of mixture water liquid gross weight, and its surplus is water;
The volume ratio of air add-on and mixture water liquid is 3:1.
The injection composition for crude oil underground catalytic oxidation Self-heating of the present embodiment obtains by the following method:
Aluminium sesquioxide particle, sodium lauryl sulphate and Xylo-Mucine are added to the water, obtain mixture water liquid;
By this mixture water liquid ultrasonic dispersion 30min at 50 DEG C of temperature, obtain finely dispersed nanocatalyst fluid 0.1L;
By this nanocatalyst fluid and 0.3L air mixed, obtain described injection composition.
Embodiment 2
The present embodiment provides a kind of injection composition for crude oil underground catalytic oxidation Self-heating, said composition is the three-phase stable dispersion being made up of the sodium lauryl sulphate of water and Xylo-Mucine, the ruthenium tetroxide nano particle of solid phase and the air of gas phase, comprises following raw material composition:
By percentage to the quality, the content of sodium lauryl sulphate is 0.1% of mixture water liquid (nanocatalyst and water by the anion surfactant of water, auxiliary agent, solid phase form) gross weight, the content of Xylo-Mucine is 0.1% of mixture water liquid gross weight, particle diameter is that the content of the ruthenium tetroxide nano particle of 30nm is 0.1% of mixture water liquid gross weight, and its surplus is water;
The volume ratio of air add-on and mixture water liquid is 3:1.
The injection composition for crude oil underground catalytic oxidation Self-heating of the present embodiment obtains by the following method:
Ruthenium tetroxide nano particle, sodium lauryl sulphate and Xylo-Mucine are added to the water, obtain mixture water liquid;
By this mixture water liquid ultrasonic dispersion 30min at 50 DEG C of temperature, obtain finely dispersed nanocatalyst fluid 0.1L;
By this nanocatalyst fluid and 0.3L air mixed, obtain described injection composition.
Embodiment 3
The present embodiment provides a kind of injection composition for crude oil underground catalytic oxidation Self-heating, said composition is the three-phase stable dispersion being made up of the sodium lauryl sulphate of water and Xylo-Mucine, the molybdenum trioxide nano particle of solid phase and the air of gas phase, comprises following raw material composition:
By percentage to the quality, the content of sodium lauryl sulphate is 0.1% of mixture water liquid (nanocatalyst and water by the anion surfactant of water, auxiliary agent, solid phase form) gross weight, the content of Xylo-Mucine is 0.1% of mixture water liquid gross weight, particle diameter is that the content of the molybdenum trioxide nano particle of 30nm is 0.3% of mixture water liquid gross weight, and its surplus is water;
The volume ratio of air add-on and mixture water liquid is 3:1.
The injection composition for crude oil underground catalytic oxidation Self-heating of the present embodiment obtains by the following method:
Molybdenum trioxide nano particle, sodium lauryl sulphate and Xylo-Mucine are added to the water, obtain mixture water liquid;
By this mixture water liquid ultrasonic dispersion 30min at 50 DEG C of temperature, obtain finely dispersed nanocatalyst fluid 0.1L;
By this nanocatalyst fluid and 0.3L air mixed, obtain described injection composition.
Embodiment 4
The present embodiment provides a kind of injection composition for crude oil underground catalytic oxidation Self-heating, said composition is the three-phase stable dispersion being made up of the sodium lauryl sulphate of water and Xylo-Mucine, the nickel oxide nanoparticle of solid phase and the air of molybdenum trioxide nano particle and gas phase, comprises following raw material composition:
By percentage to the quality, the content of sodium lauryl sulphate is 0.3% of mixture water liquid (nanocatalyst and water by the anion surfactant of water, auxiliary agent, solid phase form) gross weight, the content of Xylo-Mucine is 0.1% of mixture water liquid gross weight, particle diameter is that the nickel oxide nanoparticle of 10nm and the content of the molybdenum trioxide nano particle that particle diameter is 30nm are respectively 0.15% of mixture water liquid gross weight, and its surplus is water;
The volume ratio of air add-on and mixture water liquid is 3:1.
The injection composition for crude oil underground catalytic oxidation Self-heating of the present embodiment obtains by the following method:
Nickel oxide nanoparticle, molybdenum trioxide nano particle, sodium lauryl sulphate and Xylo-Mucine are added to the water, obtain mixture water liquid;
By this mixture water liquid ultrasonic dispersion 30min at 50 DEG C of temperature, obtain finely dispersed nanocatalyst fluid 0.1L;
By this nanocatalyst fluid and 0.3L air mixed, obtain described injection composition.
Embodiment 5
The present embodiment provides a kind of injection composition for crude oil underground catalytic oxidation Self-heating, said composition is the three-phase stable dispersion being made up of the air of the sodium lauryl sulphate of water and Xylo-Mucine, the nickel oxide of solid phase and the mixing nano particle of Manganse Dioxide, gas phase, comprises following raw material composition:
By percentage to the quality, the content of sodium lauryl sulphate is 0.3% of mixture water liquid (nanocatalyst and water by the anion surfactant of water, auxiliary agent, solid phase form) gross weight, the content of Xylo-Mucine is 0.3% of mixture water liquid gross weight, particle diameter is that the nickel oxide nanoparticle of 10nm and the content of the manganese dioxide nano particle that particle diameter is 30mn are respectively 0.15% of mixture water liquid gross weight, and its surplus is water;
The volume ratio of air add-on and mixture water liquid is 7:1.
The injection composition for crude oil underground catalytic oxidation Self-heating of the present embodiment obtains by the following method:
Nickel oxide nanoparticle, manganese dioxide nano particle, sodium lauryl sulphate and Xylo-Mucine are added to the water, obtain mixture water liquid;
By this mixture water liquid ultrasonic dispersion 30min at 50 DEG C of temperature, obtain finely dispersed nanocatalyst fluid 0.1L;
By this nanocatalyst fluid and 0.7L air mixed, obtain described injection composition.
Embodiment 6
The injection composition that the present embodiment obtains embodiment 1 is for large-scale three dimensional physical simulation displacement test.
Experiment adopts 1/4 inverted nine-spot pattern, and a note three is adopted, the long 0.5m of sand-packed model used, wide 0.5m, high 0.25m.Back-up sand simulation core porosity is 32%.
This experiment is carried out according to following steps:
At 90 DEG C by model in saturated oil, dewatered oil viscosity is 10142mPas(30 DEG C);
Temperature in model is risen to 150 DEG C, then by the injection composition of embodiment 1 the speed injection model with 100mL/min;
Oxidizing reaction starts at 150 DEG C, continuous heating, and test swept volume and recovery ratio, observe core temperature simultaneously and change, from starting oxidizing reaction, through about 6h, reaction starts violent, occur obviously heating up, temperature now, greatly about 200 DEG C, at this moment stops heating.
Taking air injection technology as contrast, test swept volume and recovery ratio: adopt above-mentioned sand-packed model, model vacuumized, at 90 DEG C by model in saturated oil, dewatered oil viscosity is 10142mPas(30 DEG C); Model is warming up to 450 DEG C, injects air, test swept volume and recovery ratio.
Taking the volume of sand in the model feeding through to as swept volume, calculate recovery ratio with the crude oil overflowing, experimental result shows, compare air injection technology, swept volume 64.2% is increased to 70.6% of the present embodiment method by what adopt air injection technology, and recovery ratio is from adopting 52% of air injection technology to bring up to 60% of the present embodiment method.
Embodiment 7
The injection composition that the present embodiment obtains embodiment 2 is for large-scale three dimensional physical simulation displacement test.
Experiment adopts 1/4 inverted nine-spot pattern, and a note three is adopted, the long 0.5m of sand-packed model used, wide 0.5m, high 0.25m.Back-up sand simulation core porosity is 32%.
This experiment is carried out according to following steps:
At 90 DEG C by model in saturated oil, dewatered oil viscosity is 10142mPas(30 DEG C);
Temperature in model is risen to 150 DEG C, then by the injection composition of embodiment 2 the speed injection model with 100mL/min; Oxidizing reaction starts at 150 DEG C, continuous heating, and test swept volume and recovery ratio, from starting oxidizing reaction, through about 6h, reaction starts violent, occurs obviously heating up, and temperature now, greatly about 200 DEG C, at this moment stops heating.
Taking air injection technology as contrast, test swept volume and recovery ratio: adopt above-mentioned sand-packed model, model vacuumized, at 90 DEG C by model in saturated oil, dewatered oil viscosity is 10142mPas(30 DEG C); Model is warming up to 450 DEG C, injects air, test swept volume and recovery ratio.
Experimental result shows, compares air injection technology, and swept volume 64.2% is brought up to 72.9% of the present embodiment method by what adopt air injection technology, and recovery ratio 52% is brought up to 62% of the present embodiment method by what adopt air injection technology.
Embodiment 8
The injection composition that the present embodiment obtains embodiment 5 is for large-scale three dimensional physical simulation displacement test.
Experiment adopts 1/4 inverted nine-spot pattern, and a note three is adopted, and sand-packed model used is rectangle, long 0.5m, wide 0.5m, high 0.25m.Back-up sand simulation core porosity is 32%.
This experiment is carried out according to following steps:
At 90 DEG C by model in saturated oil, dewatered oil viscosity is 10142mPas(30 DEG C);
Temperature in model is risen to 150 DEG C, then by the injection composition of embodiment 5 the speed injection model with 100mL/min; Oxidizing reaction starts at 150 DEG C, continuous heating, and test swept volume and recovery ratio, from starting oxidizing reaction, through about 6h, reaction starts violent, occurs obviously heating up, and now temperature, greatly about 200 DEG C, at this moment stops heating.
Taking air injection technology as contrast, test swept volume and recovery ratio: adopt above-mentioned sand-packed model, model vacuumized, at 90 DEG C by model in saturated oil, dewatered oil viscosity is 10142mPas(30 DEG C); Model is warming up to 450 DEG C, injects air, test swept volume and recovery ratio.
Experimental result shows, compares air injection technology, and swept volume 64.2% is brought up to 78.8% of the present embodiment method by what adopt air injection technology, and recovery ratio 52% is brought up to 67% of the present embodiment method by what adopt air injection technology.
Therefore, the above-mentioned injection composition for crude oil underground catalytic oxidation Self-heating, can realize required underground in-situ catalytic oxidation efficient solid nano catalyzer and air are synchronously carried to underground, avoid the problem of underground air, catalyst separating, can effectively avoid air has channeling, fingering and onlap, can improve air injection and fall glutinous swept volume, finally improve oil recovery factor.In addition, there is oxidizing reaction in catalysis crude oil, can effectively avoid vigorous oxidation to react the coking causing and stop up stratum under comparatively gentle condition.
Claims (10)
1. for an injection composition for crude oil underground catalytic oxidation Self-heating, the three-phase stable dispersion that its anion surfactant by water and auxiliary agent, the nanocatalyst of solid phase and the air of gas phase form, comprises following raw material composition:
Taking anion surfactant, auxiliary agent, the nanocatalyst of solid phase and the mass percent sum of water of water as 100%, the content of anion surfactant is 0.1%-1%, the content of auxiliary agent is 0.1%-1%, and the content of nanocatalyst is 0.1%-1%, and its surplus is water;
The volume ratio of the total amount of the add-on of air and water, auxiliary agent, solid phase and water is (3-7): 1.
2. the injection composition for crude oil underground catalytic oxidation Self-heating according to claim 1, is characterized in that: described nanocatalyst is metal oxide particle, and the particle diameter of described particle is 10nm-30nm.
3. the injection composition for crude oil underground catalytic oxidation Self-heating according to claim 2, is characterized in that: described metal oxide comprises one or more the combination in oxide compound, the oxide compound of molybdenum and the oxide compound of manganese of oxide compound, copper of oxide compound, the nickel of oxide compound, the cobalt of oxide compound, the iron of oxide compound, the ruthenium of oxide compound, the chromium of aluminium.
4. the injection composition for crude oil underground catalytic oxidation Self-heating according to claim 3, is characterized in that: described metal oxide comprises one or more the combination in aluminium sesquioxide, chromium sesquioxide, ruthenium tetroxide, ferric oxide, Z 250, iron protoxide, cobalt sesquioxide, nickel oxide, cupric oxide, molybdic oxide, manganese oxide, Manganse Dioxide and manganic oxide.
5. the injection composition for crude oil underground catalytic oxidation Self-heating according to claim 1, it is characterized in that: described anion surfactant comprises one or more the combination in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and polyoxyethylenated alcohol sodium sulfate, preferably, the fatty alcohol carbon number of described polyoxyethylenated alcohol sodium sulfate is 12-14, and Soxylat A 25-7 chain footing is 2-3.
6. the injection composition for crude oil underground catalytic oxidation Self-heating according to claim 1, is characterized in that: described auxiliary agent is to have the water-soluble substances that increases glutinous effect.
7. the injection composition for crude oil underground catalytic oxidation Self-heating according to claim 6, is characterized in that: described auxiliary agent comprises one or more the combination in xanthan gum, Xylo-Mucine and polyacrylamide.
8. the preparation method of the injection composition for crude oil underground catalytic oxidation Self-heating described in claim 1-7 any one, comprises the steps:
Nanocatalyst, anion surfactant and auxiliary agent are added to the water, obtain mixture water liquid;
By the ultrasonic dispersion at 20 DEG C-60 DEG C of this mixture water liquid, obtain finely dispersed nanocatalyst fluid;
This nanocatalyst fluid is mixed with air, obtain described injection composition.
9. preparation method according to claim 8, is characterized in that: the ultrasonic dispersion at 50 DEG C of described mixture water liquid, obtains finely dispersed nanocatalyst fluid.
10. the application of glutinous displacement medicament falls in the injection composition for crude oil underground catalytic oxidation Self-heating described in claim 1-7 any one as oil production.
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