CN103242817B - Emulsified penetration-driving oil recovery agent and preparation method thereof - Google Patents
Emulsified penetration-driving oil recovery agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an emulsified penetration-driving oil recovery agent and a preparation method thereof. The emulsified penetration-driving oil recovery agent consists of the following components by weight percent: 0.1 to 0.2 percent of anionic/nonionic polymer, 0.01 to 0.03 percent of anionic polyacrylamide, 0.01 to 0.05 percent of coactivating agent and the balance of water, wherein the negative nonionic polymer is TH3100. The preparation method of the emulsified penetration-driving oil recovery agent comprises the following steps of: preparing the TH3100 into an aqueous solution with the concentration of 5 to 10 wt%; preparing the anionic polyacrylamide into an aqueous solution with the concentration of 0.1 to 0.2 wt%; preparing the coactivating agent into an aqueous solution with the concentration of 0.1 to 0.5 wt%; and mixing the three aqueous solutions, supplementing the residual water and stirring uniformly to obtain the emulsified penetration-driving oil recovery agent. The emulsified penetration-driving oil recovery agent has good solubility, can be mixed with water to form a uniform solution, does not have light oil, can form O/W emulsion when encountering crude oil in an aqueous phase, achieves good deoiling and oil washing effects, and is a good oil recovery agent for S/P binary displacement.
Description
Technical field
The present invention relates to a kind of oil-in-water type to drive and ooze type oil recovery agent and preparation method thereof, belong to technical field of petroleum extraction.
Background technology
In order to reduce the external dependence degree of crude oil in China, tertiary oil recovery technology becomes history the dominant technology of China's maturing field in decades, alkali/polymkeric substance/tensio-active agent ternary chemical combined flooding technology is ripe, the obvious a kind of technology of raising recovery ratio, serves on record vital role to the stable and high yields of some elephants.But in application and implementation process, also there is the series of problems such as fouling, corrosion and Produced Liquid oily water separation difficulty, and hence, limit the further broadened application of this technology.Therefore, alkali-free binary chemical combined flooding technology causes and pays close attention to widely.But according to the Evaluating and screening standard in past, particularly harsh to the performance requriements of the tensio-active agent in binary chemistry composite displacement system under alkali-free condition---interfacial tension must reach ultralow, therefore seldom has promoting agent can reach this requirement at alkali-free system.Although the synergy of polymkeric substance/promoting agent still can keep visco-elasticity and the interfacial activity of system, if but with standard-required in the past reach ultra low interfacial tension just seem difficulty, the promoting agent that can reach this requirement is also few, add the requirement of economy and practicality, adopt new judgement criteria searching and develop the oil recovery agent system meeting the good binary chemical combined flooding of oil displacement efficiency extremely urgent, become the key issue affecting the application of binary chemical combined flooding technology.
CN1597835A discloses a kind of micro-emulsion type oil-displacing agent, and its weight consists of: emulsifying agent 15-50%, and fraction oil of petroleum 40-80% helps emulsion 0.5-5%, water surplus.Wherein, emulsifying agent is polyolefin carboxylic acid's ester and/or polyolefin carboxylic acid's Soxylat A 25-7, is composited with polyolefin carboxylic acid's Soxylat A 25-7 sulphonate and/or phosphoric acid ester, or only uses polyolefin carboxylic acid's Soxylat A 25-7 sulphonate and/or phosphoric acid ester; In each component, polyolefinic number-average molecular weight is 500-3000, and polyolefine is the polymkeric substance of carbon four or C_5 olefins.Oxy-compound is selected from monoethanolamine, diethanolamine, trolamine, ethylene glycol, glycerine, sorbyl alcohol and tetramethylolmethane; Fraction oil of petroleum comprises: gasoline, kerosene, diesel oil; Emulsion is helped to be R
lcOOH or R
2cOH, wherein R
l, R
2c
4-C
20straight chain or the alkane of isomery, help emulsion amount ranges to be 2-4%.The viscosity of this emulsifying agent is 20-3000 (100 DEG C of mm
2/ s), emulsifier scope is 10-60w%, preferably 30-50w%.This is a kind of water-in-oil emulsion oil-displacing agent, can add other component again during use according to oil field reality.
CN101684406A discloses anti-salt temperature-resistant high-efficient oil-displacing agent applicable and preparation method thereof, formulated according to weight percent by following component: Soxylat A 25-7 sulfonated alkyl naphathalene 25-30%, permeate agent 8-15%, nonionogenic tenside 10-15%, organic solvent 15-20%, the compositions such as water 20-42%.Permeate agent is mixture that is a kind of in certain herbaceous plants with big flowers base Soxylat A 25-7, pentadecyl Soxylat A 25-7 or its any proportioning; Nonionogenic tenside is mixture that is a kind of in fatty alcohol-polyoxyethylene ether, glycerine fatty acid fat, sorbitol polyoxyethylene ether or its any proportioning; Organic solvent is a kind of mixture of or its any proportioning of methyl alcohol, ethanol, ethylene glycol, Virahol.This oil-displacing agent effective active thing content, when 0.4-1.0%, can effectively reduce interfacial tension to 10
-2-10
-3mN/m.
Above oil-displacing agent for binary combination flooding oil-displacing agent, moiety is many, containing organic solvent or organic hydrocarbon component (lightweight oil) etc., cost is higher, preparation is more complicated, the former is oil-in-water emulsify type oil-displacing agent, the latter is ultralow for judgement criteria with interfacial tension, all be applicable to binary combination flooding system, do not provide oil displacement efficiency.
Summary of the invention
In order to overcome prior art to requiring in promoting agent/polymkeric substance (S/P) system that the interfacial activity of promoting agent reaches the limitation of ultralow requirement and the complexity problem of existing oil-displacing agent composition, the object of this invention is to provide a kind of oil-in-water type to drive and ooze type oil recovery agent, with appropriate emulsification and drive, ooze combination, the principle of taking into account multi-functional, economy and practicality, develop that Oil Displacing Capacity is excellent, cheap, the alkali-free compound flooding oil-in-water type of safety and environmental protection drives and oozes type oil recovery agent.
For achieving the above object, the invention provides a kind of oil-in-water type to drive and ooze type oil recovery agent, by percentage to the quality, this oil-in-water type drives and oozes type oil recovery agent and have following one-tenth and be grouped into: anion-nonionic type polymkeric substance 0.1-0.2%, anion-polyacrylamide 0.01-0.03%, cosurfactant 0.01-0.05%, and all the other are water; Wherein, anion-nonionic type polymkeric substance is TH3100.
TH3100(carboxylate salt-sulfonate-nonionic terpolymer, also known as TH-3100) be containing several functions base (-COOH ,-SO in a kind of molecule
3h) New Type Water Treatment Chemicals.TH3100 is driven the host of oozing type oil recovery agent as oil-in-water type of the present invention, both there is good interfacial activity, washability is strong, there is again stronger visco-elasticity and involve ability.
According to specific embodiment of the invention scheme, anion-polyacrylamide assists to drive penetration enhancer, good with host compatibility, can oil-in-water type be regulated to drive to ooze the visco-elasticity of type oil recovery agent system, mobility ratio, emulsifying property, de-oiling ability and volumetric conformance efficiency better, and then improve recovery ratio.Preferably, above-mentioned oil-in-water type drives the molecular weight oozing the anionic polypropylene amine that type oil recovery agent adopts is 1600-2500 ten thousand.
According to specific embodiment of the invention scheme, preferably, above-mentioned oil-in-water type drives and oozes the cosurfactant that type oil recovery agent adopts and be made up of sodium polyacrylate and aerosol-OT salt, the mass ratio of the two is 1:1, wherein, sodium polyacrylate has dissemination and scale effect, and aerosol-OT salt has emulsification and osmosis.
Present invention also offers above-mentioned oil-in-water type and drive the preparation method of oozing type oil recovery agent, it comprises the following steps:
Anion-nonionic type polymkeric substance TH3100 is mixed with the aqueous solution that concentration is 5-10wt%;
Anion-polyacrylamide is mixed with the aqueous solution that concentration is 0.1-0.2wt%;
Cosurfactant is mixed with the aqueous solution that concentration is 0.1-0.5wt%;
Above-mentioned three kinds of aqueous solution are supplemented remaining water, stirs, obtain described oil-in-water type and drive and ooze type oil recovery agent.
The displacement of reservoir oil and de-washing oil effect can represent by the value of chemical flooding recovery ratio and de-oiling rate, chemical flooding recovery ratio=(displacing the quality containing crude oil in the quality/rock core of oil) × 100%; De-oiling rate=(deviating from the quality of original oil in oily quality/oil-sand or rock core) × 100%.
Oil-in-water type provided by the invention drives and oozes type oil recovery agent and have the following advantages:
(1) adopt TH3100 as host, there is the obvious displacement of reservoir oil, washing oil effect, overcome highly basic and there is the formation damage and the problem such as fouling, burn into Produced Liquid difficult treatment that cause;
(2) adopt anion-polyacrylamide as assistant agent, assist enhancement effective with host, system constituent kind is few, and preparation is convenient, does not need to add large-scale dosing equipment, reduces running cost;
(3) this oil-in-water type drives that to ooze type oil recovery agent solvability good, can be mixed into uniform solution, not add lightweight oil, run into crude oil and can form O/W type milk sap in aqueous phase with water, and de-oiling, washing oil are effective;
(4) this oil-in-water type drives and oozes alkali-free (NaOH, Na in type oil recovery agent
2cO
3, NaHCO
3deng), be that good S/P binary is driven and used oil recovery agent.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
In following examples, the rock core adopted is that (length is respectively 20cm, 30cm for the natural Berea core of natural exposure rock core and imported from America, diameter is respectively 2.5cm, 3.8cm), crude oil and stratum Simulated Water are respectively crude oil and the water of Dagang Oilfield and Daqing oil field, and Dagang Oilfield water salinity is 8768mg/L, in-place oil viscosity 9.9mPas(53.6 DEG C).Daqing oil field water salinity is 5679mg/L, oil viscosity 10.0mPas(45 DEG C);
TH3100 is carboxylate salt-sulfonate-nonionic terpolymer, is produced by Shanghai Hao Kang Chemical Co., Ltd., and be excellent water treatment dirt dispersion agent, solid content 43-44wt%, density is not less than 1.15g/cm
3, pH is 2.1-2.8.
Aerosol-OT salt is produced by company of Jin Long Chemical Co., Ltd. of Huantai County of Shandong Province, and the trade mark is penetrant t, and active constituent content is not less than 30%, pH=5.0-7.0.
Sodium polyacrylate is produced by company of Jin Long Chemical Co., Ltd. of Huantai County of Shandong Province, and the trade mark is PAAS, and wherein, solid content is 30-50wt%, and free monomer is (with CH
2=CH-COOH counts) content is 0.5-1wt%, pH value is 6-8;
The oil field that produced by Beijing permanent dimerization work Group Co., Ltd of polyacrylamide with anion-polyacrylamide (HPAM), working substance content 88wt%, molecular-weight average 1600-2500 ten thousand.
Other reagent are all from being purchased.
Experimental technique:
(1) oil-in-water type drives the preparation of oozing type oil recovery agent
Be the TH3100 aqueous solution of 5-10wt% by concentration, the cosurfactant of concentration to be the 0.1-0.3wt%HPAM aqueous solution and concentration be 0.1-0.5wt% (is made up of sodium polyacrylate and aerosol-OT salt, the mass ratio of the two is 1:1) strong solution such as the aqueous solution is diluted to expection concentration by appropriate grand celebration (or huge port) oil field stratum Simulated Water, then by three kinds of aqueous solution, the oil-in-water type of amount obtaining expecting drives that to ooze type oil recovery agent stand-by, and the emulsifying property of gained oil recovery agent is 3 and 4 etc.
(2) oil-sand de-oiling experiment (imbibition de-oiling experiment)
Oil-in-water type prepared by step (1) drive ooze type oil recovery agent, viscosity is 10mPas, d=0.8294g/cm when adopting 45 DEG C
3the oil-sand prepared of Daqing crude oil or 53.6 DEG C time viscosity be 9.9mPas, d=0.8603g/cm
3the oil-sand prepared of Crude Oil In Dagang carry out the static de-oiling experiment of normal pressure, normal pressure de-oiling bottle (the i.e. Self-imbibition instrument that provides of ZL201120075849.7 is provided in experiment, it is introduced here as a reference in full), observed and recorded result, calculates the result de-oiling rate value of 24 hours.
(3) rock core de-oiling or oil displacement experiment
When adopting 45 DEG C, viscosity is 10mPas, d=0.8294g/cm
3daqing crude oil or 53.6 DEG C time viscosity be 9.9mPas, d=0.8603g/cm
3the different rock core of Crude Oil In Dagang saturated permeability, adopt step (1) oil-in-water type prepared to drive to ooze type oil recovery agent and carry out the static de-oiling experiment of normal pressure or conventional oil displacement experiment, normal pressure de-oiling bottle (the i.e. Self-imbibition instrument that provides of ZL201120075849.7 is provided in experiment, it is introduced here as a reference in full), the concrete operations of conventional oil displacement test (chemical flooding), see SY/T6424-2000 " composite oil-displacing system performance test methods ", records and are calculated and reach de-oiling rate value when imbibition balances or calculational chemistry drives overall recovery factor value.It is 0.3PV that oil-in-water type drives the injection rate of oozing type oil recovery agent.
Embodiment 1
(1) oil-sand logistics organizations
1) drive according to (1) preparation oil-in-water type in experimental technique above and ooze type oil recovery agent and adopt oil-sand to carry out de-oiling experiment according to (2).
Prepare three kinds of oil-in-water types to drive and ooze type oil recovery agent, salinity is respectively 12700mg/L, 13700mg/L, 14700mg/L, and wherein, the content of TH3100 is 0.2wt%, and the content of assistant agent HPAM is 0.01wt%, and the content of cosurfactant is 0.02wt%;
Use huge port oil-sand (100-160 order, aging 120 hours) to carry out de-oiling experiment, record three kinds of oil-in-water types and drive 24 hours de-oiling rates of oozing type oil recovery agent and be respectively 86.79,87.32,89.45, all more than 86.79%.
2) drive according to (1) preparation oil-in-water type in experimental technique above and ooze type oil recovery agent and adopt oil-sand to carry out de-oiling experiment according to (2).
Prepare four kinds of oil-in-water types to drive and ooze type oil recovery agent, salinity is respectively 8700mg/L, 18700mg/L, 28700mg/L, 38700mg/L, and wherein, the content of TH3100 is 0.2wt%, and the content of assistant agent HPAM is 0.01wt%, and the content of cosurfactant is 0.03wt%;
Use huge port oil-sand (100-160 order, aging 120 hours) to carry out de-oiling experiment, record four kinds of oil-in-water types and drive 24 hours de-oiling rates of oozing type oil recovery agent and be respectively 76.93%, 79.21%, 82.22%, 88.07%, de-oiling rate average out to 81.61%.
3) drive according to (1) preparation oil-in-water type in experimental technique above and ooze type oil recovery agent and adopt oil-sand to carry out de-oiling experiment according to (2).
Prepare two kinds of oil-in-water types to drive and ooze type oil recovery agent, salinity is respectively 18700mg/L, and wherein, the content of TH3100 is 0.2wt%, and the content of assistant agent HPAM is 0.01wt%, and the content of cosurfactant is 0.05wt%;
Use huge port oil-sand (>=160 orders and 100-160 order, aging 172 hours) to carry out de-oiling experiment, record two kinds of oil-in-water types and drive 24 hours de-oiling rates of oozing type oil recovery agent and be respectively 73.98% and 79.87%, average de-oiling rate 76.93%.
4) drive according to (1) preparation oil-in-water type in experimental technique above and ooze type oil recovery agent and adopt oil-sand to carry out de-oiling experiment according to (2).
Prepare two kinds of oil-in-water types to drive and ooze type oil recovery agent, salinity is respectively 8700mg/L, 18700mg/L, and wherein, the content of TH3100 is 0.2wt%, and the content of assistant agent HPAM is 0.01wt%, and the content of cosurfactant is 0.02wt%;
Use huge port oil-sand (100-160 order, aging 192 hours) to carry out de-oiling experiment, record two kinds of oil-in-water types and drive 24 hours de-oiling rates of oozing type oil recovery agent and be respectively 83.20%, 77.31%, de-oiling rate average out to 80.26%.
5) drive according to (1) preparation oil-in-water type in experimental technique above and ooze type oil recovery agent and adopt oil-sand to carry out de-oiling experiment according to (2).
Different, that system viscosity the is different 6 groups of oil-in-water types of preparation assistant agent amount drive and ooze type oil recovery agent sample, wherein, the content of host TH3100 is 0.2wt%, the content of cosurfactant is 0.01wt%, content and the system viscosity of assistant agent HPAM are as shown in table 1, and oil-in-water type drives that the interfacial tension of oozing type oil recovery agent is 2.78mN/m, salinity is 18700mg/L;
Use huge port oil-sand (100-160 order, aging 72 hours) to carry out de-oiling experiment, test result is as shown in table 1.
Table 1
| Sample number | 1 | 2 | 3 | 4 | 5 | 6 |
| Assistant agent content/wt% | 0 | 0.02 | 0.03 | 0.04 | 0.05 | 0.06 |
| System viscosity/mPas | 0.2 | 1.3 | 2.15 | 3.0 | 3.15 | 5.20 |
| 24 hours de-oiling rate/% | 70.35 | 81.10 | 70.37 | 70.27 | 71.55 | 66.71 |
As can be seen from the result of table 1, the average de-oiling rate 71.73% of 6 samples, de-oiling rate first increases rear reduction along with the increase of assistant agent content, the increase of viscosity, and when assistant agent is 0.02wt%, de-oiling effect is best.
6) drive according to (1) preparation oil-in-water type in experimental technique above and ooze type oil recovery agent and adopt oil-sand to carry out de-oiling experiment according to (2).
Different, that system viscosity the is different 4 groups of oil-in-water types of preparation assistant agent amount drive and ooze type oil recovery agent sample, wherein, the content of host TH3100 is 0.2wt%, the content of cosurfactant is 0.02wt%, content and the system viscosity of assistant agent HPAM are as shown in table 2, and oil-in-water type drives that the interfacial tension of oozing type oil recovery agent is 2.78mN/m, salinity is 18700mg/L;
Use Daqing oil sand (100-160 order, aging 192 hours) to carry out de-oiling experiment, test result is as shown in table 2.
Table 2
| Sample number | 1 | 2 | 3 | 4 |
| Assistant agent content/wt% | 0 | 0.01 | 0.02 | 0.04 |
| System viscosity/mPas | 0.2 | 0.5 | 1.3 | 3.0 |
| Average de-oiling rate/% | 83.46 | 78.80 | 83.12 | 71.12 |
As can be seen from the data of table 2, average de-oiling rate is 79.13%, oil-in-water type drive ooze that in type oil recovery agent, assistant agent content is at 0.01-0.02wt% time comparatively suitable.
7) comparative example
The oil-displacing agent prepared according to (1) in experimental technique above also adopts oil-sand to carry out de-oiling experiment according to (2).
Adopt the sulfonated petro-leum series products that the actual oil-displacing agent KPS(Xinjiang Oilfield of Xinjiang Oilfield is produced) prepare two kinds of oil-displacing agents that salinity is respectively 8700mg/L and 18700mg/L, adopt huge port oil-sand (100-160 order, aging 93 hours) carry out de-oiling experiment, the 24 hours de-oiling rates recording two kinds of oil-displacing agents are respectively 53.68% and 62.63%, and average de-oiling rate is 58.16%.
In embodiment 1 1) to 6) oil-sand de-oiling experimental result in example shows, no matter to Daqing oil sand, or huge port oil-sand, oil-in-water type drive ooze type oil recovery agent average de-oiling rate all higher than 70%, the oil-displacing agent KPS successful of use actual in Karamay Oil Fields in Xinjiang will be got well.
(2) rock core logistics organizations
Embodiment 2
1) drive according to (1) preparation oil-in-water type in experimental technique above and ooze type oil recovery agent and adopt corresponding crude oil saturated core according to (3) and carry out rock core de-oiling experiment, adopt crude oil and the water of Dagang Oilfield in experiment, adopt perm-plug method to be respectively the natural exposure rock core of 5.03mD and 103mD.Oil-in-water type drives and oozes consisting of of type oil recovery agent: host 0.2wt%, assistant agent 0.01wt%, cosurfactant 0.02wt%, and surplus is water; It is 8700mg/L that oil-in-water type drives the salinity of oozing type oil recovery agent, records its static de-oiling rate for two kinds of rock cores be respectively 32.26% and 31.79%, average out to 32.03% through experiment.
2) drive according to (1) preparation oil-in-water type in experimental technique above and ooze type oil recovery agent and adopt corresponding crude oil saturated core according to (3) and carry out rock core de-oiling experiment, adopt rate of permeation to be respectively 3 natural exposure rock cores of 85.3mD, 102mD and 120mD in experiment, adopt crude oil and the water of Dagang Oilfield.Oil-in-water type drives and oozes consisting of of type oil recovery agent: host 0.3wt%, assistant agent 0.02wt%, cosurfactant 0.01wt%, and surplus is water; Oil-in-water type drives the salinity of oozing type oil recovery agent and is respectively 18700mg/L, and interfacial tension is respectively 2.725mN/m, records its static de-oiling rate for three kinds of rock cores be respectively 17.17%, 30.86% and 35.93%, average out to 27.99% through experiment.
3) drive according to (1) preparation three kinds of oil-in-water types in experimental technique above and ooze type oil recovery agent and adopt corresponding crude oil saturated core according to (3) and carry out rock core de-oiling experiment, adopt crude oil and the water of Dagang Oilfield in experiment, adopt perm-plug method to be respectively the import Berea core of 90.7mD and 96.9mD.Oil-in-water type drives and oozes consisting of of type oil recovery agent: host 0.2wt%, assistant agent 0.01wt%, cosurfactant 0.02wt%, and surplus is water; It is 8700mg/L that oil-in-water type drives the salinity of oozing type oil recovery agent.Oil-displacing agent injection rate is 0.3PV, through experiment record: at waterflood recovery efficiency factor be 35.0% and 35.5% basis on, the recovery ratio of chemical flooding is respectively 19.2% and 19.4%.
Can be found out by the above results, oil-in-water type drive ooze type oil recovery agent static rock core de-oiling rate higher than 25%, for the chemical flooding recovery ratio of the low permeability cores lower than 100mD higher than 19%, illustrate this oil-in-water type drive the displacement of reservoir oil of oozing type oil recovery agent and imbibition de-oiling effect all good, under hypotonic condition, also there is good oil displacement efficiency.
Claims (3)
1. an oil-in-water type drives and oozes type oil recovery agent, by percentage to the quality, this oil-in-water type drives and oozes type oil recovery agent and have following one-tenth and be grouped into: anion-nonionic type polymkeric substance 0.1-0.2%, anion-polyacrylamide 0.01-0.03%, cosurfactant 0.01-0.05%, and all the other are water; Wherein, described anion-nonionic type polymkeric substance is TH3100; Wherein, cosurfactant is made up of sodium polyacrylate and aerosol-OT salt, and the mass ratio of the two is 1:1.
2. oil-in-water type according to claim 1 drives and oozes type oil recovery agent, and wherein, the molecular weight of described anionic polypropylene amine is 1600-2500 ten thousand.
3. the oil-in-water type described in claim 1 or 2 drives the preparation method of oozing type oil recovery agent, and it comprises the following steps:
Anion-nonionic type polymkeric substance TH3100 is mixed with the aqueous solution that concentration is 5-10wt%;
Anion-polyacrylamide is mixed with the aqueous solution that concentration is 0.1-0.2wt%;
Cosurfactant is mixed with the aqueous solution that concentration is 0.1-0.5wt%;
Above-mentioned three kinds of aqueous solution are supplemented remaining water, stirs, obtain described oil-in-water type and drive and ooze type oil recovery agent.
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| 疏水缔合聚合物驱油能力的三种重要影响因素;朱怀江等;《石油学报》;20050525;第26卷(第03期);52-55 * |
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| CN103242817A (en) | 2013-08-14 |
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