CN104650843B - A kind of reducing viscosity by emulsification type displacement composition suitable for heavy crude reservoir - Google Patents
A kind of reducing viscosity by emulsification type displacement composition suitable for heavy crude reservoir Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
- C09K8/584—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 surfactants
Abstract
The invention provides a kind of reducing viscosity by emulsification type displacement composition suitable for heavy crude reservoir.By weight percentage, it should include suitable for the reducing viscosity by emulsification type displacement composition composition composition of heavy crude reservoir：Anionic polymer 0.1 0.3%, nonionic surface active agent 0.01 0.1%, emulsion stabilizer 0.02 0.12%, appropriate inorganic salts and water surplus.The constituent cost of the displacement composition that the present invention is provided is relatively low, prepare simple, and biological degradability is good, safety and environmental protection, and the displacement composition using the present invention is good to the thinning effect and washing oil effect of viscous crude, and oil displacement efficiency is high.
Description
Technical field
The present invention relates to a kind of reducing viscosity by emulsification type displacement composition suitable for heavy crude reservoir, belong in field of petroleum exploitation
Chemical combined flooding technical field.
Background technology
Viscous crude foreign countries are called " heavy oil ", and the whole world there are about in 10,000,000,000,000 tons of residual petroleum resources 70% above is heavy oil resources.
So, the exploitation of viscous crude occupies very important position in future source of energy strategy.There is abundant viscous crude resource in China, verify and
Control reserve, up to 1,600,000,000 tons, is the fourth-largest viscous crude producing country of the world after the U.S., Canada and Venezuela.Emphasis point
Cloth is in oil fields such as triumph, the Liaohe River, Henan, Xinjiang.The land viscous crude resource of China accounts for more than the 20% of oil total resources, verifies
It is about 4,000,000,000 tons with control reserve, is found that more than 70 viscous crude field in 12 basins at present.Domestic annual heavy oil production accounts for original
The 10% of oil yield, but still the super-viscous oil oil in place for having about 7.0 hundred million tons fails to employ.China's heavy oil asphalt matter content is relatively low,
Gum level is higher, and viscosity is high, relative density is higher.It is divided into common heavy oil (viscosity 50-10000mPas), special thick oil
(10000-50000mPas) and super-viscous oil (>It is 50000mPas) several.It is general have that the content of wax is few, gassiness is few, easily solidification,
The features such as poor fluidity.The general 30-50% of asphalt content, alkane and arene content are generally less than 50%.So, China is main
Using the thermal recovery technology heavy crude producing such as hot-water flooding, steam injection, Electromagnetic Heating, combustion in situ, and long-term thermal recovery to pass through in production
The problem of often facing three aspects：(1) reservoir crude oil is bigger because light components are largely lost in Crude viscosity；(2) reservoir rocks are moistened
Moist wet, the capillary resistance increase that becomes more aobvious oil；(3) oil reservoir individual well moisture content is high, and flood is serious.At present, thermal recovery recovery ratio
It is 40-50% at present, also has more than half reserves viscous crude to need to take more preferable method mined.
Non- thermal recovery technology include it is cold adopt, chemical method and microbial method etc., and be mainly reducing viscosity by emulsification method in chemical method, i.e.,
Crude viscosity is reduced by chemical agent to make it easy to flow the method to improve recovery ratio.The glutinous method of chemistry drop has compared with heating exploitation
The characteristics of cost is low, technique is simple, equipment requirement is not high, effect is good, but the consumption and economy of reagent, the feature of environmental protection determine it
The prospect of application.It is singly that viscous crude visbreaking agent type of merchandize is various, has by neopelex and APES
The viscous crude visbreaking agent mixed, has heatproof visbreaking agent N- alkyl-γ-bis-quaternary ammonium salt cationic surfactant, there is drag reduction drop
Glutinous agent (being made up of carboxymethyl polyethers, sodium carbonate, sodium alkyl sulfate and PF-C), there is anti-salt type viscous crude visbreaking agent-APEO
Hydroxy-propanesulfonic acid salt etc..These visbreaking agent thinning effects can be more than 95%, but there is also deficiency, such as alkylphenol-polyethenoxy
The degraded intermediate of ether material is considered as to human body or unfavorable and disabled by the area such as America and Europe to environment.Drop containing sodium carbonate
CO in glutinous agent3 2-It is easy to and Ca in stratum2+/Mg2+Ion fouling and clogging stratum, though some visbreaking agents take into account the property of temperature-resistant anti-salt
Can, but washing oil, oil displacement efficiency be not obvious.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of reducing viscosity by emulsification type suitable for heavy crude reservoir
Displacement composition.The displacement composition has a variety of functions such as glutinous washing oil, drop, emulsification, the displacement of reservoir oil.
To reach above-mentioned purpose, the invention provides a kind of reducing viscosity by emulsification type displacement composition suitable for heavy crude reservoir,
By weight percentage, its composition composition includes：Anionic polymer 0.1-0.3%, nonionic surface active agent 0.01-
0.1%th, emulsion stabilizer 0.02-0.12%, appropriate inorganic salts and water surplus.
The above-mentioned reducing viscosity by emulsification type displacement composition suitable for heavy crude reservoir, it is preferable that the anionic gathers
Compound includes the anionic polymer for containing carboxyl (- COOH) in molecule.It is highly preferred that the anionic polymer includes
Sodium Polyacrylate (PAAS).Particularly preferably, the low molecule amount that the anionic polymer includes molecular weight 2000-3000 is gathered
PAA.The anionic polymer mainly plays a part of washing oil, the displacement of reservoir oil in displacement composition.
The above-mentioned reducing viscosity by emulsification type displacement composition suitable for heavy crude reservoir, it is preferable that the non-ionic table
Face activating agent includes one or more of combinations in APG (APG), Tween 80 (T80) and polysorbate85 (T85).More preferably
Ground, the APG includes APG0814 and/or APG0810.The nonionic surface active agent is main in displacement composition
It is to play a part of enhancing emulsification, drop to stick and washing oil.
The above-mentioned reducing viscosity by emulsification type displacement composition suitable for heavy crude reservoir, it is preferable that the emulsion stabilizer
Including polyacrylamide.It is highly preferred that the emulsion stabilizer including mean molecule quantity be 24,000,000, degree of hydrolysis be 20-25%,
The anion-polyacrylamide that 75 DEG C of heatproof.The anion-polyacrylamide has good viscosity and breast below 80 DEG C
Change stable effect.Particularly preferably, the emulsion stabilizer is the KY-6A of the permanent dimerization work Group Co., Ltd production in Beijing.
The above-mentioned reducing viscosity by emulsification type displacement composition suitable for heavy crude reservoir, it is preferable that the group of the inorganic salts
Into and content is made up of the ion of stratum water and content and mineralising angle value are determined, the inorganic salts include KCl, NaCl,
MgCl2、Na2SO4、CaCl2、Na2CO3And NaHCO3In one or more of combinations.
According to the embodiment of the present invention, it is preferable that the above-mentioned reducing viscosity by emulsification type displacement of reservoir oil suitable for heavy crude reservoir
Composition is through the following steps that prepare：
(1) anionic polymer is configured to the aqueous solution that mass concentration is 5-10%；
(2) nonionic surface active agent is configured to the aqueous solution that mass concentration is 1-5%；
(3) emulsion stabilizer is configured to the aqueous solution that mass concentration is 2-4%；
(4) inorganic salts are configured to inorganic salt solution according to the ion of stratum water composition and content and mineralising angle value
(concentration for the inorganic salt solution that the step is prepared need to consider the dilution of next step, make in the displacement composition that finally gives
Inorganic salt concentration it is consistent with the ion concentration of stratum water)；
(5) after the aqueous solution for obtaining step (1), (2) and (3) is mixed, then the inorganic salt solution obtained with step (4)
The content for being diluted to anionic polymer, nonionic surface active agent, emulsion stabilizer and inorganic salts meets requirement (respectively
Content of material, which is met, requires to be to meet above-mentioned anionic polymer 0.1-0.3%, nonionic surface active agent 0.01-
0.1%th, the requirement of emulsion stabilizer 0.02-0.12% and inorganic salts and stratum aqueous phase symbol), and stir, obtain described
The reducing viscosity by emulsification type displacement composition suitable for heavy crude reservoir.
In the present invention, the reducing viscosity by emulsification type displacement composition uses anionic polymer, non-ionic surfactant
The components such as agent, emulsion stabilizer, produce synergy, and breast can be formed quickly with the crude oil effect of heavy crude reservoir in application
Shape liquid and increase the mobility of crude oil, and can be carried out by the emulsified state in aqueous phase improve recovery ratio.The displacement of reservoir oil
Composition formation emulsion stability is good, oil displacement efficiency is good, on the one hand can peel off residual oil, can in addition, stripping down
Form relatively stable emulsified state with oil, aqueous systems, the 3rd, can be increased by viscosity reduction crude oil fluidity, reduce it is viscous
Resistance improves oil displacement efficiency, and then improves recovery ratio.
The reducing viscosity by emulsification type displacement composition suitable for heavy crude reservoir that the present invention is provided can solve the problem that common heavy oil and spy
Problem present in thickened oil recovery present situation and technology, uses environmental type water treatment agent and commercial surfactant, polymer
It is combined, obtains with multi-functional oil recovery agents such as washing oil, glutinous drop, emulsification, the displacement of reservoir oils.The displacement composition of the present invention has
(1) good to the thinning effect of common heavy oil and special thick oil, (2) are good to the washing oil effect of medium grain size oil-sand, (3) chemical flooding displacement of reservoir oil
Efficiency is higher, and (4) are free of alkali, to stratum fanout free region, the advantages of composition environmental protection easily biological-degradable.In summary, it should be applied to thick
The reducing viscosity by emulsification type displacement composition of oil reservoir is environmentally friendly, good to stratum fanout free region, biological degradability, good economy performance, group
Into composition be easy to purchase, it is good and cheap, prepare convenient, emulsifiability is good, displacement efficiency is high, effect substantially, be a kind of environment-friendly type,
The glutinous type oil recovery agent of drop.
Embodiment
In order to which technical characteristic, purpose and beneficial effect to the present invention are more clearly understood from, now to the skill of the present invention
Art scheme carry out it is described further below, but it is not intended that to the present invention can practical range restriction.
Experiment material and method：Experiment uses the Liaohe River and Xinjiang block common heavy oil and special thick oil.Liaohe River formation temperature
80 DEG C, formation water salinity is 2575.85mg/L, and oil density is 0.9235g/cm3, Crude viscosity 4652mPas.Xinjiang
Formation temperature is 50 DEG C, and Xinjiang 1# blocks formation water salinity is 4648mg/L, and the formation water salinity of Xinjiang 2# blocks is
10895mg/L, Crude viscosity is respectively 34268mPas and 2339mPas, and oil density is 0.9341g/cm3With
0.9212g/cm3.The ion composition and content of three kinds of stratum water with mineralising angle value (unit is mg/L) as shown in table 1.
Table 1
| Ion is constituted | K+ | Na+ | Ca2+ | Mg2+ | Cl- | SO4 2- | CO3 2- | HCO3 - | Total salinity |
| The Liaohe River | 15.2 | 798.9 | 19.0 | 9.95 | 224.4 | 12.2 | 0 | 1496.2 | 2575.85 |
| Xinjiang 1# | 44.8 | 1587.8 | 135.0 | 119.2 | 1171.5 | 258.5 | 332.8 | 998.7 | 4648.3 |
| Xinjiang 2# | 1293.1 | 3896.4 | 231.6 | 165.8 | 3621.7 | 376.2 | 284.7 | 1025.5 | 10895.0 |
Displacement efficiency：It is formulated using the dehydration degassed crude of correspondence block with medium grain size (80-100 mesh) quartz sand
Oil-sand, sand oil mass ratio be 7:1, aging more than 7 days is stand-by at the formation temperature.Washing oil process is using gas at the formation temperature
First shaken 2 hours in bath oscillator, then 5 hours are incubated in insulating box, determine the amount for separating out oil, calculate displacement efficiency (specific step
Suddenly referring to relevant regulations in " binary combination flooding surfactant technology specification " Q/SY1583-2013 company standards).
Emulsion stability and displacement efficiency index：According to company standard " binary is driven and uses surfactant technology specification " (Q/
SY1583-2013 specified content is carried out in the relevant provision in).
Interfacial tension：Using U.S. Texas-500 type spinning drop interfacial tensiometers, determine at the formation temperature.
Viscosity：Using the U-shaped Brookfield viscosity apparatus of U.S. LVDV- III, survey at the formation temperature or at specific temperature
It is fixed.
Embodiment 1
Different types of industrial activated dose and simulated formation water are taken to Liaohe River block crude oil (oil density=d=
0.9137g/cm3) prepare oil-sand (80-100 mesh) washing oil effect.Washing oil process：Weigh a certain amount of oil-sand be put into washing oil bottle in,
It is injected separately into after various doses (being prepared using corresponding simulated formation water) prepared that to be put into gas bath oscillator insulation concussion 2 small
When (concussion speed=150-160r/min), then take out and be put into insulating box (55 DEG C) the record results that are incubated 5 hours, calculating is washed
Oily efficiency (quality/original oil-sand of displacement efficiency=precipitation oil contains quality × 100% of oil), experimental result is as shown in table 2.
Table 2
Go out the simulated formation water in the Liaohe River oily area from the experimental results does not have washing oil energy substantially to the simulation oil-sand of the block
Power, cation surfactant trimethyl chloromethane ammonium does not have washing oil effect yet.Other anion-nonionics, nonionic business
Surfactant and polymer and oil industry oil displacement agent have a washing oil effect of different sizes, but most preferably two kinds it is non-from
Sub- surfactant.
Embodiment 2
Oil-sand, aging 20 days at 80 DEG C, when emulsification experiment is with 80 DEG C of crude oil are simulated using 80-100 mesh Liaohe River block
Viscosity is 4652mPas.It is injected separately into various complexing agents (PAAS and another additive, using corresponding simulation prepared
Stratum water is prepared), 5 hours are incubated again after being shaken 2 hours in gas bath oscillator, carry out displacement efficiency test experiments, as a result such as
(various doses of concentration % refers both to mass concentration in table 3, herein, unless otherwise instructed, and concentration % refers both to quality shown in table 3
Concentration).
Table 3
The system viscosity of complexing agent is not high, emulsion stability preferably, displacement efficiency most preferably PAAS and APG group
Close, the combination displacement efficiency with T80 is also higher.It is in sepia shape with Liaohe River block profit generation emulsion, emulsion stability exists
More than 20% person has 3 kinds, makes crude oil viscosity lowering rate all more than 98%, thinning effect is preferable.
Embodiment 3
Oil-sand is simulated using 80-100 mesh Liaohe River block, aging 20 days at 55 DEG C are injected separately into prepare various
Complexing agent (APG0814 different from mass concentration PAAS is prepared using corresponding simulated formation water), shakes in gas bath oscillator
Swing and be incubated 5 hours after 2 hours again, carry out displacement efficiency test experiments, as a result as shown in table 4.
Table 4
PAAS contents be 0.2%, APG0814 contents from 0.02%-0.10%, this four groups of experimental results show displacement efficiencies
Above 60%, it is extraordinary effect.Wherein most preferably both mass ratioes are 5:1 combination.
Embodiment 4
Oil-sand is simulated using 80-100 mesh Liaohe River block, aging 20 days at 80 DEG C are injected separately into prepare various
Complexing agent (is prepared) using corresponding simulated formation water, the concussion (concussion speed=148-152r/min) 2 in gas bath oscillator
5 hours are incubated again after hour, carry out displacement efficiency test experiments, as a result as shown in table 5.
Table 5
When Tween 80 mass content be when 0.05%, PAAS contents are more than 0.2% washing oil effect also reached 50% with
On.And when KY-6A contents are certain, washing oil effect is more preferable during PAAS content increases.This explanation, PAAS and Tween 80 and polyacrylamide
Amine has preferable concertedness, also needs suitable mass ratio.Also, what the interfacial tension of PAAS and polymeric system had reaches
10-3Level ultralow mN/m, it is 10 to have 3 groups of agent-2mN/m.Therefore the interfacial tension of this oil displacement agent system is not necessarily ultralow, but
Emulsifiability is emulsifying oil recovery agent preferably.
Embodiment 5
Washing oil experiment is injected separately into the various complexing agents prepared using 80-100 mesh Xinjiang simulation oil-sand (aging 25 days)
(being prepared using corresponding simulated formation water), is shaken 2 hours in gas bath oscillator with 158-160r/min speed, then 50
5 hours are incubated at DEG C, displacement efficiency test experiments are carried out, as a result as shown in table 6.Profit mass ratio is 1 in emulsion:7, crude oil
Viscosity is 34268mPas, and oil density is 0.9341g/cm3。
Table 6
It can be seen that, intermixture is good to the washing oil effect of the oil-sand of Xinjiang block, more than emulsion stability more than medium
(30%), glutinous rate drops all more than 99%.
Embodiment 6
Physical simulation experiment uses Xinjiang profit, and (for 34268mPas, oil density is 0.9341g/ to Crude viscosity
cm3).Displacement composition is prepared using the inorganic salt solution (specific ion composition and content are as shown in table 1) of simulated formation water,
The salinity for preparing obtained displacement composition (aqueous solution) is 4648mg/L.Rock core selects imported from America Berea core, experiment
Temperature 50 C, oil displacement experiment uses normal experiment flow.Displacement process is using 3 slugs：Water drive is injected to after aqueous 98%
The KY-6A aqueous solution (preparation of simulated formation water) of 0.2PV mass concentration 0.1%, is then injected into 0.3PV displacement composition,
Water drive is to aqueous more than 98% end after finally carrying out, and experimental result is as shown in table 7.
Table 7
Three groups of rock core displacement tests as a result, it was confirmed that the present embodiment provide displacement composition emulsifiability it is good, chemical flooding
Oil displacement efficiency average out to 24.99% is suitable with the effect of industrial strong base ternary composite driving oil displacement agent more than 20%.
Claims (5)
1. a kind of reducing viscosity by emulsification type displacement composition suitable for heavy crude reservoir, by weight percentage, its composition composition include：
It is anionic polymer 0.1-0.3%, nonionic surface active agent 0.01-0.1%, emulsion stabilizer 0.02-0.04%, inorganic
Appropriate salt and water surplus；
The anionic polymer is Sodium Polyacrylate；
One or more of combinations of the nonionic surface active agent in APG, Tween 80 and polysorbate85；
The emulsion stabilizer is polyacrylamide.
2. the reducing viscosity by emulsification type displacement composition according to claim 1 suitable for heavy crude reservoir, wherein, the alkyl sugar
Glycosides is APG0814 and/or APG0810.
3. the reducing viscosity by emulsification type displacement composition according to claim 1 suitable for heavy crude reservoir, wherein, the emulsification is steady
It is that mean molecule quantity is that 24,000,000, degree of hydrolysis is 20-25%, the anion-polyacrylamide of 75 DEG C of heatproof to determine agent.
4. the reducing viscosity by emulsification type displacement composition according to claim 1 suitable for heavy crude reservoir, wherein, the inorganic salts
Composition and content is made up of the ion of stratum water and content and mineralising angle value are determined, the inorganic salts be selected from KCl,
NaCl、MgCl2、Na2SO4、CaCl2、Na2CO3And NaHCO3In one or more of combinations.
5. the reducing viscosity by emulsification type displacement composition according to claim 1 suitable for heavy crude reservoir, it is by following step
Suddenly prepare：
（1）Anionic polymer is configured to the aqueous solution that mass concentration is 5-10%；
（2）Nonionic surface active agent is configured to the aqueous solution that mass concentration is 1-5%；
（3）Emulsion stabilizer is configured to the aqueous solution that mass concentration is 2-4%；
（4）Inorganic salts are configured to inorganic salt solution according to the ion of stratum water composition and content and mineralising angle value；
（5）By step（1）、（2）With（3）After obtained aqueous solution mixing, then use step（4）Obtained inorganic salt solution dilution
Content to anionic polymer, nonionic surface active agent, emulsion stabilizer and inorganic salts meets requirement, and stirs
Uniformly, the described reducing viscosity by emulsification type displacement composition suitable for heavy crude reservoir is obtained.
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| CN107605444B (en) * | 2016-07-12 | 2020-01-24 | 中国石油化工股份有限公司 | Polymer flooding method for heavy oil reservoir |
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| CN109812249B (en) * | 2017-11-20 | 2023-08-08 | 中国石油化工股份有限公司 | Oil reservoir oil displacement method |
| CN108441199A (en) * | 2018-03-23 | 2018-08-24 | 北京捷贝通石油技术股份有限公司 | A kind of environment-friendly highly efficient heavy crude thinner |
| CN108865096A (en) * | 2018-06-08 | 2018-11-23 | 烟台智本知识产权运营管理有限公司 | A kind of thickened oil recovery high efficiency composition thinner |
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| CN114763737A (en) * | 2021-01-13 | 2022-07-19 | 中国石油天然气股份有限公司 | Method for determining self-emulsifying viscosity-reducing oil displacement system and application |
| CN113528109B (en) * | 2021-06-02 | 2022-08-02 | 中国石油大学(北京) | Viscosity reducer, preparation method and application thereof |
| CN115029122B (en) * | 2022-06-22 | 2024-03-15 | 中国石油大学(华东) | Cellulose nanocrystalline synergistic emulsion oil displacement agent and preparation method and application thereof |
| CN116285932B (en) * | 2023-05-22 | 2023-08-15 | 德仕能源科技集团股份有限公司 | Viscous oil viscosity reducer for polymer flooding and preparation method and application thereof |
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