CN105368429A - Surfactant for high-temperature and high-salt oil reservoir displacement - Google Patents
Surfactant for high-temperature and high-salt oil reservoir displacement Download PDFInfo
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Abstract
The invention relates to a surfactant for high-temperature and high-salt oil reservoir displacement and a preparing method. The surfactant mainly solves the problems that a surfactant serving as an oil displacement agent system in the prior art is high in cost and poor in high-temperature resistance and salt resistance. A non-ionic surfactant shown in the formula (1) and an anionic surfactant shown in the formula (2) are adopted; R1 and R2 are aliphatic groups of C4-C40 or aryl groups substituted by saturated and unsaturated alkyl groups of linear chains or branched chains of C4-C30; Z1 is -R01Y1; R01 is selected from an alkylene group or hydroxyl substituted alkylene of C1-C5, Y1 is selected from SO3M or COON, M and N are independently selected from hydrogen, alkali metal or radical groups shown as the formula NR3(R4)(R5)(R6), R3, R4, R5 and R6 are independently selected from H, (CH2)pOH or (CH2)qCH3, p is equal to 2-4, and q is equal to 0-5.
Description
Technical field
The present invention relates to the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil and preparation method.
Background technology
Improve recovery efficiency technique, the strengthening be namely often referred to (EOR) and improve (IOR) recovery efficiency technique abroad, can be summarized as six aspects such as improving ecology, chemical flooding, heavy crude heat extraction, gas drive, microbe oil production and Physical oil recovery.At present, the raising recovery efficiency technique entering mining site mass-producing application concentrates on thermal recovery, gas drive and chemical flooding three major types, and wherein chemical flooding output is 5.18 × 10
4m
3/ more than d, accounts for 14.7% of world EOR ultimate production.Chemical flooding is by adding chemical agent in the aqueous solution, change inject the physicochemical property of fluid and rheological property and with the interaction characteristic of reservoir rock and improve a kind of enhancements of recovery ratio, fast development is able in China, its major cause is China's reservoir is that nonmarine deposit nonuniformity is stronger, terrestrial origin of petroleum viscosity of crude is higher, in EOR method, be more suitable for chemical flooding.
According to chemical constitution and the molecular structure difference of tensio-active agent, tensio-active agent can be divided into ionic and the large class of non-ionic type two.In current tertiary oil recovery research, the kind of tensio-active agent used is maximum with anionic, is secondly non-ionic type and amphoteric ion type, and it is cationic for applying minimum.The patent US3927716 of Mobil Oil Corp., US4018281, US4216097 report the result adopting caustic flooding, tensio-active agent or caustic flooding and use the zwitterionics displacement of reservoir oil in succession, the zwitterionics adopted is carboxylic acid or the sulfonate type beet alkali surface activator of different chain length, at total mineralising 62000 ~ 160000mg/L, in the simulation salt solution of calcium ions and magnesium ions 1500 ~ 18000mg/L, 10 are reached to the interfacial tension of Texas Southern crude oil
-1~ 10
-4mN/m.The patent US4370243 of Mobil Oil Corp. reports and adopts oil-soluble alcohol, the flooding system of sulphonic acid betaine and quaternary ammonium salt composition, this system both can play the effect of tensio-active agent, also the effect of mobility control agent can be played, wherein quaternary ammonium salt to be oleophilic group carbon chain length be 16 ~ 20 cats product, the octadecyl dihydroxy ethyl propyl sulfonic acid betaine salt of employing 2wt% and the n-hexyl alcohol of 1.0% are as oil-displacing agent, after injecting 1.9PV, crude oil gets final product 100% and displaces, but surfactant adsorption loss reaches 6mg/g more greatly, 2.0% tetraethylammonium bromide adding relative low price on this basis as sacrifice agent to reduce surfactant adsorption amount.The patent US8211837 of Texas ,Usa university application, report adopt cheap and simple linear alcohol at high temperature catalytic dimerization be obtained by reacting the long carbon alcohol of collateralization, sulfuric acid esterification is carried out with after propylene oxide, ethylene oxide polymerization, relative to the sulfonate surfactant of costliness, low cost has synthesized large hydrophilic group polyether thiourea acid salt surfactant, due to the existence of large hydrophilic radical, thus high temperature stability performance is excellent in the basic conditions to make this sulfate surfactant, the branched-chain alcoho polyether thiourea hydrochlorate (C of 0.3%
32-7PO-6EO vitriol) with 0.3% internal olefin sulphonates (C
20 ~ 24iOS) salt brine solution mixes with the crude oil of identical amount at 85 DEG C, and its solubilization parameter is 14.The tensio-active agent that foreign study uses, because usage quantity is large, cost is high, receives certain restriction in actual applications as oil-displacing agent.What use cats product also has report, as Chinese patent CN1528853, CN1817431, CN1066137 etc. in succession report that bisamide type is cationic, fluorine-containing cationic type and containing pyridyl cation Gemini surfactant, but because positively charged ion has, absorption loss is large, high in cost of production shortcoming, limits its use at Oil Field.
Summary of the invention
One of technical problem to be solved by this invention is that the tensio-active agent Presence of an interface activity mainly formed as oil-displacing agent system in prior art is low, the problem of temperature resistant antisalt performance difference, provides a kind of tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil newly.The aqueous solution for the tensio-active agent of the high temperature and high salt oil deposit displacement of reservoir oil can form 10 with crude oil in 0.005 ~ 0.6% scope
-2~ 10
-4mN/m low interfacial tension.
Two of technical problem to be solved by this invention is preparation methods of the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil described in one of above-mentioned technical problem.
Three of technical problem to be solved by this invention is another kind of preparation methods of the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil described in one of above-mentioned technical problem.
Four of technical problem to be solved by this invention is the tensio-active agent application in the displacement of reservoir oil of oil field for the high temperature and high salt oil deposit displacement of reservoir oil described in one of above-mentioned technical problem.
In order to one of solve the problems of the technologies described above, the technical solution used in the present invention is as follows: for the tensio-active agent of the high temperature and high salt oil deposit displacement of reservoir oil, comprise the anion surfactant shown in the nonionogenic tenside shown in formula (1) and formula (2), the mass ratio of wherein said anion surfactant and described nonionogenic tenside is (0.1 ~ 1): 1; More preferably (0.1 ~ 0.6): 1;
R
1and R
2for being identical or not identical C
4~ C
40aliphatic group or by C
4~ C
30the aryl of the saturated and unsaturated alkyl replacement of straight or branched; M1, m2, m3 or m4 are independently selected from 0 ~ 50, but m1 and m2, m3 and m4 can not be 0 simultaneously; N1 and n2 is independently selected from 0 ~ 100, but n1 and n2 can not be 0 simultaneously; R1, r2, r3 or r4 are independently selected from 0 ~ 50, but r1 and r2, r3 and r4 can not be 0 simultaneously; S1 and s2 is independently selected from 0 ~ 100, but s1 and s2 can not be 0 simultaneously; Z
1for-R
01y
1; R
01be selected from C
1~ C
5alkylidene group or hydroxyl substituted alkylene, Y
1be selected from SO
3m or COON, M and N are selected from hydrogen, basic metal or by formula NR
3(R
4) (R
5) (R
6) shown group, R
3, R
4,r
5,r
6for being independently selected from H, (CH
2)
poH or (CH
2)
qcH
3, the arbitrary integer in p=2 ~ 4, q=0 ~ 5.
In technique scheme, preferred described R
1or R
2in at least one be C
6~ C
20alkyl or by C
8~ C
16the phenyl that alkyl replaces.
In technique scheme, preferred p=2, q=0 ~ 1.
In technique scheme, preferred m1+m2=2 ~ 10, m3+m4=5 ~ 30, n1+n2=2 ~ 20; And/or r1+r2=2 ~ 10, r3+r4=5 ~ 30, s1+s2=2 ~ 20.
The key of tensio-active agent that the present invention is used for the high temperature and high salt oil deposit displacement of reservoir oil is active princlple is the anion surfactant shown in the nonionogenic tenside shown in formula (1) and formula (2), those skilled in the art will know that, consider for the ease of transport and the aspect such as storage or onsite application, various supply form can be adopted, such as water-free solid-state form, or moisture solid-state form, or moisture cream form, or aqueous solution form; Aqueous solution form comprises the form being made into concentrated solution with water, is directly made into the solution form of on-the-spot displacement of reservoir oil desired concn, and such as key active ingredient content is the solution of 0.005 ~ 0.6wt% is in mass the form that the on-the-spot displacement of reservoir oil is comparatively suitable for; Wherein, not having particular requirement to water, can be deionized water, can also be the water containing inorganic mineral, and can be tap water, oil field stratum water or oilfield injection water containing the water of inorganic mineral.
The present invention is used for the tensio-active agent of the high temperature and high salt oil deposit displacement of reservoir oil, described nonionogenic tenside and described anion surfactant can be obtained by mixing in required ratio, preferably obtain with the following technical scheme for technical solution problem two or for the technical scheme of technical solution problem three.
For solve the problems of the technologies described above two, the technical solution adopted in the present invention is as follows: the preparation method of the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil that one of above-mentioned technical problem is described, comprises the following steps:
A, basic catalyst exist under, R
1nH
2r is obtained successively with aequum oxyethane, propylene oxide, reacting ethylene oxide
1n ((CH
2cH
2o)
m1(CHCH
3cH
2o)
n1(CH
2cH
2o)
m3h) ((CH
2cH
2o)
m2) (CHCH
3cH
2o)
n2(CH
2cH
2o)
m4h);
B, the product that step a is obtained and X
1r
01y
01and alkali metal hydroxide or alkali metal alcoholates are with mol ratio (2 ~ 10): 1:(1 ~ 10) in a solvent, within 3 ~ 15 hours, obtain the mixture of the anion surfactant containing the nonionogenic tenside shown in formula (1) and formula (3) depicted in temperature of reaction 50 ~ 120 DEG C reaction;
Wherein, Z
01for-R
01y
01; Y
01be selected from SO
3m
1or COON
1, M
1and N
1for basic metal, X
1be selected from chlorine, bromine or iodine.
In technique scheme, the R described in step b
1n ((CH
2cH
2o)
m1(CHCH
3cH
2o)
n1(CH
2cH
2o)
m3h) ((CH
2cH
2o)
m2) (CHCH
3cH
2o)
n2(CH
2cH
2o)
m4h): X
1r
01y
01: the mol ratio of alkali metal hydroxide or alkali metal alcoholates is preferably (3 ~ 5): 1: (1.1 ~ 2).
In technique scheme, the solvent described in step b is preferably from C
3~ C
8ketone and C
6~ C
9aromatic hydrocarbons at least one.
In technique scheme, the optional alkali metal hydroxide of described basic catalyst (such as sodium hydroxide or potassium hydroxide), alkali metal alcoholates (such as sodium methylate, potassium methylate, sodium ethylate, potassium ethylate).
As long as carried out the reaction of step b, those skilled in the art without the separation of complexity, only can need distill removal solvent, can obtain the described tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil of saliferous and excesses of basic catalysts.In order to obtain the sterling only containing formula (1) and formula (2), can implement without the need to paying creative work those skilled in the art after step b.
Such as, M is worked as in order to what obtain not saliferous and excesses of basic catalysts by the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil of anion surfactant shown in formula (1) described nonionogenic tenside and formula (3)
1or N
1for product during H, step c and steps d can be comprised further:
Add pH=1 ~ 3 that acid regulates aqueous phase in c, the reaction mixture that obtains in step b, be separated and obtain organic phase;
D, the concentrated organic phase obtained obtain desired product.
Again such as, M is worked as in order to what obtain not saliferous and excesses of basic catalysts by the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil of anion surfactant shown in formula (1) described nonionogenic tenside and formula (3)
1or N
1for basic metal or by formula NR
3(R
4) (R
5) (R
6) shown in the product of group, can on the basis of step c with required basic metal or formula NR
3(R
4) (R
5) (R
6) the corresponding alkali neutralization of shown group, then remove solvent described in organic phase.
Basic metal required described in technique scheme or formula NR
3(R
4) (R
5) (R
6) the shown corresponding alkali of group, such as corresponding to basic metal alkali is selected from alkali metal hydroxide, alkaline carbonate, alkali metal hydrocarbonate, alkalimetal oxide or alkali metal alcoholates etc., with NR
3(R
4) (R
5) (R
6) the corresponding alkali of described group is selected from ammonia, thanomin, diethanolamine, trolamine, triethylamine, quaternary ammonium hydroxide etc.
XR
2y
1example have but be not limited to an alkali metal salt, 2-monochloroethane sulfonic acid alkali metal salts etc. of chloroacetic an alkali metal salt (such as sodium chloroacetate), 3-chlorine-2-hydroxyl propanesulfonic acid.
In technique scheme, the R described in step b
1n ((CH
2cH
2o)
m1(CHCH
3cH
2o)
n1(CH
2cH
2o)
m3h) ((CH
2cH
2o)
m2) (CHCH
3cH
2o)
n2(CH
2cH
2o)
m4h): X
1r
01y
01: the mol ratio of alkali metal hydroxide or alkali metal alcoholates is preferably (3 ~ 5): 1: (1.1 ~ 2).
In technique scheme, the solvent described in step b is preferably from C
3~ C
8ketone and C
6~ C
9aromatic hydrocarbons at least one, such as, by least one in acetone, butanone, pentanone, the material group that forms from benzene, toluene or dimethylbenzene, trimethylbenzene, ethylbenzene and diethylbenzene.
In order to solve the problems of the technologies described above three, technical scheme of the present invention is as follows: the described preparation method for the tensio-active agent of the high temperature and high salt oil deposit displacement of reservoir oil of one of above-mentioned technical problem, comprises the following steps:
B product that above-mentioned steps a obtains by () and 1,3-third sultone and alkali metal hydroxide or alkali metal alcoholates are with mol ratio (2 ~ 10): 1:(1 ~ 10) in a solvent, within 3 ~ 15 hours, obtain the mixture containing the nonionogenic tenside shown in formula (1) and the anion surfactant shown in formula (4) in temperature of reaction 50 ~ 120 DEG C reaction;
Wherein Z
03for-CH
2cH
2cH
2sO
3m
2; M
2for basic metal.
In technique scheme, the R described in step (b)
1n ((CH
2cH
2o)
m1(CHCH
3cH
2o)
n1(CH
2cH
2o)
m3h) ((CH
2cH
2o)
m2) (CHCH
3cH
2o)
n2(CH
2cH
2o)
m4h): 1,3-third sultone: the mol ratio of alkali metal hydroxide or alkali metal alcoholates is preferably (3 ~ 5): 1: (1.1 ~ 2).
In technique scheme, the solvent described in step (b) is preferably from C
3~ C
8ketone and C
6~ C
9aromatic hydrocarbons at least one.
As long as carried out the reaction of step (b), those skilled in the art without the separation of complexity, only can need distill removal solvent, can obtain the described tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil of saliferous and excesses of basic catalysts.In order to obtain the sterling only containing formula (1) and formula (4), can implement without the need to paying creative work those skilled in the art after step (b).
Such as, M is worked as in order to what obtain not saliferous and excesses of basic catalysts by the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil of anion surfactant shown in formula (1) described nonionogenic tenside and formula (4)
2for product during H, step (c) and step (d) can be comprised further:
Add pH=1 ~ 3 that acid regulates aqueous phase in c reaction mixture that () obtains in step (b), be separated and obtain organic phase;
D () concentrated organic phase obtained obtains desired product.
Again such as, M is worked as in order to what obtain not saliferous and excesses of basic catalysts by the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil of anion surfactant shown in formula (1) described nonionogenic tenside and formula (4)
3for basic metal or by formula NR
3(R
4) (R
5) (R
6) shown in the product of group, can on the basis of step (c) with required basic metal or formula NR
3(R
4) (R
5) (R
6) the corresponding alkali neutralization of shown group, then remove solvent described in organic phase.
Basic metal required described in technique scheme or formula NR
3(R
4) (R
5) (R
6) the shown corresponding alkali of group, such as corresponding to basic metal alkali is selected from alkali metal hydroxide, alkaline carbonate, alkali metal hydrocarbonate, alkalimetal oxide or alkali metal alcoholates etc., with NR
3(R
4) (R
5) (R
6) the corresponding alkali of described group is selected from ammonia, thanomin, diethanolamine, trolamine, triethylamine, quaternary ammonium hydroxide etc.
In order to solve the problems of the technologies described above four, technical scheme of the present invention is as follows: the described application of tensio-active agent in the displacement of reservoir oil of oil field for the high temperature and high salt oil deposit displacement of reservoir oil, total mineralization 30000 ~ the 35000mg/L of the formation brine of described high temperature and high salt oil deposit, wherein Ca
2+be 1000 ~ 1500mg/L, Mg
2+be 200 ~ 600mg/L, HCO
3 -be 5 ~ 40mg/L; Viscosity of crude is 5 ~ 15mPa.s; Formation temperature is 75 ~ 90 DEG C.
In the present patent application file, relate to the described dosage of surfactant for the high temperature and high salt oil deposit displacement of reservoir oil or concentration, all with the total amount of the anion surfactant shown in the nonionogenic tenside shown in formula (1) and formula (2).
Adopt the present invention to be used for the tensio-active agent of the high temperature and high salt oil deposit displacement of reservoir oil, by percentage to the quality, consumption is can form 10 with underground crude oil under the condition of 0.025 ~ 0.6wt%
-1~ 10
-4the low interfacial tension of mN/m, still can keep lower value at the stable lower aging 90 days rear interface tension force of oil reservoir, achieve good technique effect.
Accompanying drawing explanation
Fig. 1 a ~ 1c is that different concns S-1 ~ S-8 analog salt aqueous solution is to the oil water interfacial tension figure of oil from Shengli oil field.
Fig. 2 a ~ 2c be 0.3% S-1 ~ S-8 analog salt aqueous solution after different digestion time to the oil water interfacial tension figure of oil from Shengli oil field.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The anion surfactant structural formula of preparation is as follows, wherein R
1carbochain be distributed as: C
1272.3wt%, C
1427.7wt%, m
1+ m
2=3, n
1+ n
2=20, m
3+ m
4=8.
192.6 grams (1 mole) mixing, 12/14 (C are added in the 5L pressure reactor that whipping appts is housed
12 ~ 14) amine, 9.5 grams of potassium hydroxide, when being heated to 80 ~ 90 DEG C, open vacuum system, dewater 1 hour under a high vacuum, then nitrogen replacement is used 3 ~ 4 times, system temperature of reaction is adjusted to 110 DEG C and slowly passes into 132.9 grams of (3.02 moles) oxyethane, control pressure≤0.50MPa, after reacting ethylene oxide terminates, 1171.6 grams of (20.2 moles) propylene oxide are slowly passed in 150 DEG C, control pressure≤0.60MPa, is adjusted to 130 DEG C again and slowly passes into 354.2 grams of (8.05 moles) oxyethane after propylene oxide reaction terminates by temperature.After reaction terminates, be cooled to 90 DEG C, vacuum removing low-boiling-point substance, neutralization after cooling, dehydration, obtain mixing 12/14 (C
12 ~ 14) 1764.9 grams, amine polyoxyethylene (3) polyoxypropylene (20) polyoxyethylene (8) ether, yield 96.1%.
Mix 12/14 (C
12 ~ 14) 1102.0 grams, amine polyoxyethylene (3) polyoxypropylene (20) polyoxyethylene (8) ether (0.6 mole) and 12 grams of (0.3 mole) sodium hydroxide and 500 milliliters of toluene/dimethylbenzene (v/v=1) are mixed in the four-hole boiling flask of 2500 milliliters that are furnished with mechanical stirring, thermometer and reflux condensing tube, be heated to 80 DEG C, add 23.3 grams of (0.2 mole) sodium chloroacetates enters in reaction flask in batches, is warming up to back flow reaction 3 hours after adding.Cooling, with 15wt% sulfuric acid acidation, divide and anhydrate and inorganic salt, steaming desolventizes, and the mixture obtained is analyzed through high performance liquid chromatography (HPLC), mixes 12/14 (C in product
12 ~ 14) amine polyoxyethylene (3) polyoxypropylene (20) polyoxyethylene (8) ether acetic acid with mix 12/14 (C
12 ~ 14) mass ratio of amine polyoxyethylene (3) polyoxypropylene (20) polyoxyethylene (8) ether is 0.54:1.The mixture obtained is mixed with water, with the pH=13 of the aqueous sodium hydroxide solution regulation system of 20wt%, obtains required nonionic and anion compounded surfactant S-1.
[embodiment 2]
With [embodiment 1], difference is mixing 12/14 (C
12 ~ 14) amine polyoxyethylene (3) polyoxypropylene (20) polyoxyethylene (8) ether and sodium chloroacetate react after without the need to adding acid treatment, namely back flow reaction is after 3 hours, change water distilling apparatus into, solvent toluene/dimethylbenzene (v/v=1) is removed in distillation, residuum adds water and stirs, and obtains nonionic and the anion compounded surfactant S-2 of sodium chloride-containing and sodium hydroxide.
[embodiment 3]
The anion surfactant structural formula of preparation is as follows, wherein, and m
1+ m
2=8, n
1+ n
2=16, m
3+ m
4=15.
261 grams of (1 mole) dodecyl polyanilines are added in the 5L pressure reactor that whipping appts is housed, 5.2 grams of sodium hydroxide and 13.1 grams of Anhydrous potassium carbonates, carry out dewatering and nitrogen replacement with [embodiment 1], system temperature of reaction is adjusted to 110 DEG C and slowly passes into 354.2 grams of (8.05 moles) oxyethane, control pressure≤0.50MPa, after reacting ethylene oxide terminates, 933.8 grams of (16.1 moles) propylene oxide are slowly passed in 150 DEG C, control pressure≤0.60MPa, after propylene oxide reaction terminates, again temperature is adjusted to 140 DEG C slowly passes into 664.4 grams of (15.1 moles) oxyethane.After reaction terminates, with [embodiment 1] aftertreatment, obtain dodecyl polyaniline polyoxyethylene (8) polyoxypropylene (16) polyoxyethylene (15) ether gram, yield 95.2%.
1319.4 grams, dodecyl polyaniline polyoxyethylene (8) polyoxypropylene (16) polyoxyethylene (15) ether (0.6 mole) is mixed in the four-hole boiling flask of 2500 milliliters that are furnished with mechanical stirring, thermometer and reflux condensing tube with 13.4 grams of (0.24 mole) potassium hydroxide and 500 milliliters of toluene/benzene (v/v=1), be heated to 60 DEG C, divide and add 39.3 grams of (0.2 mole) 3-chlorine-2-hydroxyl propanesulfonates for 3 times, be warming up to back flow reaction after adding 9 hours.Cooling, with 20wt% hcl acidifying, divide and anhydrate and inorganic salt, steaming desolventizes, the mixture obtained is analyzed through high performance liquid chromatography (HPLC), and the mass ratio of dodecyl polyaniline polyoxyethylene (8) polyoxypropylene (16) polyoxyethylene (15) ether hydroxy-propanesulfonic acid and dodecyl polyaniline polyoxyethylene (8) polyoxypropylene (16) polyoxyethylene (15) ether is 0.54:1.The mixture obtained is mixed with water, with the pH=12 of the potassium hydroxide aqueous solution regulation system of 30wt%, obtains required nonionic and anion compounded surfactant S-3.
[embodiment 4]
With [embodiment 3], difference is dodecyl polyaniline polyoxyethylene (8) polyoxypropylene (16) polyoxyethylene (15) ether and 3-chlorine-2-hydroxyl propanesulfonate after reacting without the need to adding acid treatment, namely back flow reaction is after 9 hours, change water distilling apparatus into, solvent toluene/benzene (v/v=1) is removed in distillation, residuum adds water and stirs, and obtains nonionic and the anion compounded surfactant S-4 of chloride containing potassium and potassium hydroxide.
[embodiment 5]
The anion surfactant structural formula of preparation is as follows, wherein, and m
1+ m
2=4, n
1+ n
2=3, m
3+ m
4=20.
270 grams of (1 mole) stearylamines are added in the 5L pressure reactor that whipping appts is housed, 13.5 gram potassium hydroxide, when being heated to 80 ~ 90 DEG C, open vacuum system, dewater 1 hour under a high vacuum, then nitrogen replacement is used 3 ~ 4 times, system temperature of reaction is adjusted to 110 DEG C and slowly passes into 176.9 grams of (4.02 moles) oxyethane, control pressure≤0.50MPa, after reacting ethylene oxide terminates, 174.0 grams of (3 moles) propylene oxide are slowly passed in 150 DEG C, control pressure≤0.60MPa, after propylene oxide reaction terminates, again temperature is adjusted to 140 DEG C slowly passes into 893.2 grams of (20.3 moles) oxyethane.After reaction terminates, be cooled to 90 DEG C, vacuum removing low-boiling-point substance, neutralization after cooling, dehydration, obtain 1450.5 grams, stearylamine polyoxyethylene (4) polyoxypropylene (3) polyoxyethylene (20) ether, yield 96.7%.
750 grams, stearylamine polyoxyethylene (4) polyoxypropylene (3) polyoxyethylene (20) ether (0.5 mole) is mixed in the four-hole boiling flask of 2500 milliliters that are furnished with mechanical stirring, thermometer and reflux condensing tube with 7.5 grams of (0.11 mole) sodium ethylates and 700 milliliters of cyclopentanone, be heated to 60 DEG C, divide and add 12.2 grams of (0.1 moles) 1 for 3 times, 3-third sultone, is warming up to back flow reaction 3 hours after adding.Cooling, with 30wt% phosphoric acid, divide and anhydrate and inorganic salt, steaming desolventizes, the mixture obtained is analyzed through high performance liquid chromatography (HPLC), and the mass ratio of stearylamine polyoxyethylene (4) polyoxypropylene (3) polyoxyethylene (20) ether propanesulfonic acid and two stearylamine polyoxyethylene (4) polyoxypropylene (3) polyoxyethylene (20) ethers is 0.27:1.Being mixed with water by the mixture obtained, take concentration as the pH=12 of the triethylamine regulation system of 95wt%, obtains required nonionic and anion compounded surfactant S-5.
[embodiment 6]
The anion surfactant structural formula of preparation is as follows, wherein, and m
1+ m
2=5, n
1+ n
2=20, m
3+ m
4=10.
158 grams of (1 mole) decyl amine, 6.0 grams of potassium hydroxide are added in the 5L pressure reactor that whipping appts is housed, carry out dewatering and nitrogen replacement with [embodiment 1], system temperature of reaction is adjusted to 110 DEG C and slowly passes into 222.2 grams of (5.05 moles) oxyethane, control pressure≤0.60MPa, after reacting ethylene oxide terminates, 1165.8 grams of (20.1 moles) propylene oxide are slowly passed in 140 DEG C, control pressure≤0.60MPa, is adjusted to 150 DEG C again and slowly passes into 444.4 grams 10.1 moles after propylene oxide reaction terminates by temperature) oxyethane.After reaction terminates, with [embodiment 1] aftertreatment, obtain 1896.9 grams, decyl amine polyoxyethylene (5) polyoxypropylene (20) polyoxyethylene (10) ether, yield 95.9%.
1186.8 grams, decyl amine polyoxyethylene (5) polyoxypropylene (20) polyoxyethylene (10) ether (0.6 mole) is mixed in the four-hole boiling flask of 2500 milliliters that are furnished with mechanical stirring, thermometer and reflux condensing tube with 22.4 grams of (0.4 mole) potassium hydroxide and 600 milliliters of benzene, be heated to 50 DEG C points and add 33.3 grams of (0.2 mole) 2-monochloroethane sodium sulfonates for 3 times, be warming up to back flow reaction after adding 10 hours.Cooling, with 20wt% hcl acidifying, divide and anhydrate and inorganic salt, steaming desolventizes, the mixture obtained is analyzed through high performance liquid chromatography (HPLC), and the mass ratio of decyl amine polyoxyethylene (5) polyoxypropylene (20) polyoxyethylene (10) ether ethyl sulfonic acid and decyl amine polyoxyethylene (5) polyoxypropylene (20) polyoxyethylene (10) ether is 0.54:1.The mixture obtained is mixed with water, with the pH=13 of the diethanolamine aqueous solution regulation system of 75wt%, obtains required nonionic and anion compounded surfactant S-6.
[embodiment 7]
The anion surfactant structural formula of preparation is as follows, wherein, and m
1+ m
2=3, n
1+ n
2=10, m
3+ m
4=25.
298 grams of (1 mole) 20 amine, 4.8 grams of potassium hydroxide are added in the 5L pressure reactor that whipping appts is housed, carry out dewatering and nitrogen replacement with [embodiment 1], system temperature of reaction is adjusted to 110 DEG C and slowly passes into 132 grams of (3 moles) oxyethane, control pressure≤0.60MPa, after reacting ethylene oxide terminates, 585.8 grams of (10.1 moles) propylene oxide are slowly passed in 130 DEG C, control pressure≤0.60MPa, is adjusted to 140 DEG C again and slowly passes into 1113.2 grams of (25.3 moles) oxyethane after propylene oxide reaction terminates by temperature.After reaction terminates, with [embodiment 1] aftertreatment, obtain 2057.3 grams, 20 amine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (25) ether, yield 97.5%.
20 1055 grams, amine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (25) ethers (0.5 mole) are mixed in the four-hole boiling flask of 2500 milliliters that are furnished with mechanical stirring, thermometer and reflux condensing tube with 8 grams of (0.2 mole) sodium hydroxide and 800 milliliters of ethylbenzene, be heated to 60 DEG C points and add 16.7 grams of (0.1 mole) 2-monochloroethane sodium sulfonates for 3 times, after adding, be warming up to 120 DEG C of reactions 6 hours.Cooling, with 35wt% sulfuric acid acidation, divide and anhydrate and inorganic salt, steaming desolventizes, the mixture obtained is analyzed through high performance liquid chromatography (HPLC), and the mass ratio of 20 amine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (25) ether ethyl sulfonic acids and 20 amine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (25) ethers is 0.27:1.The mixture obtained is mixed with water, with the pH=13 of the aqueous sodium hydroxide solution regulation system of 20%, obtains required nonionic and anion compounded surfactant S-7.
[embodiment 8]
With [embodiment 7], difference is 20 amine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (25) ethers and 2-monochloroethane sodium sulfonate after reacting without the need to adding acid treatment, namely 120 DEG C of reactions are warming up to after 6 hours, change water distilling apparatus into, solvent ethylbenzene is removed in distillation, residuum adds water and stirs, and obtains nonionic and the anion compounded surfactant S-8 of sodium chloride-containing and sodium hydroxide.
[embodiment 9]
Preparation Shengli Oil Field high temperature and high salt block simulation salt solution, specifically consists of: total mineralization 32000mg/L, wherein Ca
2+for 1200mg/L, Mg
2+for 400mg/L, HCO
3 -for 20mg/L, all the other are sodium-chlor.
Oil water interfacial tension mensuration crude oil comes to oil field, and use after dehydration, viscosity of crude is 10mPa.s.The TX500 type that oil water interfacial tension is produced by Texas ,Usa university rotates and drips interfacial tensimeter mensuration.
By tensio-active agent S-1 ~ S-8 with analog salt water dissolution, measure different concns surfactant soln to the oil water interfacial tension of crude oil, the results are shown in Figure shown in 1a ~ 1c.
The tensio-active agent analog salt aqueous solution of 0.3wt% is loaded in 20 milliliters of peace a word used in place name bottles, after sealing, put into baking oven, measure the oil water interfacial tension of different digestion time rear surfaces promoting agent simulation salt solution pair and crude oil, see shown in Fig. 2 a ~ 2c.
[comparative example 1]
By the contrast table surface-active agent of 0.3wt% with analog salt water dissolution, carry out interface performance determination test with [embodiment 9], and compared with the tensio-active agent prepared with corresponding embodiment, the concentration of tensio-active agent is the results are shown in Table shown in 1.
In table 1, S-9 is mixing 12/14 (C
12 ~ 14) amine polyoxyethylene (3) polyoxypropylene (20) polyoxyethylene (8) ether; S-10 is dodecyl polyaniline polyoxyethylene (8) polyoxypropylene (16) polyoxyethylene (15) ether; S-11 is stearylamine polyoxyethylene (4) polyoxypropylene (3) polyoxyethylene (20) ether; S-12 is decyl amine polyoxyethylene (5) polyoxypropylene (20) polyoxyethylene (10) ether; S-13 is 20 amine polyoxyethylene (3) polyoxypropylene (10) polyoxyethylene (25) ethers.
[comparative example 2]
With [embodiment 1], difference is, be not that successively proceed step by step reacts, but after both being mixed, a step is reacted with propylene oxide and oxyethane.Namely slowly pass into 1171.6 grams of (20.2 moles) propylene oxide and 487.1 grams of (11.07 moles) ethylene oxide mixture at 110 ~ 150 DEG C, all the other are identical, obtain nonionic and anion compounded surfactant S-14.Carry out interface performance determination test with [embodiment 9], and compared with the tensio-active agent prepared with corresponding embodiment, the concentration of tensio-active agent is 0.3wt%, the results are shown in Table shown in 2.
[comparative example 3]
With [embodiment 3], difference is, be not that successively proceed step by step reacts, but after both being mixed, a step is reacted with propylene oxide and oxyethane.Namely 933.8 grams of (16.1 moles) propylene oxide and 1018.6 grams of (23.15 moles) ethylene oxide mixture are slowly passed at 110 ~ 150 DEG C, control pressure≤0.60MPa, all the other are identical, obtain nonionic and anion compounded surfactant S-15.Carry out interface performance determination test with [embodiment 9], and compared with the tensio-active agent prepared with corresponding embodiment, the concentration of tensio-active agent is 0.3wt%, the results are shown in Table shown in 2.
[comparative example 4]
With [embodiment 6], difference is, be not that successively proceed step by step reacts, but after both being mixed, a step is reacted with propylene oxide and oxyethane.Namely slowly pass into 1165.8 grams of (20.1 moles) propylene oxide and 666.6 grams of (15.15 moles) ethylene oxide mixture at 110 ~ 150 DEG C, all the other are identical, obtain nonionic and anion compounded surfactant S-16.Carry out interface performance determination test with [embodiment 9], and compared with the tensio-active agent prepared with corresponding embodiment, the concentration of tensio-active agent is 0.3wt%, the results are shown in Table shown in 2.
[comparative example 5]
With [embodiment 1], difference is, the consumption of sodium chloroacetate changes 349.5 grams (3 moles) into, the consumption of sodium ethylate changes into 163.7 grams (2.4 moles), all the other are identical, steam the product obtained after desolventizing to analyze through (HPLC), mixing 12/14 (C
12 ~ 14) amine polyoxyethylene (3) polyoxypropylene (20) polyoxyethylene (8) ether oxalic acid with mix 12/14 (C
12 ~ 14) mass ratio of amine polyoxyethylene (3) polyoxypropylene (20) polyoxyethylene (8) ether is 1:0.023.Take concentration as the pH=13 of the sodium hydroxide regulation system of 20wt%, add mixing 12/14 (C
12 ~ 14) amine polyoxyethylene (3) polyoxypropylene (20) polyoxyethylene (8) ether makes mixing 12/14 (C
12 ~ 14) amine polyoxyethylene (3) polyoxypropylene (20) polyoxyethylene (8) ether oxalic acid with mix 12/14 (C
12 ~ 14) mass ratio of amine polyoxyethylene (3) polyoxypropylene (20) polyoxyethylene (8) ether is obtain tensio-active agent S-17 after 0.54:1 mixes.Carry out interface performance determination test with [embodiment 9], and compared with the tensio-active agent prepared with corresponding embodiment, the concentration of tensio-active agent is 0.3wt%, the results are shown in Table shown in 2.
Table 1
| Tensio-active agent | Temperature (DEG C) | IFT(mN/m) |
| S-1 | 85 | 0.00067 |
| S-2 | 85 | 0.00099 |
| S-9 | 85 | 0.205 |
| S-3 | 90 | 0.00077 |
| S-4 | 90 | 0.00092 |
| S-10 | 90 | 0.0872 |
| S-5 | 90 | 0.00288 |
| S-11 | 90 | 0.0874 |
| S-6 | 80 | 0.00177 |
| S-12 | 80 | 0.0745 |
| S-7 | 80 | 0.00243 |
| S-8 | 80 | 0.00082 |
| S-13 | 80 | 0.0633 |
Table 2
| Tensio-active agent | Temperature (DEG C) | IFT(mN/m) |
| S-1 | 85 | 0.00067 |
| S-2 | 85 | 0.00099 |
| S-14 | 85 | 0.00654 |
| S-3 | 90 | 0.00077 |
| S-4 | 90 | 0.00092 |
| S-15 | 90 | 0.00821 |
| S-6 | 80 | 0.00177 |
| S-16 | 80 | 0.01202 |
| S-1 | 85 | 0.00067 |
| S-17 | 85 | 0.3354 |
Claims (10)
1. for the tensio-active agent of the high temperature and high salt oil deposit displacement of reservoir oil, comprise the anion surfactant shown in the nonionogenic tenside shown in formula (1) and formula (2), the mass ratio of wherein said anion surfactant and described nonionogenic tenside is (0.1 ~ 1): 1;
R
1and R
2for identical or not identical C
4~ C
40aliphatic group or by C
4~ C
30the aryl of the saturated and unsaturated alkyl replacement of straight or branched; M1, m2, m3 or m4 are independently selected from 0 ~ 50, but m1 and m2, m3 and m4 can not be 0 simultaneously; N1 and n2 is independently selected from 0 ~ 100, but n1 and n2 can not be 0 simultaneously; R1, r2, r3 or r4 are independently selected from 0 ~ 50, but r1 and r2, r3 and r4 can not be 0 simultaneously; S1 and s2 is independently selected from 0 ~ 100, but s1 and s2 can not be 0 simultaneously; Z
1for-R
01y
1; R
01be selected from C
1~ C
5alkylidene group or hydroxyl substituted alkylene, Y
1be selected from SO
3m or COON, M and N are selected from hydrogen, basic metal or by formula NR
3(R
4) (R
5) (R
6) shown group, R
3, R
4,r
5,r
6for being independently selected from H, (CH
2)
poH or (CH
2)
qcH
3, the arbitrary integer in p=2 ~ 4, q=0 ~ 5.
2. the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil according to claim 1, is characterized in that described R
1or R
2in at least one be C
6~ C
20alkyl or by C
8~ C
16the phenyl that alkyl replaces.
3. the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil according to claim 1, is characterized in that p=2, q=0 ~ 1.
4. the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil according to claim 1, is characterized in that m1+m2=2 ~ 10, m3+m4=5 ~ 30, n1+n2=2 ~ 20; And/or r1+r2=2 ~ 10, r3+r4=5 ~ 30, s1+s2=2 ~ 20.
5. the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil according to claim 1, comprises the following steps:
A, basic catalyst exist under, R
1nH
2r is obtained successively with aequum oxyethane, propylene oxide, reacting ethylene oxide
1n ((CH
2cH
2o)
m1(CHCH
3cH
2o)
n1(CH
2cH
2o)
m3h) ((CH
2cH
2o)
m2) (CHCH
3cH
2o)
n2(CH
2cH
2o)
m4h);
B, the product that step a is obtained and X
1r
01y
01and alkali metal hydroxide or alkali metal alcoholates are with mol ratio (2 ~ 10): 1:(1 ~ 10) in a solvent, within 3 ~ 15 hours, obtain the mixture of the anion surfactant containing the nonionogenic tenside shown in formula (1) and formula (3) depicted in temperature of reaction 50 ~ 120 DEG C reaction;
Wherein, Z
01for-R
01y
01; Y
01be selected from SO
3m
1or COON
1, M
1and N
1for basic metal, X
1be selected from chlorine, bromine or iodine.
6. the preparation method of the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil according to claim 5, is characterized in that the R described in step b
1n ((CH
2cH
2o)
m1(CHCH
3cH
2o)
n1(CH
2cH
2o)
m3h) ((CH
2cH
2o)
m2) (CHCH
3cH
2o)
n2(CH
2cH
2o)
m4h): X
1r
01y
01: the mol ratio of alkali metal hydroxide or alkali metal alcoholates is (3 ~ 5): 1: (1.1 ~ 2).
7. the preparation method of the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil according to claim 5, is characterized in that the solvent described in step b is selected from C
3~ C
8ketone and C
6~ C
9aromatic hydrocarbons at least one.
8. the preparation method of the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil according to claim 1, comprises the following steps:
B product and 1 that claim 5 step a obtains by (), 3-third sultone and alkali metal hydroxide or alkali metal alcoholates are with mol ratio (2 ~ 10): 1:(1 ~ 10) in a solvent, within 3 ~ 15 hours, obtain the mixture containing the nonionogenic tenside shown in formula (1) and the anion surfactant shown in formula (4) in temperature of reaction 50 ~ 120 DEG C reaction;
Wherein Z
03for-CH
2cH
2cH
2sO
3m
2; M
2for basic metal.
9. the preparation method of the tensio-active agent for the high temperature and high salt oil deposit displacement of reservoir oil according to claim 8, is characterized in that the R described in step (b)
1n ((CH
2cH
2o)
m1(CHCH
3cH
2o)
n1(CH
2cH
2o)
m3h) ((CH
2cH
2o)
m2) (CHCH
3cH
2o)
n2(CH
2cH
2o)
m4h): 1,3-third sultone: the mol ratio of alkali metal hydroxide or alkali metal alcoholates is (3 ~ 5): 1: (1.1 ~ 2).
10. the application of tensio-active agent in the displacement of reservoir oil of oil field for the high temperature and high salt oil deposit displacement of reservoir oil according to claim 1, is characterized in that the total mineralization 30000 ~ 35000mg/L of the formation brine of described high temperature and high salt oil deposit, wherein Ca
2+be 1000 ~ 1500mg/L, Mg
2+be 200 ~ 600mg/L, HCO
3 -be 5 ~ 40mg/L; Viscosity of crude is 5 ~ 15mPa.s; Formation temperature is 75 ~ 90 DEG C.
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| CN102277148A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Composition for improving recovery ratio of crude oil and preparation method thereof |
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2014
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| CN102277148A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Composition for improving recovery ratio of crude oil and preparation method thereof |
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| DE102012003224A1 (en) * | 2012-02-20 | 2013-08-22 | Sasol Germany Gmbh | Drilling fluid, use and method using the drilling fluid |
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