CN102373049B - Oil displacement method used for improving recovery efficiency of tertiary oil recovery - Google Patents
Oil displacement method used for improving recovery efficiency of tertiary oil recovery Download PDFInfo
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Abstract
The invention relates to an oil displacement method used for improving recovery efficiency of tertiary oil recovery and mainly aims to overcome the problems of poor temperature resistance and salt resistance and low oil displacement efficiency of polymer-containing oil displacement agents used in the prior art. According to the oil displacement method used for improving recovery efficiency of tertiary oil recovery, under the injection water conditions that an oil displacement temperature is greater than 70 DEG C, a total salinity is 20000 mg/L and the total amount of calcium ions and magnesium ions is greater than 500 mg/L, underground dehydrated crude oil is allowed to contact with the oil displacement composition so as to fully displace the crude oil in rock core, wherein, the oil displacement composition used in the method comprises, by weight, (1) 0.01 to 3.0% of temperature resistant salt resistant anionic polyacrylamide, (2) 0.01 to 5.0% of a fatty alcohol polyoxyethylene ether carboxylate surfactant, and (3) 92.0 to 99.98% of injection water. The method provided in the invention enables the above-mentioned problem to be well overcome and can be used in tertiary oil recovery.
Description
Technical field
The present invention relates to a kind of flooding method that is used to improve the tertiary oil recovery recovery ratio.
Background technology
The world economy fast development constantly increases the demand of the energy especially oil.Therefore, the oil recovery factor (EOR) in raising oil field becomes an important component part of oil play business planning in the world day by day.
Domestic each elephant through once, secondary oil recovery, crude oil water content constantly increases, the part elephant successively enters tertiary phase.Tertiary oil recovery be meant utilize natural energy exploit with the artificial supplementary energy of traditional usefulness (water filling, gas injection) afterwards, utilize physics, new technology chemistry, biological carries out the development scheme that mine tailing recovers the oil.Main by injection chemical substance, steam, gas (mixed phase) or microorganism etc., thus sweeping phase and water-oil interface character or crude oil physical properties changed.Polymer flooding is the main technique methods of tertiary oil recovery, and oil-displacement mechanism is clear, and technology is simple relatively, and technology reaches its maturity, and is one and effectively improves the recovery efficiency technique measure.The oil-displacement mechanism of polymkeric substance mainly is a viscosity of utilizing the water-soluble polyacrylamide molecular chain, improves the mobility ratio of displacing fluid, improves efficiency of displacement and swept volume, thereby reaches the purpose that improves recovery ratio.
Because the tertiary oil recovery cycle is long, deep layer oil temperature height, therefore, the used for tertiary oil recovery polymkeric substance must have good tackify, heatproof, salt resistance, stable performance.High volence metal ion in the oil reservoir is (as Ca in addition
2+, Mg
2+) PAM is separated, thereby reduced the tackify effect of PAM; Molecular rupture takes place in PAM easily under this external shearing action, thereby causes soltion viscosity to reduce significantly, thereby is difficult to satisfy the demand of deep two, three class oil reservoir high temperature and high salinities.In recent years, the research of used for tertiary oil recovery temperature resistant antisalt polymkeric substance both at home and abroad can be divided into two general orientation, i.e. the chemical modification of extra high molecular polymer and polymkeric substance.The anion-polyacrylamide of high molecular weight is to improve most widely used a kind of polymkeric substance in the oil recovery factor at present, and it can be formed by polyacrylamide hydrolysis under alkaline condition, also can obtain by third rare acid amides and acrylic acid copolymer.
In recent years, the research of relevant anion-polyacrylamide mainly concentrates on the improvement of initiator system, polymerization process and method for hydrolysis etc.CN1865299 and CN 1498908A finish polyreaction by the synergistic effect of three sections composite initiation series initiators, and colloid is pulverized back adding solid alkali and is hydrolyzed in hydrolyzer; CN1746198 adopts cohydrolysis technology, the multiple auxiliary agent single stage method reaction of polynary initiation, molecular weight 2073～2,317 ten thousand; CN101157736A has introduced polynary water-soluble azo initiator, various auxiliary agent, needs the very low temperature initiated polymerization; CN1240799 adds excessive solid alkali and mixes with polymer billet, finishes the posthydrolysis reaction under hot and humid; CN1542027 has adopted the mixture of ternary initiator system and sodium bicarbonate and yellow soda ash as hydrolytic reagent, and has added bicarbonate of ammonia as whipping agent, and the residual list of product is lower.The described technology of CN101029107 and CN101029099 causes down at 0 ℃, the hydrolytic reagent cohydrolysis that adds coated processing, uv-radiation mode initiated polymerization, polymkeric substance blob of viscose granulation post-reinforcing body alkali or spray add high density alkali lye as hydrolytic reagent, finish hydrolysis reaction fast by the microwave radiation mode; CN101514240A has adopted aqueous solution dispersion polymerization, and the product that obtains is 22～30% the aqueous solution, and molecular weight has only 120～14,000,000.By above patent as can be seen, though aspect molecular weight that improves anion-polyacrylamide or the dissolution rate bigger improvement is being arranged by all means, but in the less concern of temperature resistant antisalt aspect of performance, some technology or method are comparatively complicated, industrial production or can be subjected to some restrictions in the tertiary oil recovery practical application.At present in the tertiary oil recovery, the polymkeric substance that can satisfy the temperature resistant antisalt requirement then seldom, be not price too the higher position be unstable properties.So at the harsh oil reservoir of those high temperature and high salts, we ought to seek a kind ofly have sufficiently high molecular weight, and had the polymkeric substance of higher solution apparent viscosity in salt solution, and its preparation method will possess the industrial production feasibility.Compound and the application in tertiary oil recovery of method for producing polymer, binary that is suitable for high temperature and high salt just of the present invention.
Summary of the invention
Technical problem to be solved by this invention is that the oil-displacing agent that contains polymkeric substance in the prior art exists the temperature resistant antisalt performance can not satisfy the problem that tertiary oil recovery requires, oil displacement efficiency is low, and a kind of flooding method that is used to improve the tertiary oil recovery recovery ratio is provided.This method will contain temperature resistant antisalt anion-polyacrylamide composition and be used for oil displacement process, and it is low to have a working concentration, the high characteristics of oil displacement efficiency under the high temperature and high salt condition.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of flooding method that is used to improve the tertiary oil recovery recovery ratio, the composition that the displacement of reservoir oil is used is in displacement of reservoir oil temperature＞70 ℃, the about 20000mg/L of total mineralization, under the injection water condition of the total amount of calcium ion and magnesium ion greater than 500mg/L, underground dewatered oil is contacted with displacement of reservoir oil composition, the abundant displacement of the crude oil in the rock core is come out, wherein said displacement of reservoir oil composition comprises following component by weight percentage:
(1) 0.01～3.0% temperature resistant antisalt anion-polyacrylamide;
(2) 0.01～5.0% aliphatic alcohol polyethenoxy ether carboxylate tensio-active agent;
(3) 92.0～99.98% injection water;
Wherein (1) component temperature resistant antisalt anion-polyacrylamide is pressed GBT12005.10-92 Molecular Weight for Polyacrylamide Mw and is measured (viscosimetry) mensuration intrinsic viscosity [η], and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is 2053～3,330 ten thousand, is 19334mg/L in total mineralization, wherein the total amount of calcium ion and magnesium ion is in the aqueous solution of 514mg/L, and 1500mg/L polymer concentration solution is at 65 ℃, 7.34s
-1Under apparent viscosity be 20.3～26.8mps, at 75 ℃, 7.34s
-1Under apparent viscosity be 17.8～22.1mps.
In the technique scheme, displacement of reservoir oil temperature is preferably 70～80 ℃, and described injection water total mineralization is preferably 10000～30000mg/L, the preferred 200～1000mg/L of the total amount of calcium ion and magnesium ion; Polymkeric substance is selected from above-mentioned temperature resistant antisalt anion-polyacrylamide, and tensio-active agent is selected from aliphatic alcohol polyethenoxy ether carboxylate, and the ethoxy group is counted n and is preferably 2～8.
This flooding method concrete operations step may further comprise the steps:
A) acrylamide monomer being made into mass concentration is 10～40% aqueous solution I;
B) letting nitrogen in and deoxidizing adds composite initiation system: compositions with respect to monomer mass concentration 0.02～5% after 10～40 minutes in the solution I, the solution II;
C) letting nitrogen in and deoxidizing caused down at 5～25 ℃ after 10～40 minutes in the solution II, and polymerization gets gluey product I after 2～10 hours;
D) gluey product I is shredded the reaction 1～5 hour that is hydrolyzed of alkali lye that the back adds mass concentration 5～50%, wherein temperature is 80～95 ℃, gluey product II;
E) with gluey product II drying, after pulverizing, sieving the fine particulate anion-polyacrylamide;
F) with the anion-polyacrylamide of aequum, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate and injection water uniform mixing, 5～35 ℃ were stirred 1～3 hour, obtain required composition, by weight percentage, the proportioning of anion-polyacrylamide, aliphatic alcohol polyethenoxy ether carboxylate and injection water is 0.01～3.0%: 0.01～5.0%: 92.0～99.98;
G) be 10000～30000mg/L, Ca with total mineralization earlier
2++ Mg
2+The injection water that is 200～1000mg/L is saturated with rock core, measure the volume of voids (PV) of rock core, carry out saturated with dewatered oil then, carry out the imitation oil displacement experiment test under 70～80 ℃ of temperature: first water drive is to moisture 92%, the displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) synthetic with composition after, water drive is calculated the percentage ratio that improves oil recovery factor to moisture 99%.
In the technique scheme, the composite initiation system: compositions comprises following component by weight percentage: (a) 0.5～20% persulphate; (b) 0.1～40% sulphite or bisul-phite; (c) 0.5～20% by NR
1R
2R
3The representative tertiary amine compounds or by N
+R
4R
5R
6R
7The representative quaternary ammonium compounds or by NH
2R
8The fat amine compound of representative, R in the formula
1～R
7All be selected from C
1～C
14Straight or branched alkyl or alkyl derivative, R
8Be selected from C
1～C
18Straight or branched alkyl or alkyl derivative; (d) 10～80% urea, thiocarbamide or ammoniacal liquor; (e) 5～60% disodium ethylene diamine tetraacetate.
The composition that is used to improve the tertiary oil recovery recovery ratio that the present invention is prepared, owing to adopted the composite initiation system: compositions, and it is supporting with it with preferred technology, so reacting balance, help chainpropagation, product is the molecular weight height not only, also shows higher apparent viscosity in the salt solution of certain salinity; Wherein the function monomer of Tian Jiaing may make the more special structure of polymer formation, makes it have temperature resistant antisalt performance preferably simultaneously; Adopted posthydrolysis technology, polymerization and hydrolysis reaction are all accurately controlled, can obtain the product of higher molecular weight and certain degree of hydrolysis; Technical process is comparatively easy, helps suitability for industrialized production.The displacement of reservoir oil of using preparation technology provided by the present invention to make temperature resistant antisalt anion-polyacrylamide, molecular weight 〉=2,000 ten thousand, (the salt solution total mineralization 20000mgL of the apparent viscosity 〉=20mPas in salt solution
-1About, Ca
2++ Mg
2+〉=500mgL
-1).
Adopt the flooding method that is used to improve the tertiary oil recovery recovery ratio of the present invention, can be used for 70～80 ℃ of formation temperature, total mineralization is 10000～30000mg/L, the total amount of calcium ion and magnesium ion is that the Shengli Oil Field of 200～1000mg/L wins Tuo Er district's crude oil and water, form the above-mentioned composition oil-displacing agent with consumption 0.1～0.3wt% temperature resistant antisalt anion-polyacrylamide and 0.1～0.3wt% aliphatic alcohol polyethenoxy ether carboxylate, measure the dynamic interface tension value between this oil-displacing agent aqueous solution and the Shengli Oil Field victory Tuo Er district crude oil, can reach 10
-3～10
-4The ultra low interfacial tension of mN/m, can on the water drive basis, can reach 15.6% by (water drive improves oil recovery factor and reaches 40.6%) raising oil recovery factor through the indoor evaluation of physical simulation displacement test at this oil-displacing agent on high temperature, the high salinity reservoir, obtain better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
The 125g acrylamide monomer is added in the 335g deionized water, after the dissolving that stirs is complete, NaOH solution with 5% is regulated pH value to 8, logical then nitrogen 30min, and bath temperature transferred to 15 ℃, the ammonium persulfate aqueous solution 10g that adds 0.125wt% respectively, the aqueous solution of sodium bisulfite 9g of 0.0963wt%, the DMAEMA aqueous solution 10g of 0.125wt%, the ammoniacal liquor 10g of 0.5wt%, 0.16% disodium ethylene diamine tetraacetate (EDTA-disodium) aqueous solution 10g rises to 45 ℃ gradually with temperature of reaction behind the 30min, take out blob of viscose behind the reaction 4h, after being ground into particulate state, add 10% the NaOH aqueous solution 140 grams, at 90 ℃ of following hydrolysis reaction 2h, dry 6h under 75 ℃ of vacuum smashes screening back sampling analysis with pulverizer then.
By GBT12005.2-89 polyacrylamide determination of solid content method test solid content is 90.39%, by GBT12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method test degree of hydrolysis is 21.6%, press the GBT12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is 2,256 ten thousand, is 19334mg/L in total mineralization, wherein the total amount of calcium ion and magnesium ion is in the aqueous solution of 514mg/L, and 1500mg/L polymer concentration solution is at 65 ℃, 7.34s
-1Under apparent viscosity be 20.3mps, at 75 ℃, 7.34s
-1Under apparent viscosity be 17.8mps.
The synthetic temperature resistant antisalt anion-polyacrylamide 0.15wt% of institute, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.25wt% and 99.6wt% Shengli Oil Field are won Tuo Er district victory injection water uniform mixing, 20 ℃ were stirred 2 hours, and obtained required displacement of reservoir oil composition.At 75 ℃ of temperature, salinity 19334mg/L, Ca
2++ Mg
2+In the water of 514mg/L, the apparent viscosity that records this composition is 18.2mPa.s.; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0078mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROOKFIELD III type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
Earlier with salinity 19334mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the injection water of 514mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core
2) saturated, the volume of voids (PV) of measuring rock core is 50.2%, winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field then carries out saturated, carry out the imitation oil displacement experiment test under 75 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.6%, again the displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) synthetic with composition after, water drive records on the water drive basis and can improve oil recovery factor 14.9% again to moisture 99%.
[embodiment 2]
The 125g acrylamide monomer is added in the 344g deionized water, after the dissolving that stirs is complete, NaOH solution with 5% is regulated pH value to 8, logical then nitrogen 30min, and bath temperature transferred to 10 ℃, the persulfate aqueous solution 10g that adds 0.125wt% respectively, the aqueous solution of sodium bisulfite 10g of 0.0963wt%, the DMAEMA aqueous solution 10g of 0.125wt%, urea 1.25g, disodium ethylene diamine tetraacetate (EDTA-disodium) 0.64g rises to 42 ℃ gradually with temperature of reaction behind the 30min, take out blob of viscose behind the reaction 5h, after being ground into particulate state, add 10% the NaOH aqueous solution 145 grams, at 90 ℃ of following hydrolysis reaction 2h, dry 6h under 75 ℃ of vacuum smashes screening back sampling analysis with pulverizer then.
By GBT12005.2-89 polyacrylamide determination of solid content method test solid content is 90.23%, by GBT12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method test degree of hydrolysis is 19.8%, press the GBT12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is 2,372 ten thousand, is 19334mg/L in total mineralization, wherein the total amount of calcium ion and magnesium ion is in the aqueous solution of 514mg/L, and 1500mg/L polymer concentration solution is at 65 ℃, 7.34s
-1Under apparent viscosity be 21.3mps, at 75 ℃, 7.34s
-1Under apparent viscosity be 18.3mps.
The synthetic temperature resistant antisalt anion-polyacrylamide 0.15wt% of institute, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.35wt% and 99.5wt% Shengli Oil Field are won Tuo Er district victory injection water uniform mixing, 20 ℃ were stirred 2 hours, and obtained required displacement of reservoir oil composition.At 75 ℃ of temperature, salinity 19334mg/L, Ca
2++ Mg
2+In the water of 514mg/L, the apparent viscosity that records this composition is 18.6mPa.s.; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0069mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROOKFIELD III type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
Earlier with salinity 19334mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the injection water of 514mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core
2) saturated, the volume of voids (PV) of measuring rock core is 51.8%, winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field then carries out saturated, carry out the imitation oil displacement experiment test under 75 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.7%, again the displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) synthetic with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.1% again to moisture 99%.
[embodiment 3]
The 118g acrylamide monomer is added in the 340g deionized water, after the dissolving that stirs is complete, NaOH solution with 5% is regulated the pH value extremely, logical then nitrogen 30min, and bath temperature transferred to 18 ℃, the persulfate aqueous solution 10g that adds 0.125wt% respectively, 0.094% sodium sulfite aqueous solution 10g, the DMAEMA aqueous solution 20g of 0.125wt%, thiocarbamide 1.36g, disodium ethylene diamine tetraacetate (EDTA-disodium) 1.31g rises to 48 ℃ gradually with temperature of reaction behind the 30min, take out blob of viscose behind the reaction 4h, after being ground into particulate state, add 10% the NaOH aqueous solution 150 grams, at 85 ℃ of following hydrolysis reaction 2.5h, dry 6h under 75 ℃ of vacuum smashes screening back sampling analysis with pulverizer then.
By GBT12005.2-89 polyacrylamide determination of solid content method test solid content is 90.39%, by GBT12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method test degree of hydrolysis is 22.3% to measure (viscosimetry) by the GBT12005.10-92 Molecular Weight for Polyacrylamide and measure intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is 2,558 ten thousand, is 19334mg/L in total mineralization, wherein the total amount of calcium ion and magnesium ion is in the aqueous solution of 514mg/L, and 1500mg/L polymer concentration solution is at 65 ℃, 7.34s
-1Under apparent viscosity be 24.7mps, at 75 ℃, 7.34s
-1Under apparent viscosity be 19.2mps.
The synthetic temperature resistant antisalt anion-polyacrylamide 0.15wt% of institute, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.25wt% and 99.6wt% Shengli Oil Field are won Tuo Er district victory injection water uniform mixing, 20 ℃ were stirred 2 hours, and obtained required displacement of reservoir oil composition.At 75 ℃ of temperature, salinity 19334mg/L, Ca
2++ Mg
2+In the water of 514mg/L, the apparent viscosity that records this composition is 19.8mPa.s.; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0048mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROOKFIELD III type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
Earlier with salinity 19334mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the injection water of 514mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core
2) saturated, the volume of voids (PV) of measuring rock core is 51.6%, winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field then carries out saturated, carry out the imitation oil displacement experiment test under 78 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.4%, again the displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) synthetic with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.2% again to moisture 99%.
[embodiment 4]
The 140g acrylamide monomer is added in the 330g deionized water, after the dissolving that stirs is complete, NaOH solution with 5% is regulated pH value to 6, logical then nitrogen 30min, and bath temperature transferred to 7 ℃, the persulfate aqueous solution 10g that adds 0.125wt% respectively, the aqueous solution of sodium bisulfite 10g of 0.0963wt%, the DMAEMA aqueous solution 10g of 0.125wt%, urea 0.8g, disodium ethylene diamine tetraacetate (EDTA-disodium) 0.16g rises to 40 ℃ gradually with temperature of reaction behind the 30min, take out blob of viscose behind the reaction 5.5h, after being ground into particulate state, add 10% the NaOH aqueous solution 150 grams, at 85 ℃ of following hydrolysis reaction 3h, dry 6h under 75 ℃ of vacuum smashes screening back sampling analysis with pulverizer then.
By GBT12005.2-89 polyacrylamide determination of solid content method test solid content is 89.62%, by GBT12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method test degree of hydrolysis is 23.6% to measure (viscosimetry) by the GBT12005.10-92 Molecular Weight for Polyacrylamide and measure intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is 3,330 ten thousand, is 19334mg/L in total mineralization, wherein the total amount of calcium ion and magnesium ion is in the aqueous solution of 514mg/L, and 1500mg/L polymer concentration solution is at 65 ℃, 7.34s
-1Under apparent viscosity be 26.8mps, at 75 ℃, 7.34s
-1Under apparent viscosity be 22.1mps.
The synthetic temperature resistant antisalt anion-polyacrylamide 0.15wt% of institute, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.40wt% and 99.45wt% Shengli Oil Field are won Tuo Er district victory injection water uniform mixing, 15 ℃ were stirred 3 hours, and obtained required displacement of reservoir oil composition.At 75 ℃ of temperature, salinity 19334mg/L, Ca
2++ Mg
2+In the water of 514mg/L, the apparent viscosity that records this composition is 20.3mPa.s.; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0069mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROOKFIELD III type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
Earlier with salinity 19334mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the injection water of 514mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core
2) saturated, the volume of voids (PV) of measuring rock core is 51.2%, winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field then carries out saturated, carry out the imitation oil displacement experiment test under 75 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.2%, again the displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) synthetic with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.6% again to moisture 99%.
[embodiment 5]
The 125g acrylamide monomer is added in the 340g deionized water, after the dissolving that stirs is complete, NaOH solution with 5% is regulated pH value to 10, logical then nitrogen 30min, and bath temperature transferred to 15 ℃, the ammonium persulfate aqueous solution 10g that adds 0.125wt% respectively, the aqueous solution of sodium bisulfite 5g of 0.0963wt%, the DMAEMA aqueous solution 10g of 0.125wt%, the ammoniacal liquor 10g of 0.5wt%, 0.869wt% disodium ethylene diamine tetraacetate (EDTA-disodium) aqueous solution 10g rises to 45 ℃ gradually with temperature of reaction behind the 30min, take out blob of viscose behind the reaction 4h, after being ground into particulate state, add 10% the NaOH aqueous solution 140 grams, at 90 ℃ of following hydrolysis reaction 2h, dry 6h under 75 ℃ of vacuum smashes screening back sampling analysis with pulverizer then.
By GBT12005.2-89 polyacrylamide determination of solid content method test solid content is 91.57%, by GBT12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method test degree of hydrolysis is 21.6%, press the GBT12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is 2,053 ten thousand, is 19334mg/L in total mineralization, wherein the total amount of calcium ion and magnesium ion is in the aqueous solution of 514mg/L, and 1500mg/L polymer concentration solution is at 65 ℃, 7.34s
-1Under apparent viscosity be 21.5mps, at 75 ℃, 7.34s
-1Under apparent viscosity be 18.2mps.
The synthetic temperature resistant antisalt anion-polyacrylamide 0.15wt% of institute, above-mentioned aliphatic alcohol polyethenoxy ether carboxylate (n=4) 0.35wt% and 99.5wt% Shengli Oil Field are won Tuo Er district victory injection water uniform mixing, 25 ℃ were stirred 1.5 hours, and obtained required displacement of reservoir oil composition.At 75 ℃ of temperature, salinity 19334mg/L, Ca
2++ Mg
2+In the water of 514mg/L, the apparent viscosity that records this composition is 19.0mPa.s.; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0056mN/m between the Tuo Er district 0-141 well dewatered oil.Apparent viscosity is by the BROOKFIELD III type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces.
Earlier with salinity 19334mg/L, Ca
2++ Mg
2+(length is 30 centimetres to the injection water of 514mg/L, and diameter is 2.5 centimetres, and rate of permeation is 1.5 microns with rock core
2) saturated, the volume of voids (PV) of measuring rock core is 50.8%, winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field then carries out saturated, carry out the imitation oil displacement experiment test under 75 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.5%, again the displacement of reservoir oil of metaideophone 0.3pv (rock pore volume) step (f) synthetic with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.2% again to moisture 99%.
[comparative example 1]
The 125g acrylamide monomer is added in the 355g deionized water, after the dissolving that stirs is complete, NaOH solution with 5% is regulated pH value to 8, logical then nitrogen 30min, and bath temperature transferred to 15 ℃, the persulfate aqueous solution 10g that adds 0.125wt% respectively, the aqueous solution of sodium bisulfite 10g of 0.0963wt%, behind the 30min temperature of reaction is risen to 45 ℃ gradually, reaction is taken out blob of viscose behind the 4h, be ground into particulate state after, the NaOH aqueous solution 140 grams of adding 10%, at 90 ℃ of following hydrolysis reaction 2h, dry 6h under 75 ℃ of vacuum smashes screening back sampling analysis with pulverizer then.
By GBT12005.2-89 polyacrylamide determination of solid content method test solid content is 88.65%, by GBT12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method test degree of hydrolysis is 20.3%, press the GBT12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is 1,963 ten thousand, is 19334mg/L in total mineralization, wherein the total amount of calcium ion and magnesium ion is in the aqueous solution of 514mg/L, and 1500mg/L polymer concentration solution is at 65 ℃, 7.34s
-1Under apparent viscosity be 16.2mps, at 75 ℃, 7.34s
-1Under apparent viscosity be 13.9mps.
With [embodiment 1], record water drive and improve oil recovery factor 40.6%, the above-mentioned displacement of reservoir oil of metaideophone with composition after, record on the water drive basis and can improve oil recovery factor 10.7% again.
[comparative example 2]
The 125g acrylamide monomer is added in the 345g deionized water, after the dissolving that stirs is complete, NaOH solution with 5% is regulated pH value to 8, logical then nitrogen 30min, and bath temperature transferred to 15 ℃, the persulfate aqueous solution 10g that adds 0.125wt% respectively, the aqueous solution of sodium bisulfite 10g of 0.0963wt%, the AIBI aqueous solution 10g of 0.125wt% rises to 45 ℃ gradually with temperature of reaction behind the 30min, take out blob of viscose behind the reaction 4h, after being ground into particulate state, add 10% the NaOH aqueous solution 140 grams, at 90 ℃ of following hydrolysis reaction 2h, dry 6h under 75 ℃ of vacuum smashes screening back sampling analysis with pulverizer then.
By GBT12005.2-89 polyacrylamide determination of solid content method test solid content is 87.54%, by GBT12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method test degree of hydrolysis is 21.32%, press the GBT12005.10-92 Molecular Weight for Polyacrylamide and measure (viscosimetry) mensuration intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is 2,132 ten thousand, is 19334mg/L in total mineralization, wherein the total amount of calcium ion and magnesium ion is in the aqueous solution of 514mg/L, and 1500mg/L polymer concentration solution is at 65 ℃, 7.34s
-1Under apparent viscosity be 17.9mps, at 75 ℃, 7.34s
-1Under apparent viscosity be 14.6mps.
With [embodiment 1], record water drive and improve oil recovery factor 40.3%, the above-mentioned displacement of reservoir oil of metaideophone with composition after, record on the water drive basis and can improve oil recovery factor 11.3% again.
Claims (1)
1. flooding method that is used to improve the tertiary oil recovery recovery ratio is characterized by:
The 140g acrylamide monomer is added in the 330g deionized water, after the dissolving that stirs is complete, NaOH solution with 5% is regulated pH value to 6, logical then nitrogen 30min, and bath temperature transferred to 7 ℃, the persulfate aqueous solution 10g that adds 0.125wt% respectively, the aqueous solution of sodium bisulfite 10g of 0.0963wt%, the DMAEMA aqueous solution 10g of 0.125wt%, urea 0.8g, disodium ethylene diamine tetraacetate 0.16g rises to 40 ℃ gradually with temperature of reaction behind the 30min, take out blob of viscose behind the reaction 5.5h, after being ground into particulate state, add 10% the NaOH aqueous solution 150 grams, at 85 ℃ of following hydrolysis reaction 3h, dry 6h under 75 ℃ of vacuum smashes screening back sampling analysis with pulverizer then;
By GBT12005.2-89 polyacrylamide determination of solid content method test solid content is 89.62%, by GBT12005.6-89 partially hydrolyzed polyacrylamide degree of hydrolysis measuring method test degree of hydrolysis is 23.6% to measure (viscosimetry) by the GBT12005.10-92 Molecular Weight for Polyacrylamide and measure intrinsic viscosity, and by [η]=3.73 * 10
-4Mw
0.66Calculating molecular weight is 3,330 ten thousand, is 19334mg/L in total mineralization, wherein the total amount of calcium ion and magnesium ion is in the aqueous solution of 514mg/L, and 1500mg/L polymer concentration solution is at 65 ℃, 7.34s
-1Under apparent viscosity be 26.8mps, at 75 ℃, 7.34s
-1Under apparent viscosity be 22.1mps;
The synthetic temperature resistant antisalt anion-polyacrylamide 0.15wt% of institute, aliphatic alcohol polyethenoxy ether carboxylate 0.40wt% and 99.45wt% Shengli Oil Field are won Tuo Er district victory injection water uniform mixing, and the adduction number of EO is 4 in the described aliphatic alcohol polyethenoxy ether carboxylate; 15 ℃ were stirred 3 hours, and obtained required displacement of reservoir oil composition; At 75 ℃ of temperature, salinity 19334mg/L, Ca
2++ Mg
2+In the water of 514mg/L, the apparent viscosity that records this composition is 20.3mPa.s.; Said composition and Shengli Oil Field win the ultra low interfacial tension that forms 0.0069mN/m between the Tuo Er district 0-141 well dewatered oil; Apparent viscosity is by the BROOKFIELDIII type viscometer determining of U.S. Brookfield company, and interfacial tension is dripped interfacial tensimeter mensuration by the TX500 type rotation that Texas ,Usa university produces;
Earlier with salinity 19334mg/L, Ca
2++ Mg
2+The injection water of 514mg/L is that 30 centimetres, diameter are that 2.5 centimetres, rate of permeation are 1.5 microns with length
2Rock core is saturated; The volume of voids of measuring rock core is 51.2%, winning Tuo Er district 0-141 well dewatered oil with Shengli Oil Field then carries out saturated, carry out the imitation oil displacement experiment test under 75 ℃ of constant temperature: first water drive is to moisture 92%, record water drive and improve oil recovery factor 40.2%, again the described displacement of reservoir oil of metaideophone 0.3 rock pore volume with composition after, water drive records on the water drive basis and can improve oil recovery factor 15.6% again to moisture 99%.
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