CN102666777A - Water flooding method for secondary hydrocarbon recovery - Google Patents

Water flooding method for secondary hydrocarbon recovery Download PDF

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Publication number
CN102666777A
CN102666777A CN2010800493441A CN201080049344A CN102666777A CN 102666777 A CN102666777 A CN 102666777A CN 2010800493441 A CN2010800493441 A CN 2010800493441A CN 201080049344 A CN201080049344 A CN 201080049344A CN 102666777 A CN102666777 A CN 102666777A
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China
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compsn
water filling
mobility
hydrocarbon
thickening polymer
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Inventor
穆罕默德·亚曼·伯吕克
白江
布莱恩·弗朗西斯·霍金斯
罗伯特·约斯特
福雷德·瓦斯穆特
赵丽艳
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Alberta Innovates Technology Futures
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Alberta Innovates Technology Futures
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    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/20Displacing by water
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers

Abstract

The invention relates to a water flooding composition in a method of secondary hydrocarbon recovery. The water flooding composition includes water and a thickening polymer. The thickening polymer includes a hydroxyethyl cellulose backbone polymer having a molecular weight of between about 1,000,000 and about 2,000,000 and a hydrophobic modifier. The hydrophobic modifier has a substitution level in the thickening polymer of between about 0.1 percent and about 2 percent by weight of the thickening polymer. The hydrophobic modifier is an alkyl hydrocarbon based material containing between about 10 and about 24 unsubstituted carbon atoms per group. The thickening polymer has a concentration in the water flooding composition of between about 0.01 percent and about 1 percent by weight of the water flooding composition. The water flooding composition is formulated within these ranges so that the water flooding composition has a suitable viscosity/mobility and so that the water flooding composition is injectable.

Description

The water flood that is used for the hydrocarbon secondary recovery
Technical field
Hydrocarbon secondary recovery method, said method comprise makes the water filling compsn through containing the stratum that hydrocarbon is hidden.
Background technology
The fs of hydrocarbon production is called as the hydrocarbon primary recovery.In the hydrocarbon primary recovery, the energy in the stratum (for example pressure or potential energy) is utilized to that displacement is to recovery well from the stratum with hydrocarbon, and final displacement is to the face of land.The hydrocarbon primary recovery can be by means of artificial hoisting system pump or gas lifting equipment for example.
The subordinate phase of hydrocarbon production is called the hydrocarbon secondary recovery.In the hydrocarbon secondary recovery, the external fluid of gas or liquid form is expelled in the stratum through one or more injector well.Said external fluid plays usually passes through the stratum to one or more recovery well displacement with hydrocarbon, thus can be with the hydrocarbon output to the face of land.Said external fluid can also help to keep or improve the pressure in the stratum.
A kind of form of hydrocarbon secondary recovery is water filling.In water filling, the water filling compsn is taken as external fluid and is expelled in the stratum.Said water filling compsn comprises water and a kind of or more kinds of other materials usually, and said a kind of or more kinds of other materials is the character that said water filling compsn provides expectation.Thereby these other materials can comprise thickening material and reduce the mobility of water filling compsn through the stratum with the viscosity that improves the water filling compsn.The thickening material that is suitable for the water filling compsn is generally polymkeric substance, and the result uses the water filling of the water filling compsn that comprises thickening material to be sometimes referred to as the polymkeric substance perfusion.
The fluidic mobility is defined as the ratio of (medium that fluid passed through) rate of permeation and (said fluidic) viscosity.Therefore, mobility is the function of the character of fluidic character and fluid place environment.
Hydrocarbon in the stratum is hidden (hydrocarbon deposit) can show higher relatively viscosity and relatively low mobility.If compare with the hydrocarbon Tibetan; The water filling compsn has relatively low viscosity and higher relatively mobility; Then the water filling compsn possibly tend to move through hydrocarbon and hide perhaps bypassed hydrocarbon Tibetan, makes and can't effectively hydrocarbon be hidden to one or more recovery well displacement through the water filling compsn.
This phenomenon is called as " fingering ", and causes the reduction of " sweep efficiency " in the water filling program.Sweep efficiency is defined as the ratio of the volume that the stratum can contact with the water filling compsn in the water filling program with the volume of water filling compsn actual contact and stratum in the water filling program.
Through comprising that in the water filling compsn thereby thickening material improves the mobility of the viscosity reduction water filling compsn of water filling compsn through the stratum, can reduce fingering thus and improve sweep efficiency.
United States Patent(USP) No. 4,529,523 (Landoll) described use the water filling medium be used to strengthen the water flood that recovers the oil from the stratum of containing oil, said water filling medium comprises thickening material and can comprise the compatibility table surface-active agent.
The patent of Landoll propose to limit the water filling program validity problem comprise the persistence shortage when not miscible property and the water filling medium of high mobility, water filling compsn and the oil of water filling medium are exposed to salt/salt solution, shearing force, heat and/or biological activity.These problems of in the patent of Landoll, mentioning will overcome through the water filling medium that use contains as the water-soluble polymers of the hydrophobically modified of thickening material.
In the patent of Landoll, thickening polymer comprises polymer backbone, and said polymer backbone can be any non-ionic water-soluble polymer, comprise gather (acrylic amide), ether of cellulose, gather (ethylene oxide), natural polysaccharide glue and gather (vinyl alcohol).The nonionic characteristic of said skeleton it is said that to improving the salt tolerance be important.The molecular weight of feasible polymkeric substance is about 50,000 to 1,000,000 in the patent of Landoll.Preferred molecular weight is about 150,000 to about 800,000 in the patent of Landoll.
Polymer backbone in the patent of Landoll is modified through introducing a spot of long chain alkyl group.It is said that in the patent of Landoll, alkyl-modified dose contains usually and have an appointment 8 to about 25 carbon, preferably contains about 16 to 25 carbon.It is said that alkyl-modified dose amount is that 0.2 weight % is the amount less than 1% to the solubleness that makes polymkeric substance in water, the about 0.2 weight % that perhaps is said polymkeric substance is to about 2.0 weight %.
It is said that in the patent of Landoll the concentration of polymkeric substance in the water filling compsn is about 0.01 weight % to 2.0 weight %, be preferably about 0.1 weight % to 0.5 weight %.
In the patent of Landoll, preferred polymkeric substance is the hydroxy ethyl cellulose of hydrophobically modified, and wherein the length of alkyl chain properties-correcting agent is about 8 to about 25 carbon atoms.
In the patent of Landoll; It is said that the water-soluble polymers of the non-ionic hydrophobic modification in the patent of Landoll is particularly suitable for polymkeric substance-water perfusion medium; Because they have surfactivity, this can reduce or eliminate the use to independent tensio-active agent in the water filling program.
Yet except the water filling compsn that shows proper viscosity and mobility was provided, another purpose in preparation water filling compsn provided the water filling compsn that can inject through the stratum.If the water filling compsn can not cause obvious obstruction to the stratum through the stratum, then said water filling compsn is injectable.
Can not show enough syringeabilities if show the water filling compsn of suitable viscosity and mobility, then possibly be not suitable for as the water filling compsn.The syringeability of water filling compsn it seems a factor that will solve in the patent that is not Landoll.
Summary of the invention
Mention that in this article the lower limit of size, orientation, operating parameters, scope, scope and the upper limit of scope are not in order strict boundary to be provided for scope of the present invention; But should it be interpreted as " approximately ", the meaning of " pact " or " basically " in the scope of the instruction of this paper, unless expressly stated otherwise.
The present invention relates to the method for hydrocarbon secondary recovery, said method comprises makes the water filling compsn through containing the stratum that hydrocarbon is hidden.The present invention relates more specifically to the improvement of the composition of water filling compsn.
Water filling compsn of the present invention comprises water and thickening polymer.Wherein, said thickening polymer comprises hydroxy ethyl cellulose skeleton polymer and hydrophobically modified agent, and the molecular weight of said hydroxy ethyl cellulose skeleton polymer is about 1,000,000 to about 2,000,000, and said hydrophobically modified agent comprises the material based on alkyl hydrocarbon.
Said hydroxy ethyl cellulose skeleton polymer can be called " HEC ".Said thickening polymer can be called HEC or " HMHEC " of hydrophobically modified.
Said hydroxy ethyl cellulose skeleton polymer has hydroxyethyl molar substitution or " MS ", is the mole MV that the Mierocrystalline cellulose of every glucose anhydride unit is introduced the hydroxyethyl in the said polymkeric substance.In some embodiments, the MS of said hydroxy ethyl cellulose skeleton polymer is at least about 0.5.In some embodiments, the MS of said hydroxy ethyl cellulose skeleton polymer is at least about 1.In some embodiments, the MS of said hydroxy ethyl cellulose skeleton polymer is at least about 2.In some embodiments, the MS of said hydroxy ethyl cellulose skeleton polymer is about 2 to about 2.5.In some embodiments, the MS of said hydroxy ethyl cellulose skeleton polymer is about 2.5.
In some embodiments, said hydroxy ethyl cellulose skeleton polymer can comprise the combination of different hydroxy ethyl cellulose (HEC) polymkeric substance.
The said material based on alkyl hydrocarbon of said hydrophobically modified agent can comprise any alkyl and/or substituted alkyl or comprise alkyl and/or any combination of substituted alkyl.In some embodiments, the said material based on alkyl hydrocarbon of said hydrophobically modified agent can comprise a kind of or more kinds of alkyl and/or substituted alkyl, and said alkyl or substituted alkyl contain has an appointment 10 to about 24 unsubstituted carbon atom/groups.In some embodiments, the said material based on alkyl hydrocarbon of said hydrophobically modified agent can comprise a kind of or more kinds of alkyl and/or substituted alkyl, and said alkyl or substituted alkyl contain has an appointment 12 to about 18 unsubstituted carbon atom/groups.
" unsubstituted carbon atom " in this use is meant only direct and hydrogen and/or carbon bonded carbon atom.
Water filling compsn of the present invention can further comprise other materials except water and said thickening polymer.As the indefiniteness example; Can there be (promptly contain and be not more than about 10% sodium-chlor and/or other equivalent monovalent metal salts) with salt solution (brine) form in said water in said water filling compsn, exist as the form of kieserohalosylvite water (hard brine) (promptly contain and be not more than about 0.4% divalence and/or polyvalent metal ion for example calcium or magnesium), and/or can contain other materials or impurity.Said water filling compsn can also further comprise other materials with the performance that improves said water filling compsn or the validity of said water filling program.
Water filling compsn of the present invention is formulated into to have and the viscosity of intending the hydrocarbon Tibetan of using water flood production and/or compatible viscosity and/or the mobility of mobility.
Be meant dynamic viscosity and with (Pa.s) unit representation pascal-second under the condition in the shearing force of about 7/s to 10/s in " viscosity " of this use.In " rate of permeation " of this use with darcy (D) unit representation." mobility " in this use is the ratio of rate of permeation and viscosity, and wherein, rate of permeation is with darcy (D) unit representation, and viscosity is with in pascal-second (Pa.s) unit representation of about 7/s to the condition of the shearing force of about 10/s.
In some embodiments, if the viscosity of water filling compsn for about 2mPa.s to about 100mPa.s, then can think the viscosity of said water filling compsn and the viscosity compatibility of hydrocarbon Tibetan.In some embodiments, if the viscosity of water filling compsn for about 5mPa.s to about 50mPa.s, then can think the viscosity of said water filling compsn and the viscosity compatibility of hydrocarbon Tibetan.In some embodiments, if the viscosity of water filling compsn for about 5mPa.s to about 40mPa.s, then can think the viscosity of said water filling compsn and the viscosity compatibility of hydrocarbon Tibetan.
In some embodiments, if the ratio of the mobility that the mobility of water filling compsn and hydrocarbon are hidden is no more than 100: 1, then can think the mobility compatibility that mobility and the said hydrocarbon of said water filling compsn hidden.In some embodiments, if the ratio of the mobility that the mobility of water filling compsn and hydrocarbon are hidden is no more than 50: 1, then can think the mobility compatibility that mobility and the said hydrocarbon of said water filling compsn hidden.In some embodiments, if the ratio of the mobility that the mobility of water filling compsn and hydrocarbon are hidden is no more than 10: 1, then can think the mobility compatibility that mobility and the said hydrocarbon of said water filling compsn hidden.In some embodiments, if the ratio of the mobility that the mobility of water filling compsn and hydrocarbon are hidden is no more than 2: 1, then can think the mobility compatibility that mobility and the said hydrocarbon of said water filling compsn hidden.
Also water filling compsn of the present invention is mixed with and is expelled to plan and carries out therein in the stratum of water flood.Usually, if the water filling compsn can enough not cause obvious obstruction to the stratum through the stratum, can think that then said water filling compsn can be injected in the stratum.When a kind of or more kinds of composition of said water filling compsn separates and after said water filling compsn is through said stratum, remains in this stratum, may cause the obstruction on stratum from said water filling compsn in the water filling program.
The obstruction on stratum can be by the reduction of said water filling compsn viscosity of this water filling compsn when the stratum or the reduction indication of the concentration of thickening polymer in this water filling compsn during through the stratum by said water filling compsn.The reduction indication of the rate of permeation on this stratum when the obstruction on stratum can also be passed through the stratum by said water filling compsn.
In some embodiments, the syringeability of water filling compsn can be estimated through permeability test medium (permeable test medium) through making the water filling compsn.In some embodiments, the syringeability of water filling compsn can be through considering that this water filling compsn is through estimating with performance afterwards before the said permeability test medium.In some embodiments, the syringeability of water filling compsn can be estimated at the upstream extremity place of said permeability test medium with in the performance of the downstream end of said permeability test medium through considering this water filling compsn.In some embodiments, the syringeability of water filling compsn can through consider this water filling compsn through before the said permeability test medium, during and/or the rate of permeation of said afterwards permeability test medium estimate.
Said water filling compsn has initial viscosity at the upstream extremity place of said permeability test medium, and has final viscosity in the downstream end of said permeability test medium.In some embodiments, the syringeability of said water filling compsn can be estimated according to the said initial viscosity of said water filling compsn and the said final viscosity of said water filling compsn.In some embodiments, if said water filling compsn at said final viscosity greater than 90% of the said initial viscosity in the said water filling compsn, can think that then said water filling compsn is injectable.
Said thickening polymer is in the said water filling compsn at the upstream extremity of said permeability test medium can have starting point concentration, and in said water filling compsn, has ultimate density in the downstream end of said permeability test medium.In some embodiments, the syringeability of said water filling compsn can be estimated according to the said starting point concentration of said thickening polymer and the said ultimate density of said thickening polymer.In some embodiments; If the said ultimate density of said thickening polymer in said water filling compsn greater than 90% of the said starting point concentration of said thickening polymer in said water filling compsn, can think that then said water filling compsn is injectable.
In some embodiments; The performance of said permeability test medium can be chosen as the feasible simulation that provides the performance on the stratum that can use said water filling compsn, and/or can be chosen as and make them rule of thumb or adopt other modes can be related with the performance on said stratum.
In some embodiments, said permeability test medium has specific size and/or performance.For example, in some embodiments, said permeability test medium can have the rate of permeation less than 10 darcies.For example, in some embodiments, said permeability test medium can have and is about 10 centimetres the length between said upstream extremity and said downstream end.
As stated, water filling compsn of the present invention can be mixed with has the viscosity and/or the compatible viscosity and/or the mobility of mobility of hiding with the hydrocarbon that intend to use this water flood to produce, and is mixed with and can be expelled to plan and carries out therein in the stratum of water flood.
Confirmed as and realized that the compatibility of hiding with hydrocarbon depends on the composition of a kind of or more kinds of molecular weight of hydroxy ethyl cellulose skeleton polymer, said hydrophobically modified agent, said hydrophobically modified agent substitution value level and the concentration of said thickening polymer in said water filling compsn in said thickening polymer with being expelled to the syringeability in the stratum to the preparation that the water filling compsn carries out.
Observe,, tend to rise and the mobility of water filling compsn is tended to descend according to the viscosity of water filling compsn of the present invention along with the raising of the molecular weight of said hydroxy ethyl cellulose skeleton polymer.Also observe according to the syringeability of water filling compsn of the present invention and it seems the molecular weight that is not to depend on significantly said hydroxy ethyl cellulose skeleton polymer.
Observed increase, tended to rise and the mobility of water filling compsn is tended to descend according to the viscosity of water filling compsn of the present invention along with the quantity of unsubstituted carbon atom in the said hydrophobically modified agent.Also observe according to the syringeability of water filling compsn of the present invention along with the minimizing of the quantity of the unsubstituted carbon atom in the said hydrophobically modified agent is tended to descend.
Observed increase, tended to rise and the mobility of water filling compsn is tended to descend according to the viscosity of water filling compsn of the present invention along with the substitution value level of said hydrophobically modified agent in said thickening polymer.Also observe according to the syringeability of water filling compsn of the present invention along with the increase of the substitution value level of said hydrophobically modified agent in said thickening polymer is tended to descend.
Observed the increase along with the concentration of said thickening polymer in water filling compsn according to the present invention, the viscosity of said water filling compsn is tended to rise and the mobility of water filling compsn is tended to descend.Also observe according to the syringeability of water filling compsn of the present invention along with the increase of the concentration of said thickening polymer in said water filling compsn is tended to descend.
In water filling compsn of the present invention, exist the material except water and said thickening polymer can also influence the mobility of said water filling compsn and their syringeability.Through the indefiniteness example, the said water in water filling compsn of the present invention can exist and/or exist as kieserohalosylvite water with the salt solution form.
If the said water of having observed in water filling compsn of the present invention exists with the salt solution form and/or exists as kieserohalosylvite water, the viscosity of then said water filling compsn is tended to mobility higher and the water filling compsn and is tended to lower (comparatively purified situation property being compared with the said water in water filling compsn of the present invention).It is believed that this phenomenon owing to have in the said water of said thickening polymer of the present invention because of said water filling compsn that ion causes intramolecularly and the enhancing of intermolecular association (as mentioned below).
Said thickening polymer of the present invention can be referred to as the Mierocrystalline cellulose association polymer.In this base polymer, viscosity/mobility it is believed that with syringeability and depends at least two kinds of different mechanisms of action.First kind of mechanism of action is " entanglement ", it is believed that this mainly owing to the molecular weight of said skeleton polymer, and said entanglement increases along with the increase of the molecular weight (thereby being its length) of said skeleton polymer.
Second kind of mechanism of action is " association ", and this is owing to the existence and the hydrophobicity thereof of said hydrophobically modified agent.Do not hope to receive theoretical constraint, it is believed that a plurality of groups effect or " association " mutually in the individual molecule of thickening polymer and between the adjacent molecule of thickening polymer of said hydrophobically modified agent.
The increase of the quantity of the unsubstituted carbon atom that is provided along with said hydrophobically modified agent is risen according to the degree of association of water filling compsn of the present invention." size " that can be through increasing said hydrophobically modified agent, increase said hydrophobically modified agent in said thickening polymer the substitution value level and/or increase the concentration of said thickening polymer in said water filling compsn, increase the quantity of unsubstituted carbon atom.Along with the increase of degree of association, the viscosity of water filling compsn increases, and the mobility of said water filling compsn descends, and the syringeability of said water filling compsn reduces.
As stated, the molecular weight of said hydroxy ethyl cellulose skeleton polymer it seems does not influence the syringeability of said water filling compsn significantly.
The result; Although depend on the molecular weight of said hydroxy ethyl cellulose skeleton polymer and depend on the degree of association of said water filling compsn according to the viscosity of water filling compsn of the present invention and mobility, mainly depend on the degree of association of said water filling compsn according to the syringeability of water filling compsn of the present invention.
These phenomenons help preparing water filling compsn of the present invention, and said water filling compsn provides the suitable viscosity and/or the mobility of this water filling compsn, keep the syringeability of said water filling compsn simultaneously.
For example, with United States Patent(USP) No. 4,529; The instruction of 523 (Landoll) is compared, and water filling compsn of the present invention adopts the higher relatively skeleton polymer of molecular weight, and (molecular weight is 1,000; 000 to 2,000,000; Be different from fully limit in the patent of Landoll 50,000 to 1,000; 000 molecular weight ranges) improve the viscosity of said water filling compsn and reduce the mobility of said water filling compsn, the degree of association that adopts the appropriateness that is derived from said hydrophobically modified agent simultaneously is the syringeability that does not have the said water filling compsn of excessive influence so that the advantageous effects that has said hydrophobically modified agent to be provided.
Result as above explanation; In some embodiments, the present invention relates to the method for hydrocarbon secondary recovery, said method comprises makes the water filling compsn through containing the stratum that hydrocarbon is hidden; Wherein said method is characterised in that; Said water filling compsn comprises water and thickening polymer, the concentration of said thickening polymer be about 0.01 weight % of said water filling compsn to about 1 weight %, said thickening polymer comprises:
(a) hydroxy ethyl cellulose skeleton polymer, the molecular weight of said hydroxy ethyl cellulose skeleton polymer are about 1,000,000 to about 2,000,000; With
(b) hydrophobically modified agent; The substitution value level of said hydrophobically modified agent in said thickening polymer is that about 0.1 weight % of said thickening polymer is to about 2 weight %; Wherein, said hydrophobically modified agent comprises and contains 10 materials based on alkyl hydrocarbon to about 24 unsubstituted carbon atom/groups of having an appointment.
Wherein, said water filling compsn is formulated into the viscosity with 2mPa.s to 100mPa.s and can be expelled in the said stratum.
Result as above explanation; In some embodiments, the present invention relates to a kind of water filling preparation of compositions method of in hydrocarbon secondary recovery method, using, said secondary recovery method comprises makes said water filling compsn through containing the stratum that hydrocarbon is hidden; Wherein, said preparation method comprises:
(a) select the hydroxy ethyl cellulose skeleton polymer, the molecular weight of said hydroxy ethyl cellulose skeleton polymer is 1,000,000 to 2,000,000;
(b) select the hydrophobically modified agent, said hydrophobically modified agent comprises the material based on alkyl hydrocarbon that contains 10 to 24 unsubstituted carbon atom/groups;
(c) thickening polymer is provided; Said thickening polymer comprises said hydroxy ethyl cellulose skeleton polymer and said hydrophobically modified agent, and the substitution value level of said hydrophobically modified agent in said thickening polymer is 0.1 weight % to 2 weight % of said thickening polymer; With
(d) said thickening polymer and water are made up so that said water filling compsn to be provided, wherein, the concentration of said thickening polymer is 0.1 weight % to 1 weight % of said water filling compsn;
Wherein, the viscosity of said water filling compsn is 2mPa.s to 100mPa.s and can be expelled in the said stratum.
In some embodiments, the molecular weight of said hydroxy ethyl cellulose skeleton polymer can be about 1,300,000.
In some embodiments, the concentration of said thickening polymer in said water filling compsn can be about 0.05 weight % to 0.25 weight % of said water filling compsn.In some embodiments, the concentration of said thickening polymer in said water filling compsn can for about 0.05 weight % to about 0.2 weight %.In some embodiments, the concentration of said thickening polymer in said water filling compsn can be about 0.2 weight %.
In some embodiments, the said material based on alkyl hydrocarbon of said hydrophobically modified agent can contain and has an appointment 12 to about 18 unsubstituted carbon atom/groups.In some embodiments, the said material based on alkyl hydrocarbon of said hydrophobically modified agent can comprise multiple material.In some embodiments, the said material based on alkyl hydrocarbon of said hydrophobically modified agent can comprise dodecyl tetradecyl glycidyl ether.
The substitution value level of said hydrophobically modified agent in said thickening polymer in this use can be calculated through following method: utilize diacetyl oxide that hydroxyl is carried out acetylize; Use proton nuclear magnetic resonance (proton N MR or H NMR) technical Analysis reaction product, and compose ethanoyl CH according to NMR 3With hydrophobically modified agent CH 2Quadrature in the peak.The ratio at these two peaks is represented the substitution value level of said hydrophobically modified agent in said thickening polymer.The thickening polymer of higher molecular weight can utilize the UW effect to carry out partly hydrolysed before the acetylize, with the molecular weight that reduces them and they are at deuterochloroform (CDCl 3) in final viscosity analyze to carry out NMR.
In some embodiments, the said substitution value level of said hydrophobically modified agent in said thickening polymer can for about 0.1 weight % of said thickening polymer to about 1.5 weight %.In some embodiments, the said substitution value level of said hydrophobically modified agent in said thickening polymer can for about 0.4 weight % of said thickening polymer to about 1.2 weight %.In some embodiments, the said substitution value level of said hydrophobically modified agent in said thickening polymer can for about 0.7 weight % of said thickening polymer to about 1.2 weight %.
In some embodiments, the said water of said water filling compsn can comprise salt brine solution.In some embodiments, said salt brine solution can comprise sodium-chlor.In some specific embodiments, the concentration of said salt brine solution can be about 1 weight % of said salt brine solution.
In a specific embodiment; The molecular weight of said hydroxy ethyl cellulose skeleton polymer can be about 1; 300; 000; The said material based on alkyl hydrocarbon of said hydrophobically modified agent can comprise dodecyl tetradecyl glycidyl ether, the said substitution value level of said hydrophobically modified agent can for about 0.7 weight % of said thickening polymer to about 1 weight %, and the concentration of said thickening polymer in said water filling compsn can be about 0.2 weight % of said water filling compsn.In this specific embodiment, the said water of said water filling compsn can comprise salt brine solution.In this specific embodiment, said salt brine solution can contain the sodium-chlor of the 1 weight % that accounts for said salt brine solution.
Description of drawings
Hereinafter will be with reference to description of drawings embodiment of the present invention, wherein:
Fig. 1 sums up various thickening polymers and the composition of water filling compsn and the table of performance.
Fig. 2 is the said water filling compsn among Fig. 1 carries out filtering filtration test result through Whatman#1 strainer and layer of sand (sandpad) a table.
Fig. 3 sums up the table to the performance of the layer of sand rock core (sandpack core) of the selected water filling compsn of Fig. 1 be used for carrying out rock core displacement (coreflood) test.
Fig. 4 sums up the table to the performance of the oil of the selected water filling compsn of Fig. 1 be used for carrying out coreflooding experiment.
Fig. 5 sums up to use the selected water filling compsn of Fig. 1 to carry out the result's of coreflooding experiment table.
Fig. 6 is the synoptic diagram that is used for carrying out the equipment of the layer of sand filtration test of in Fig. 2, summing up.
Fig. 7 is the synoptic diagram that is used for carrying out the equipment of the coreflooding experiment of in Fig. 5, summing up.
Fig. 8 is the graphic representation that the data that from coreflooding experiment, obtain are shown, and said coreflooding experiment has compared the injection pressure (kPa) of passing through the function of amount (pore volume (PV)) from the conduct of the HPAM of Fig. 1 and HMHEC 1206 water filling compsns.
Fig. 9 is the graphic representation that the data that from coreflooding experiment, obtain are shown, and said coreflooding experiment has compared the injection pressure (kPa) of passing through the function of amount (pore volume (PV)) from the conduct of the HPAM of Fig. 1 and HMHEC 0603 water filling compsn.
Figure 10 is the graphic representation that the data that from coreflooding experiment, obtain are shown, and said coreflooding experiment has compared the tar productivity (per-cent of OOIP (OOIP)) of the conduct of HPAM, HMHEC 1206 and HMHEC 0603 water filling compsn from Fig. 1 through the function of amount (pore volume (PV)).
Figure 11 is the graphic representation that the data that from the layer of sand filtration test, obtain are shown; Said layer of sand filtration test compared the selected water filling compsn of Fig. 1 as the virtual viscosity (mPa.s) in the layer of sand of the function of linear velocity (foot/sky), wherein the aqueous components of water filling compsn comprises 1% NaCl.
Figure 12 is the graphic representation that the data that from the layer of sand filtration test, obtain are shown; Said layer of sand filtration test compared the selected water filling compsn of Fig. 1 as the virtual viscosity (mPa.s) in the layer of sand of the function of linear velocity (foot/sky), wherein the aqueous components of water filling compsn comprises 1% NaCl or kieserohalosylvite water.
Embodiment
The present invention relates to the method for hydrocarbon secondary recovery, said method comprises makes the water filling compsn through containing the stratum that hydrocarbon is hidden.Making the water filling compsn is that hydrocarbon is hidden to one or more recovery well displacement that is communicated with said resident fluid through a purpose on the stratum containing hydrocarbon and hide.
The result; Said method comprises that typically the water filling compsn is expelled to one or more recovery well (and it separates with said recovery well) that is communicated with said resident fluid makes that when the water filling compsn passes through said stratum the water filling compsn can be hidden hydrocarbon to the recovery well displacement.
Said method may further include and makes the water filling compsn through before the said stratum and/or other steps or the program of carrying out afterwards.
The present invention particularly relates to the preparation of water filling compsn; This preparation obtains having the viscosity compatible with intending viscosity that the hydrocarbon produced from the stratum hides and/mobility and/or the water filling compsn of mobility, and has obtained thus being expelled to the water filling compsn in the stratum.
Water filling compsn of the present invention comprises water and thickening polymer.Said thickening polymer comprises hydroxy ethyl cellulose skeleton polymer and hydrophobically modified agent.Said hydrophobically modified agent comprises the material based on alkyl hydrocarbon.Water filling compsn of the present invention can further comprise other materials and/or material.
The preparation of water filling compsn of the present invention is based on a variety of factors.
The first, the preparation of water filling compsn of the present invention is based on intending that the hydrocarbon from the stratum, produce is hidden factor and based on the mobility of water filling compsn, and this mobility must realize so that the mobility compatibility that the mobility of water filling compsn and hydrocarbon are hidden.
Usually, the ratio of the mobility that the mobility of water filling compsn and hydrocarbon are hidden is not more than about 100: 1, more preferably no more than about 50: 1, further preferably is not more than about 10: 1, and then more preferably no more than about 2: 1.
Hide for the hydrocarbon that much comprises oil, the viscosity of water filling compsn is preferably about 2mPa.s to about 100mPa.s, and more preferably about 5mPa.s is to about 50mPa.s; And then more preferably about 5mPa.s is to about 40mPa.s.
The second, the preparation of water filling compsn of the present invention also will guarantee that the water filling compsn should be expelled in the stratum based on the character factor on stratum.
Usually, if the water filling compsn does not cause tangible obstruction to the stratum through the stratum, can think that then the water filling compsn is injectable.
Can during carrying out water flood, estimate the syringeability of water filling compsn, perhaps use the water filling compsn to carry out water flood is estimated the water filling compsn before through detection water filling compsn syringeability.No matter be which kind of situation, the composition on the stratum that the sign of syringeability or the shortage of syringeability all possibly passed through with the composition of water filling compsn or character and/or water filling compsn or the variation of character are relevant.
Being used for comprising in a kind of method of using the water filling compsn to detect the water filling compsn before carrying out water flood makes the water filling compsn through the permeability test medium.
A kind of suitable permeability test medium is the layer of sand with upstream extremity and downstream end.A kind of suitable detection method is the layer of sand filtering technique.The layer of sand that this layer of sand filtering technique uses preferably has the initial rate of permeation that is lower than about 10 darcies, makes it become the reasonable representative on stratum.In a kind of test configurations, layer of sand has the initial rate of permeation of about 3 darcies.In a kind of test configurations, layer of sand has about 10 centimetres length from upstream extremity to downstream end.
The program that in layer of sand, detects the water filling compsn be included in constant or the pressure that changes and/or flow conditions under make the water filling compsn pass through layer of sand.
The water filling compsn will show the starting point concentration of thickening polymer at the upstream extremity place of layer of sand, and will show the ultimate density of thickening polymer in the downstream end of layer of sand.If the ultimate density of thickening polymer, then can be indicated the shortage of syringeability of potential obstruction and the water filling compsn of the delay of thickening polymer in layer of sand, layer of sand less than the initial concentration of thickening polymer.
Usually, in the layer of sand test, be considered to injectable in order to make the water filling compsn, the ultimate density of thickening polymer in the water filling compsn should be greater than 90% of the initial concentration of thickening polymer in the water filling compsn.
The water filling compsn will show initial viscosity at the upstream extremity place of layer of sand, and will show final viscosity in the downstream end of layer of sand.If said final viscosity, then can be indicated the shortage of syringeability of potential obstruction and the water filling compsn of the delay of thickening polymer in layer of sand, layer of sand less than said initial viscosity.
Usually, in layer of sand test, be considered to injectable in order to make the water filling compsn, the final viscosity of water filling compsn should be greater than 90% of the initial viscosity of water filling compsn.
The 3rd, the preparation of water filling compsn of the present invention is based on the factor of the influence of the following variable relevant with syringeability with the viscosity/mobility of water filling compsn:
1. the molecular weight of hydroxy ethyl cellulose skeleton polymer;
2. the composition of hydrophobically modified agent;
3. the substitution value level of hydrophobically modified agent in thickening polymer; With
4. the concentration of thickening polymer in the water filling compsn.
The 4th, the preparation of water filling compsn of the present invention is based on the salt that possibly expose the water filling compsn and/or the factor of salt water condition, and this condition stems from the water of preparation water filling compsn or the environment that the water filling compsn possibly expose.
Thickening polymer of the present invention can be referred to as the Mierocrystalline cellulose association polymer.According to the preparation of water filling compsn of the present invention factor based on the relevant theory of the mechanism of action that possibly rely on the viscosity/mobility and the syringeability of water filling compsn.
Particularly, these performances of water filling compsn it is believed that and depend on as " entanglement " of first kind of mechanism of action with as " association " of second kind of mechanism of action.
It is believed that the molecular weight that tangles mainly owing to the hydroxy ethyl cellulose skeleton polymer, and it seems and only influence the viscosity/mobility of water filling compsn.Along with the increase of the molecular weight of hydroxy ethyl cellulose skeleton polymer, the entanglement degree increases, thereby causes increase and the reduction of mobility of the viscosity of water filling compsn.
It is believed that association is owing to the existence of hydrophobically modified agent and hydrophobicity and it seems and influence the viscosity/mobility of water filling compsn and syringeability simultaneously.The increase of the quantity of the unsubstituted carbon atom that is provided along with the hydrophobically modified agent, degree of association increases." size " that can be through increasing the hydrophobically modified agent, increase said hydrophobically modified agent in said thickening polymer the substitution value level and/or increase the concentration of said thickening polymer in said water filling compsn, increase the quantity of the unsubstituted carbon atom that the hydrophobically modified agent provided.
Thereby a purpose preparing water filling compsn of the present invention is the viscosity that increases the water filling compsn reduces mobility, and it is compatible to make said viscosity/mobility and hydrocarbon hide, but makes the water filling compsn in the stratum, keep acceptable syringeability simultaneously.
As stated, it is believed that and to realize that through entanglement that increases thickening polymer and/or the degree of association that increases the water filling compsn viscosity rising/mobility of water filling compsn reduces.But, increase the mobility of viscosity/reductions reduction water filling compsn of water filling compsn through the degree of association that increases the water filling compsn, with the reduction of the syringeability that causes the water filling compsn simultaneously.The mobility that increases the viscosity/reduction water filling compsn of water filling compsn through the entanglement that increases thickening polymer it seems that the syringeability to the water filling compsn does not have remarkable influence.
As a result, can combine to tangle and the associating target viscosities/mobility that is used for realizing the water filling compsn.Along with the increase of entanglement degree, can reduce degree of association to realize target viscosities/mobility.On the contrary, along with the reduction of entanglement degree, must increase degree of association to realize target viscosities/mobility.
Yet every kind of concrete hydrophobically modified agent all shows maximum degree of association, is higher than this maximum degree of association, and the water filling compsn will be an injectable not.More particularly, for any concrete hydrophobically modified agent, increase substitution value level and/or increase thickening polymer the concentration in water filling compsn of this hydrophobically modified agent in thickening polymer and make that exceeding the limit of associating will make not injectable of water filling compsn.
As a result, the association of every kind of concrete hydrophobically modified agent limit will confirm that the target viscosities/mobility that realizes the water filling compsn makes the water filling compsn keep the required minimum entanglement (being the minimum molecular weight of hydroxy ethyl cellulose skeleton polymer) of syringeability simultaneously.
The 5th, the preparation of water filling compsn of the present invention is based on the acquired factor of cost with different hydroxy ethyl cellulose skeleton polymer material standed fors and different hydrophobically modified agent.
Other or other factor can be applied to the related concrete environment of embodiment of the present invention.
Through generalized factor more than considering, confirmed that the molecular weight ranges of the present invention that is suitable for of hydroxy ethyl cellulose skeleton polymer is about 1,000,000 to about 2,000,000.
If the molecular weight of hydroxy ethyl cellulose skeleton polymer is less than about 1,000,000, then the compatible required degree of association of viscosity/mobility in the realization of hydrophobically modified agent and stratum will make not injectable of water filling compsn.
When the molecular weight of hydroxy ethyl cellulose skeleton polymer from 1,000,000 near 2,000,000 o'clock, this skeleton polymer becomes and is difficult to obtain and the cost of this skeleton polymer possibly become expensive.As a result, the actual upper bound of the molecular weight of hydroxy ethyl cellulose skeleton polymer possibly be lower than 2,000,000.In some embodiments, according to acquired and cost, the preferred upper limit of the molecular weight of hydroxy ethyl cellulose skeleton polymer can be about 1,500,000.
Therefore, established and can have the following general policy of hiding compatible viscosity/mobility with hydrocarbon and can be expelled to the preparation of the water filling compsn in the stratum:
(a) molecular weight of hydroxy ethyl cellulose skeleton polymer is about 1,000,000 to about 2,000,000;
(b) the hydrophobically modified agent comprises and contains 10 materials based on alkyl hydrocarbon to about 24 unsubstituted carbon atom/groups of having an appointment, and preferably comprises and contains about 12 materials based on alkyl hydrocarbon to about 18 unsubstituted carbon atom/groups;
(c) the substitution value level of hydrophobically modified agent in thickening polymer is that about 0.1 weight % of said thickening polymer is to about 2 weight %; The about 0.1 weight % that is preferably said thickening polymer is to about 1.5 weight %; The about 0.4 weight % that further is preferably said thickening polymer is to about 1.2 weight %, and more preferably about 0.7 weight % of said thickening polymer is to about 1.2 weight %; With
(d) concentration of said thickening polymer in said water filling compsn be about 0.01 weight % of said water filling compsn to about 1 weight %, about 0.05 weight % of more preferably said water filling compsn is to about 0.25 weight %.
Preferably the water filling compsn is prepared in the above scope that provides to realize the target viscosities of about 2mPa.s to about 100mPa.s; Preferably to realize the target viscosities of about 5mPa.s to about 50mPa.s; More preferably realizing about 5mPa.s, and/or be no more than about 100: 1, more preferably no more than about 50: 1 with the ratio of the mobility of the mobility that realizes the water filling compsn and hydrocarbon Tibetan to the target viscosities of about 40mPa.s; Further preferably be no more than about 10: 1, further preferably be no more than about 2: 1.
The water filling compsn is prepared in the above scope that provides obtaining injectable water filling compsn, as carry out being estimated in the process at water flood or the water filling compsn estimated through detecting before the water filling compsn being used in water flood.
In plurality of applications of the present invention, owing to prepare the water filling compsn according to above scope and target viscosities, thereby can realize the syringeability of water filling compsn.More of the present invention during use, the syringeability of realizing the water filling compsn possibly require in above scope and target viscosities the preparation to the water filling compsn to carry out some changes.
Can use appropriate means to prepare thickening polymer of the present invention, said method is included in United States Patent(USP) No. 4,228,277 (Landoll), United States Patent(USP) No. 4,529,523 described concrete grammars and other currently known methodss of the prior art.
Can prepare water filling compsn of the present invention through thickening polymer and water being mixed and mixing with any other suitable material and/or material.Said water can exist with purified relatively form, exists, exists and/or can contain other materials and/or impurity as kieserohalosylvite water with the brinish form.
Embodiment 1-is by hydroxy ethyl cellulose (HEC) preparation thickening polymer (HMHEC)
Adding 10 gram molecular weights are 1,300,000 hydroxy ethyl cellulose (HEC) in the round-bottomed flask of 500mL, add 1.25 gram dodecyl tetradecyl glycidyl ethers and 87.5 gram Virahols then.Use the nitrogen purging flask then.
Give the flask equipped mechanical stirrer, and the sodium hydroxide (NaOH) that when flask is stirred, will pass through 87.5 grams 1% of nitrogen prepurge joins in the flask.
Use nitrogen simply to purge the viscosity slurry of gained, stirred 5 hours at 60 degrees centigrade then.After 5 hours, in flask, add 2 gram acetate and 100 milliliters of acetone.
After 10 minutes to 15 minutes, the content of flask is transferred in 1 liter of beaker and added about 400 milliliters of acetone when stirring, to precipitate.
The gained material is centrifugal and use 100 milliliters of washing with acetone liquid washed twice.After the dry air, when stirring, add 180 milliliters water, obtain gel.After adding 40 milliliters water in addition and using scraper to stir immediately with material transfer to dialysis tubing.Use Fu Shi conversion infrared spectrum analysis method (FTIR) to confirm removing of acetic acid sodium salt.
With material freeze-drying and grinding, obtain 9 gram thickening polymers then, form by the hydroxy ethyl cellulose (HMHEC) of the hydrophobically modified that is fluffy white solid, this thickening polymer called after HMHEC 0603.
Using similar compound method is 720,000 or 1,000 by molecular weight, and 000 HEC synthesizes other HMHEC thickening polymers, also uses dodecyl tetradecyl glycidyl ether as the hydrophobically modified agent.The name as shown in Figure 1 of these other HMHEC thickening polymers.
Embodiment 2-water filling preparation of compositions
Use the HMHEC thickening polymer of embodiment 1 to prepare multiple different water filling compsn.Use Flopaam TM3630 have prepared other a kind of water filling compsn of naming to HPAM as thickening polymer.Flopaam TMThe 3630th, by a kind of polyacrylamide polymers commonly used in the exploitation of secondary hydrocarbon of SNF Group of Andrezieux (France) manufacturing.
Through thickening polymer and water mixing are prepared the water filling compsn by thickening polymer.Said water provides with purified relatively water, perhaps provides as 1% salt solution (NaCl) solution, and be that 0.38% kieserohalosylvite water (NaCl) provides perhaps as containing 8.5% total dissolved solid and hardness.
The composition and the performance of HMHEC and HPAM water filling compsn are summarised among Fig. 1.
In Fig. 1, notice that the water filling compsn that contains HMHEC 1206 and HMHEC 0603 provides two kinds of different viscosity values in 1%NaCl.First (and being lower) viscosity number derives from the layer of sand filtration test.Second (also being higher) viscosity number derives from coreflooding experiment.Although it is clear that the reason of these data differences does not have, possibly be the thickening polymer (comparing) that the HMHEC 1206 that in the layer of sand filtration test, uses and HMHEC 0603 water filling compsn have in fact contained low concentration with the water filling compsn that in coreflooding experiment, uses.
Embodiment 3-water filling compsn-filtration test
Use one or both filtering techniques in two kinds of filtering techniques that the water filling compsn among embodiment 2 and Fig. 1 is filtered, these two kinds of filtering techniques include and make the water filling compsn through the permeability test medium.
First kind of filtering technique comprises the water filling compsn through Whatman#1 (11 μ m) strainer.Fall so that pressure gradient to be provided in the fine pressure of utilizing pressurized air to apply 100kPa across strainer.
Before filtering with the viscosity of measuring the water filling compsn afterwards to obtain initial viscosity value and final viscosity value.The reduction of the viscosity number of water filling compsn representes that not every thickening polymer all passes through strainer.It should be noted, the concentration of thickening polymer in the water filling compsn has been carried out similar measurement to obtain starting point concentration value and ultimate density value.
Also estimated the filterable of water filling compsn through specific filtration resistance (it has compared in different time filtering speed at interval):
Specific filtration resistance=(filter 23 00 gram time-time of filtrations 200 grams)/(filter 200 grams time-time that filtration 100 restrains)
Specific filtration resistance shows that greater than 1 the perviousness of strainer descends in time, explains that not all thickening polymer all passes through strainer, so blocking filter.
Second kind of filtering technique comprises that to make the water filling compsn be about 10 darcies through rate of permeation and is about 10 centimetres compacted sand layer filtration test rock core from the length of upstream extremity to downstream end.
The synoptic diagram that is used for carrying out the equipment of layer of sand filtration test provides in Fig. 6.
With reference to figure 6, filtration test equipment 20 comprises filtration test rock core 22.Filtration test rock core 22 has upstream extremity 24 and downstream end 26.The upstream extremity 24 of filtration test rock core 22 is communicated with injecting fluid container 28 fluids.Compressed air source 30 is communicated with injecting fluid container 28 fluids.Compressed air source 30 provides the means that the fluid that is contained in the injecting fluid container 28 is pressurizeed.
The downstream end 26 of filtration test rock core 22 is communicated with elute collection container 32 fluids.Use weight that scale 34 measures elute collection containers 32 weight with the fluid elute confirming to discharge from the downstream end 26 of filtration test rock core 22.Being transferred to computingmachine 36 from the data of scale 34 writes down and analyzes.
In second kind of filtering technique, falling of the transmission of measurement water filling compsn from a series of fine pressure of 3.5kPa to 100kPa through filtration test rock core 22.Measure the weight that the water filling compsn of discharging from the downstream end 26 of filtration test rock core 22 flows out thing through scale 34, and through computingmachine 36 with the function of this weight record as the time.
Sample and use the rheometer evaluation at 24 pairs of water filling compsns of upstream extremity of filtration test rock core 22 to obtain the initial viscosity value of water filling compsn.Sample and use the rheometer evaluation at 26 pairs of water filling compsns of downstream end of filtration test rock core 22 to obtain the final viscosity value of water filling compsn.
As adopting first kind of filtering technique, the viscosity degradation of water filling compsn representes that not every thickening polymer all passes through filtration test rock core 22.As adopting first kind of filtering technique, the concentration of thickening polymer in the water filling compsn has been carried out similar measurement to obtain starting point concentration value and ultimate density value.
The filtration test result of two kinds of filtering techniques is provided among Fig. 2.
Embodiment 4-water filling compsn-coreflooding experiment
Water filling compsn to selected quantity carries out coreflooding experiment uses the resulting increase of said water filling compsn with research tar productivity (with respect to the tar productivity of original water filling program acquisition).Usually; Said coreflooding experiment carries out through following mode: at first carry out perfusion of saline to obtain significant water filling value of gathering; Use one of said water filling compsn to carry out water filling, carry out second time perfusion of saline then as expulsion perfusion (chaser flood).The aqueous medium of every kind of water filling compsn all is 1% NaCl salt solution.
The synoptic diagram that is used for carrying out the equipment of said coreflooding experiment is provided among Fig. 7.
With reference to figure 7, coreflooding experiment equipment 50 comprises layer of sand coreflooding experiment rock core 52.Coreflooding experiment rock core 52 has upstream extremity 54 and downstream end 56.The upstream extremity 54 of coreflooding experiment rock core 52 is communicated with pump 58 fluids, and this pump 58 is connected with water filling source 62 with saline source 60.
The downstream end 56 of coreflooding experiment rock core 52 is communicated with back pressure regulator 64 fluids.Back pressure regulator 64 has fluid outlet 66.
Upstream pressure sensor 72 is connected with the upstream extremity 54 of coreflooding experiment rock core 52.Middle reaches pressure transmitter 74 is connected with the mid point of the length of coreflooding experiment rock core 52.
The performance of coreflooding experiment rock core 52 in a lot of tests provides in Fig. 3.For coreflooding experiment, the length of coreflooding experiment rock core 52 is about 30 centimetres.
When carrying out coreflooding experiment, at first use 1% salt solution to make the coreflooding experiment rock core saturated to obtain its salt solution rate of permeation.
Then with oil be expelled to coreflooding experiment rock core 52 with the transportable water of displacement until obtaining across the constant pressure drop of coreflooding experiment rock core 52 and stopping to produce water.The performance of oil provides in Fig. 4.
Measure the oil rate of permeation of coreflooding experiment rock core 52 then.Coreflooding experiment carries out at the pure land static pressure of the 7000kPa constant core temperature at 20 degrees centigrade.
In the upstream extremity 54 of coreflooding experiment rock core 52, carry out the initial saline perfusion through injecting 1% salt solution (NaCl) solution with the constant flow rate of 3.6ml/hr (milliliter/hour).The LV that this flow velocity equals 0.6 foot/day it is believed that it is the representative flow velocity that can anticipate in the typical hydrocarbon-bearing pool away from mine.At downstream end 56 places of coreflooding experiment rock core 52, the sample elute is collected in a series of pipes of weighing in advance with 100 minutes the timed intervals.Through upstream pressure sensor 72 and the pressure drop across coreflooding experiment rock core 52 of pressure transmitter 74 continuous monitorings in middle reaches by the salt brine solution generation of injection.Initial saline perfusion lasts till at least about 1 pore volume (PV) and has been injected in the coreflooding experiment rock core 52.
Then, the water filling compsn is expelled to continuously in the upstream extremity 54 of coreflooding experiment rock core 52, has been injected in the coreflooding experiment rock core 52 until water filling compsn at least about 2 pore volumes (PV).
At last, second part of perfusion of saline thing as expelling thing (chaser) to be expelled to the upstream extremity 54 of coreflooding experiment rock core 52, has been injected in the coreflooding experiment rock core 52 until about 1 pore volume (PV).
The result of coreflooding experiment is summarised among Fig. 5.
Filtration test result and coreflooding experiment result's analysis
With reference to figure 1, to observe when making water prepare the water filling compsn as aqueous medium, the viscosity of HPAM (SEPIGEL 305) water filling compsn is higher than the viscosity when using 1% salt solution (NaCl) or kieserohalosylvite water as aqueous medium very significantly.On the contrary, when using 1% salt solution (NaCl) or kieserohalosylvite water as aqueous medium, the viscosity of HMHEC water filling compsn generally is higher than the viscosity when making water prepare the water filling compsn as aqueous medium.The explanation of this phenomenon, HMHEC water filling compsn are used for the superior persistence (comparing with SEPIGEL 305 water filling compsn) that can show at the oily secondary recovery that saltwater environment carries out.
Still with reference to figure 1; Observe and use molecular weight higher relatively (promptly 1; 300; The HMHEC water filling compsn of 000) HEC skeleton polymer preparation often shows higher relatively viscosity (comparing with the HMHEC water filling compsn that the HEC skeleton polymer that uses molecular weight relatively low (promptly 720,000) prepares) in relatively low hydrophobic substitution value level.This phenomenon proves, uses the relative higher H EC skeleton polymer of molecular weight can realize suitably high viscosity effectively in relatively low substitution value level (thereby degree of association is lower).
Still with reference to figure 1; Observe and use HPAM water filling compsn or HMHEC 0603 water filling compsn realizing the best general effect relevant with syringeability and tar productivity qualitatively, explanation can be adopted the relative higher H EC skeleton polymer of the molecular weight with appropriate hydrophobic substitution value level to overcome by use to have the syringeability problem that the relatively low HEC skeleton polymer of molecular weight of higher hydrophobic substitution value level causes.
With reference to figure 2, observe in layer of sand filtration test HMHEC 0603 water filling compositions table reveal before two pore volumes injections with inject after highly stable consistent viscosity, show and can think that HMHEC 0603 water filling compsn satisfies the syringeability requirement.
With reference to figure 5, observe that HMHEC 0603 water filling compositions table reveals the highest tar productivity (being higher than HPAM water filling compsn a little) in coreflooding experiment, and HMHEC 1206 water filling compositions table reveal much lower tar productivity.In addition, HPAM water filling compsn and HMHEC 0603 keeps before the injection of stable and consistent and injection back viscosity, and the obvious reduction of HMHEC 1206 water filling compsns from showing viscosity after the injection before injecting.This phenomenon explanation, the HMHEC water filling compsn such as the HMHEC 0603 that contain the higher relatively skeleton polymer of molecular weight can provide and the suitable oily secondary recovery result of SEPIGEL 305 (HPAM) water filling compsn.
With reference to figure 8; Observe the water filling compsn that contains the relatively low skeleton polymer of molecular weight such as HMHEC 1206 can show required injection pressure in the water filling program lasting rising, and SEPIGEL 305 (HPAM) water filling compsn can show the required injection pressure of relatively stable unanimity in the water filling program.
With reference to figure 9; Observe the water filling compsn such as the HMHEC 0603 that contain the higher relatively skeleton polymer of molecular weight and in the injecting process, can show required injection pressure, the injection pressure that this injection pressure and SEPIGEL 305 (HPAM) water filling compsn is shown is suitable.
With reference to Figure 10; Observe the water filling compsn that contains the higher relatively skeleton polymer of molecular weight such as HMHEC 0603 and in the injecting process, can show the suitable tar productivity that is shown with SEPIGEL 305 (HPAM) water filling compsn, and the water filling compsn such as the HMHEC 1206 that contain the relatively low skeleton polymer of molecular weight can show obviously lower tar productivity in injection process.
With reference to Figure 11, observe the water filling compsn that comprises 1%NaCl for aqueous medium wherein, SEPIGEL 305 (HPAM) water filling compsn shows the virtual viscosity that the rising with flow velocity increases in the layer of sand test.A kind of explanation of this result is the influence that the transportation of polymers soln in porous medium receives shearing force and elongation viscosity simultaneously.Under the situation of HPAM water filling compsn, its elongation viscosity obviously increases when high flow rate, causes higher effective viscosity.Still with reference to Figure 10, observe the water filling compsn that comprises 1%NaCl for aqueous medium wherein, HMHEC water filling compsn often shows the virtual viscosity of relatively stable unanimity in the flow rates of being studied in the layer of sand filtration test.
With reference to Figure 12, observe the water filling compsn that contains the higher relatively skeleton polymer of molecular weight (HMHEC 0318 and HMHEC 0603) that aqueous medium wherein comprises the kieserohalosylvite aqueous solution and in the layer of sand filtration test, show higher effective viscosity (comprising comprising the virtual viscosity that the water filling compsn of HMHEC 0318 or HMHEC 0603 shown with higher relatively thickening polymer concentration (being 2000ppm) and comparing of 1%NaCl) with aqueous medium wherein in relatively low thickening polymer concentration (promptly less than 2000ppm).
In a word; Contain the higher relatively skeleton polymer of molecular weight and (be at least about 1; 000; 000) and the HMHEC water filling compsn of substitution value with hydrophobically modified agent of appropriateness the performance (with syringeability and tar productivity relevant) suitable with HPAM (SEPIGEL 305) water filling compsn of water filling compsn can be provided, and this performance is superior to the performance (relevant with persistence) of HPAM (SEPIGEL 305) water filling compsn under the situation of saltwater environment existence.
In this article, word " comprises " expression with being used for indefiniteness and comprises this word object afterwards, but does not have to get rid of the object of specifically not mentioning.The indefinite article " a " of mentioning an element is not got rid of the possibility that exists more than this element, have and have only this element only if linguistic context explicitly calls for.

Claims (45)

1. hydrocarbon secondary recovery method; Said method comprises makes the water filling compsn through containing the stratum that hydrocarbon is hidden; Said method is characterised in that; Said water filling compsn comprises water and thickening polymer, and the concentration of said thickening polymer is 0.01 weight % to 1 weight % of said water filling compsn, and said thickening polymer comprises:
(a) hydroxy ethyl cellulose skeleton polymer, the molecular weight of said hydroxy ethyl cellulose skeleton polymer are 1,000,000 to 2,000,000; With
(b) hydrophobically modified agent; The substitution value level of said hydrophobically modified agent in said thickening polymer is 0.1 weight % to 2 weight % of said thickening polymer; Wherein, said hydrophobically modified agent comprises the material based on alkyl hydrocarbon that contains 10 to 24 unsubstituted carbon atom/groups.
Wherein, said water filling compsn is formulated into the viscosity with 2mPa.s to 100mPa.s and can be expelled in the said stratum.
2. method according to claim 1, wherein, the concentration of said thickening polymer in said water filling compsn is 0.05 weight % to 0.25 weight % of said water filling compsn.
3. method according to claim 2, wherein, the said material based on alkyl hydrocarbon of said hydrophobically modified agent contains 12 to 18 unsubstituted carbon atom/groups.
4. method according to claim 3, wherein, the said substitution value level of said hydrophobically modified agent in said thickening polymer is 0.1 weight % to 1.5 weight % of said thickening polymer.
5. method according to claim 4, wherein, said hydrocarbon is hidden has mobility, and wherein said water filling compsn has mobility, and the ratio of the said mobility of the said mobility of wherein said water filling compsn and said hydrocarbon Tibetan is not more than 100: 1.
6. method according to claim 5; Wherein, Said water filling compsn is suitable for arriving through said permeability test medium from the upstream extremity of permeability test medium the downstream end of said permeability test medium; The initial rate of permeation of wherein said permeability test medium is less than 10 darcies; Make said thickening polymer be in the said water filling compsn and have starting point concentration at the said upstream extremity of said permeability test medium; And the said downstream end at said permeability test medium has ultimate density in said water filling compsn, and makes the said ultimate density of said thickening polymer in said water filling compsn greater than 90% of the said starting point concentration of said thickening polymer in said water filling compsn.
7. method according to claim 6, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 50: 1.
8. method according to claim 7, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 10: 1.
9. method according to claim 8, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 2: 1.
10. method according to claim 5; Wherein, Said water filling compsn is suitable for arriving through said permeability test medium from the upstream extremity of permeability test medium the downstream end of said permeability test medium; The initial rate of permeation of wherein said permeability test medium is less than 10 darcies; Make said water filling compsn have initial viscosity, and have final viscosity, and make the said final viscosity of said water filling compsn greater than 90% of the said initial viscosity of said water filling compsn in the said downstream end of said permeability test medium at the said upstream extremity place of said permeability test medium.
11. method according to claim 10, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 50: 1.
12. method according to claim 11, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 10: 1.
13. method according to claim 12, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 2: 1.
14. method according to claim 4; Wherein, Said water filling compsn is suitable for arriving through said permeability test medium from the upstream extremity of permeability test medium the downstream end of said permeability test medium; The initial rate of permeation of wherein said permeability test medium is less than 10 darcies; Make said thickening polymer be in the said water filling compsn and have starting point concentration at the said upstream extremity of said permeability test medium; And the said downstream end at said permeability test medium has ultimate density in said water filling compsn, and makes the said ultimate density of said thickening polymer in said water filling compsn greater than 90% of the said starting point concentration of said thickening polymer in said water filling compsn.
15. method according to claim 14, wherein, the viscosity of said water filling compsn is 2mPa.s to 50mPa.s.
16. method according to claim 4; Wherein, Said water filling compsn is suitable for arriving through said permeability test medium from the upstream extremity of permeability test medium the downstream end of said permeability test medium; The initial rate of permeation of wherein said permeability test medium is less than 10 darcies; Make said water filling compsn have initial viscosity, and have final viscosity, and make the said final viscosity of said water filling compsn greater than 90% of the said initial viscosity of said water filling compsn in the said downstream end of said permeability test medium at the said upstream extremity place of said permeability test medium.
17. method according to claim 16, wherein, the viscosity of said water filling compsn is 2mPa.s to 50mPa.s.
18. method according to claim 4, wherein, the molecular weight of the said hydroxy ethyl cellulose skeleton polymer of said water filling compsn is 1,300,000.
19. method according to claim 18, wherein, said hydrocarbon is hidden has mobility, and wherein said water filling compsn has mobility, and the ratio of the said mobility of the said mobility of wherein said water filling compsn and said hydrocarbon Tibetan is not more than 100: 1.
20. method according to claim 19, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 50: 1.
21. method according to claim 20, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 10: 1.
22. method according to claim 21, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 2: 1.
23. method according to claim 18, wherein, the viscosity of said water filling compsn is 2mPa.s to 50mPa.s.
24. method according to claim 4, wherein, the said material based on alkyl hydrocarbon of said hydrophobically modified agent comprises dodecyl tetradecyl glycidyl ether.
25. method according to claim 24, wherein, said hydrocarbon is hidden has mobility, and wherein said water filling compsn has mobility, and the ratio of the said mobility of the said mobility of wherein said water filling compsn and said hydrocarbon Tibetan is not more than 100: 1.
26. method according to claim 25, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 50: 1.
27. method according to claim 26, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 10: 1.
28. method according to claim 27, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 2: 1.
29. method according to claim 24, wherein, the viscosity of said water filling compsn is 2mPa.s to 50mPa.s.
30. method according to claim 4, wherein, the said substitution value level of said hydrophobically modified agent in said thickening polymer is 0.7 weight % to 1 weight % of said thickening polymer.
31. method according to claim 30, wherein, said hydrocarbon is hidden has mobility, and wherein said water filling compsn has mobility, and the ratio of the said mobility of the said mobility of wherein said water filling compsn and said hydrocarbon Tibetan is not more than 100: 1.
32. method according to claim 31, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 50: 1.
33. method according to claim 32, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 10: 1.
34. method according to claim 33, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 2: 1.
35. method according to claim 30, wherein, the viscosity of said water filling compsn is 2mPa.s to 50mPa.s.
36. method according to claim 4, wherein, the concentration of said thickening polymer in said water filling compsn is 0.2 weight % of said water filling compsn.
37. method according to claim 36, wherein, said hydrocarbon is hidden has mobility, and wherein said water filling compsn has mobility, and the ratio of the said mobility of the said mobility of wherein said water filling compsn and said hydrocarbon Tibetan is not more than 100: 1.
38. according to the described method of claim 37, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 50: 1.
39. according to the described method of claim 38, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 10: 1.
40. according to the described method of claim 39, wherein, the said ratio of the said mobility that the said mobility of said water filling compsn and said hydrocarbon are hidden is not more than 2: 1.
41. method according to claim 36, wherein, the viscosity of said water filling compsn is 2mPa.s to 50mPa.s.
42. method according to claim 4; Wherein, The molecular weight of the said hydroxy ethyl cellulose skeleton polymer of said water filling compsn is 1; 300,000, the said material based on alkyl hydrocarbon of wherein said hydrophobically modified agent comprises dodecyl tetradecyl glycidyl ether; The said substitution value level of wherein said said hydrophobically modified agent in said thickening polymer is 0.7 weight % to 1 weight % of said thickening polymer, and the concentration of wherein said thickening polymer in said water filling compsn is 0.2 weight % of said water filling compsn.
43. according to the described method of claim 42, wherein, the said water of said water filling compsn comprises salt brine solution.
44. according to the described method of claim 43, wherein, said salt brine solution contains the sodium-chlor of the 1 weight % that accounts for said salt brine solution.
Make said water filling compsn through containing the stratum that hydrocarbon is hidden 45. a water filling preparation of compositions method of in hydrocarbon secondary recovery method, using, said hydrocarbon secondary recovery method comprise, wherein, said preparation method comprises:
(a) select the hydroxy ethyl cellulose skeleton polymer, the molecular weight of said hydroxy ethyl cellulose skeleton polymer is 1,000,000 to 2,000,000;
(b) select the hydrophobically modified agent, said hydrophobically modified agent comprises the material based on alkyl hydrocarbon that contains 10 to 24 unsubstituted carbon atom/groups;
(c) thickening polymer is provided; Said thickening polymer comprises said hydroxy ethyl cellulose skeleton polymer and said hydrophobically modified agent, and the substitution value level of said hydrophobically modified agent in said thickening polymer is 0.1 weight % to 2 weight % of said thickening polymer; With
(d) said thickening polymer and water are made up so that said water filling compsn to be provided, wherein, the concentration of said thickening polymer is 0.1 weight % to 1 weight % of said water filling compsn;
Wherein, the viscosity of said water filling compsn is 2mPa.s to 100mPa.s and can be expelled in the said stratum.
CN2010800493441A 2009-10-30 2010-09-27 Water flooding method for secondary hydrocarbon recovery Pending CN102666777A (en)

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