CN103666411A - Compound oil base emulsifier containing fatty alcohol polyoxyethylene polypropylene ether sulfonate and preparation method of compound oil base emulsifier - Google Patents
Compound oil base emulsifier containing fatty alcohol polyoxyethylene polypropylene ether sulfonate and preparation method of compound oil base emulsifier Download PDFInfo
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Abstract
The invention relates to a compound oil base emulsifier containing fatty alcohol polyoxyethylene polypropylene ether sulfonate and a preparation method of the compound oil base emulsifier, which mainly solve the problem that the emulsion of the oil base drilling fluid has poor stability and does not resist salt and temperature. According to the compound oil base emulsifier containing fatty alcohol polyoxyethylene polypropylene ether sulfonate, a non-ionic surface active agent, an anionic surfactant, oil and water and a preparation method thereof, the problem is well solved. The compound oil base emulsifier can be used in special drilling operation of special wells and offshore horizontal wells with strong water sensitivity, high temperature stratum and large displacement.
Description
Technical field
The present invention relates to composite oil base emulsifying agent of a kind of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate and preparation method thereof.
Background technology
Along with continuous minimizing and the exploitation difficulty of prospective oil, countries in the world have been strengthened the input to deep formation Oil And Gas Exploration And Development one after another, develop an urgent demand that new oil reservoir has become current each major oil companies' development.China's hydrocarbon resources to be verified is mainly distributed in Tarim Basin, Zhunger Basin, Qaidam, tells the basins such as Kazakhstan, Sichuan, 73% of its stock number is imbedded in deep layer, and underground condition complex, so deep-well and ultra deep well oil gas drilling and supporting development technique have become the key factor of restriction petrol resources exploitation.Along with the increase of depth of stratum, the formation temperature of deep-well, ultra deep well also can be more and more higher, and can the hot environment on stratum maintain stable performance to drilling fluid and bring great challenge.
Drilling fluid is as the important component part of drilling engineering, and its performance is directly connected to drilling quality, drilling cost and the drilling period of deep-well, ultra deep well.With respect to water-base drilling fluid; oil base drilling fluid has stronger anti-collapse inhibition, oilness and good reservoir protection performance; especially strong water-sensitive and high temperature, ultrahigh-temperature stratum can be met, or the special drilling well needs that turn such as large displacement exceptional well and marine horizontal well need to be bored.Oil base drilling fluid, claims again invert mud, oil, water, emulsifying agent, fluid loss agent, equilibrium of activation agent, flow pattern regulator etc., consists of.Between 5～30%, (water content is generally called full oil base drilling fluid 5% with interior to normally used invert mud water content, be not called invert mud), but high temperature resistance reaches the content of water in 180 ℃ of above invert muds generally 5～10%, seldom surpasses 15%.The content of water increases, taking bits property, filtration reduction and suspension, rheological all improves, but thermostability and elctrical stability be variation all, as CN1660958 has reported a kind of synthetic base drilling fluid, the mixture that the primary emulsion using is AESA and polyoxyethylene nonylphenol ether, although still have good rheological and emulsion-breaking voltage at 150 ℃ after aging 16 hours, water-content is up to 25%, and the performance under higher temperature and water-content has no report.Oil base drilling fluid is because base fluid be take oil as main, therefore expensive, cost is high, full oil base drilling fluid is all the more so, as CN101215461 has reported a kind of complete-oil synthetic base drilling fluid, the emulsifying agent of use is one or more the mixture in long chain fatty acid acid amides, long alkyl chain length Phenylsulfonic acid calcium, polyolefine carboxylicesters, although have low toxicity, environmental protection, to advantages such as reservoir damage are little, but its preparation cost is high, has limited it and promoted the use of.
Of less types as oil base drilling fluid emulsifying agent is provided in the market, and the emulsifying agent kind that report is used for intensified oil reduction is relatively many, as US4485873, US4545912, CN100531884 etc. have reported that polyxyethylated alkylphenol acetate, two tail chain polyoxyethylene sulfonate, alkyl-fragrant benzyl-polyethenoxy ether negatively charged ion surfactant are in the application aspect intensified oil reduction, but do not relate to its purposes aspect well-drilling liquid emulgent.
Oil base drilling fluid develops slower owing to being subject to the restriction of cost, environmental requirement always, the block of application is also less, along with existing oilfield reserve declines day by day, and the exploitation in new exploratory area can run into various bad grounds and environment, what be badly in need of excellent property prepares oil base drilling fluid emulsifying agent, and to solve, existing oil base drilling fluid emulsion-stabilizing performance is poor, the problem of salt tolerant, non-heatproof not.By improving the ratio of water in oil base drilling fluid, reach the Cost Problems that reduces oil base drilling fluid, for the operation of widespread use oil base drilling fluid provides technical guarantee.In the described this high-moisture situation just of invention, be suitable for preparing the preparation method of the oil base composite emulsifier that stability and high efficiency oil base drilling fluid uses.
Summary of the invention
One of technical problem to be solved by this invention is poor, the problem of salt tolerant, non-heatproof not of oil base drilling fluid emulsion-stabilizing performance in prior art, and a kind of new composite oil base emulsifying agent of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate is provided.Oil base drilling fluid with the composite oil base emulsifying agent preparation of this fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate has advantages of that heat-resistant salt-resistant performance is good, emulsion-stabilizing performance is good.Two of technical problem to be solved by this invention is to provide a kind of preparation method of the fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate composite oil base emulsifying agent corresponding with one of technical solution problem.
In order one of to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the composite oil base emulsifying agent of a kind of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate, comprises following component in mass fraction:
The aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate of (1) 0.5～6 part;
The nonionogenic tenside of (2) 0.5～5 parts;
The anion surfactant of (3) 0.1～3 parts;
The oil of (4) 5～50 parts;
The water of (5) 0.1～1 parts;
Wherein the general molecular formula of (1) component is:
In formula: M is any one ion being selected from hydrogen, calcium, magnesium, barium, zinc, aluminium or iron, and R is C
8～C
30alkyl, m is the adduction number of ethoxy group EO, its span is any one integer in 1～10, n is the adduction number of the PO of propoxy-group, its span is any one integer in 1～40, x span is any one integer in 1～3.
In technique scheme, described ion preferred version is hydrogen, calcium, magnesium or zinc; R preferred version is C
8～C
20alkyl; M preferred version is any one integer in 1～6; N preferred version is any one integer in 3～35; X preferred version is 1 or 2.Described nonionogenic tenside preferred version is selected from this dish or tween or higher fatty acid amide.This described dish series of surfactants preferred version is selected from least one in this dish 20, this dish 40, this dish 60, span 80 or this dish 85; Tween series of surfactants preferred version is selected from least one in polysorbas20, polysorbate40, polysorbate60, tween 80 or polysorbate85; Higher fatty acid amide series of surfactants preferred version is selected from least one in lauroyl diethanolamine, cocounut oil acyl diethanolamine, myristoyl diethanolamine, palmitoleoyl diethanolamine, oleoyl diethanolamine or hard acyl diethanolamine.Described anion surfactant preferred version is chain alkyl sulfuric acid or long-chain alkyl benzene sulfonate.Described chain alkyl sulfuric acid preferred version is selected from carbon chain length C
12～C
18sodium sulfate; Long-chain alkyl benzene sulfonate is selected from carbon chain length C
12～C
24benzene sulfonic acid sodium salt; Described oily preferred version is selected from white oil or whiteruss; Described water preferred version is selected from deionized water.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of the composite oil base emulsifying agent of a kind of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate, comprises the following steps:
(a) preparation of aliphatic alcohol polyethenoxy polyethenoxy ether:
By fatty alcohol and oxyethane, propylene oxide, by required proportioning, in temperature of reaction, be 85～160 ℃, pressure is less than under 0.80MPa gauge pressure condition, and calcium barium bimetal compound is catalyzer, reacts to obtain aliphatic alcohol polyethenoxy polyethenoxy ether; Wherein the mol ratio of fatty alcohol and oxyethane, propylene oxide is 1: 1～15: 1～50, and catalyst levels is 1.0～8.0 % of fatty alcohol quality;
(b) preparation of chloro fat alcohol polyoxyethylene poly-oxygen propylene aether:
The aliphatic alcohol polyethenoxy polyethenoxy ether of step (a) synthesized is reacted 3～10 hours at 70～100 ℃ by required proportioning with thionyl chloride, pyridine by required proportioning, excessive thionyl chloride is extracted in decompression out, in and layering remove inorganic salt, vacuum-drying obtains chloro fat alcohol polyoxyethylene poly-oxygen propylene aether; Wherein, the mol ratio of aliphatic alcohol polyethenoxy polyethenoxy ether, thionyl chloride and pyridine is 1: 1～3: 0.5～2.5;
(c) preparation of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonic acid (x=1)
The chloro fat alcohol polyoxyethylene poly-oxygen propylene aether of step (b) synthesized is placed in to reactor, the solvent 1 that adds required proportioning, mixture and the water of ammediol, sulphonating agent S-WAT or S-WAT and sodium bisulfite, at 90～150 ℃, react 3～9 hours, then through steaming water, aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonic acid (x=1) neutralizes, desalts and to obtain.Wherein, sulfonated reagent is the mixture of S-WAT or S-WAT and sodium bisulfite, and the mol ratio of chloro fat alcohol polyoxyethylene poly-oxygen propylene aether and sulfonated reagent is 1: 1.5～2.5,1, ammediol consumption is 4～10% of reactant quality, and water consumption is 5～20% of reactant quality;
(d) preparation of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate (x=2 or 3)
By the aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonic acid of step (c) synthesized by required proportioning and water, M (OH)
xor MO (M
2o
3) add respectively in autoclave, in temperature of reaction, be 50～120 ℃, the reaction times is 0.5～5 hour, under 0.60MPa gauge pressure condition, reacts to obtain aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate; Wherein the mol ratio of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonic acid and oxyhydroxide or oxide compound is 1.5～3: 1, and the mass percent that water accounts for the total material of reaction is 60～90%, M (OH)
xor MO (M
2o
3) Average Particle Diameters be 200nm～200 μ m;
(e) aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate, nonionogenic tenside, anion surfactant, base oil and the water of aequum are added in reaction flask successively, be warming up to 30～80 ℃ and stir 1～4 hour, obtain required composite oil base emulsifying agent.In mass fraction, the proportioning of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate, nonionogenic tenside, anion surfactant, oil and water is 0.5～6 part: 0.5～5 part: 0.1～3 part: 5～50 parts: 0.5～3 part.
In technique scheme, (a) the temperature of reaction preferable range in step is 120～160 ℃, and pressure preferable range is 0.30～0.60MPa gauge pressure; Fatty alcohol and oxyethane, propylene oxide mole preferably than being 1: 1～5: 5～35, catalyst levels is preferably 2.5～5.0% of fatty alcohol quality; (b) in step the mol ratio of aliphatic alcohol polyethenoxy polyethenoxy ether, thionyl chloride and pyridine be preferably 1: 1.5～2.5: 1～2, temperature of reaction is preferably 75～90 ℃, the reaction times is preferably 4～8 hours; (c) in step the mol ratio of chloro fat alcohol polyoxyethylene poly-oxygen propylene aether and sulfonated reagent be preferably 1: 1.5～2,1, ammediol consumption is preferably 5～8% of reactant quality, water consumption is preferably 10～15% of reactant quality, temperature of reaction is preferably 110～140 ℃, and the reaction times is preferably 4～8 hours; (d) aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonic acid and M (OH) in step
xor MO (M
2o
3) mol ratio be preferably 1.8～2.5: 1, water account for reaction total material mass percent be preferably 70～85%, M (OH)
xor MO (M
2o
3) Average Particle Diameters be preferably 400nm～100 μ m, temperature of reaction is preferably 60～90 ℃, the reaction times is preferably 1～3 hour; (e) in mass fraction, the consumption preferable range of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate is 1～4 part, the consumption preferable range of nonionogenic tenside is 1～4 part, the consumption preferable range of anion surfactant is 0.5～1 part, the consumption preferable range of oil is 10～40 parts, the consumption preferable range of water is 0.3～0.7 part, and temperature of reaction is preferably 40～70 ℃, and churning time is preferably 2～3 hours.
The composite oil base emulsifying agent of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate prepared by the present invention, owing to containing polyoxyethylene, polyoxypropylene non-ionic group and azochlorosulfonate acid anion group in aliphatic alcohol polyethenoxy polyethenoxy ether sulfonate molecules structure simultaneously, make the salt tolerant advantage of its heat resistance that has anion surfactant concurrently and nonionogenic tenside, between each tensio-active agent, have well collaborative Emulsification effect, be a kind of composite oil base emulsifying agent for oil base drilling fluid that is suitable for high temperature and high salt stratum simultaneously.
The oil base drilling fluid of the composite oil base emulsifying agent of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate prepared by employing the present invention, its chief component comprises following component: 70～90 parts of base oils, 10～30 parts, water, 1～5 part of emulsifying agent, 2～5 parts of organophilic clays, 0.5～3 part of fluid loss agent, 0.5～3 part of pH adjusting agent.This oil base drilling fluid heatproof reaches 180 ℃, API filtration≤3ml, high temperature ageing front and back emulsion-breaking voltage >=800V, is that a kind of heat-resistant salt-resistant excellent property, filter loss are little, the oil base drilling fluid system of good emulsion stability, has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonic acid (x=1).
Fig. 2 is the infrared spectrogram of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate (x=2 or 3).
Aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonic acid and salt prepared by the present invention can characterize by the following method: after synthetics is purified, application U.S. Nicolet-380 FT-IR spectrograph, adopts pressing potassium bromide troche or liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), determine the chemical structure of sample, to reach the Infrared Characterization to compound of the present invention.
As shown in Figure 1, wave number 2921cm
-1, 2851cm
-1for methyl on alkyl chain and the flexible characteristic peak of methylene radical C-H, at wave number 725 cm
-1there is the characteristic peak waving in chain alkyl C-H face; Wave number 1713cm
-1charateristic avsorption band for carboxylic acid; 1350cm
-1the peak of the left and right characteristic peak that is sulfonate is that antisymmetric stretching vibration and the vibration of skeleton carbon due to S=O causes; Wave number 1115cm
-1absorption peak for C-O-C key.
As shown in Figure 2, wave number 2915cm
-1, 2860cm
-1for methyl on alkyl chain and the flexible characteristic peak of methylene radical C-H, at wave number 725 cm
-1there is the characteristic peak waving in chain alkyl C-H face; Wave number 1616cm
-1charateristic avsorption band for carboxylate salt; 1352cm
-1peak, left and right is the characteristic peak of sulfonate, is to cause due to the antisymmetric stretching vibration of S=O and the vibration of skeleton carbon; Wave number 1110cm
-1absorption peak for C-O-C key.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
(a) lauryl alcohol polyoxyethylene poly-oxygen propylene aether (m=3, n=15) is synthetic
To being equipped with in the reactor of condensing works, whipping appts and gas distributor, add 186 grams of (1 mole) lauryl alcohols, 3.0 grams of calcium oxide and 2.6 grams of barium oxide, when logical nitrogen limit, limit is heated to 135 ℃, add 20 grams of water, stirring reaction 1 hour.Remove after moisture, be cooled to 80 ℃, the sulfuric acid (20wt%) that slowly drips catalyst neutralisation theoretical amount makes the calcium barium bimetallic catalyst reaction solution system of high reactivity, highly selective, system temperature is heated to 80～90 ℃, open vacuum system, under high vacuum, dewater 2 hours, then use nitrogen purging 3～4 times, system temperature of reaction is adjusted to 150 ℃ and slowly passes into 132 grams of (3 moles) oxyethane, control pressure≤0.40MPa, after reacting ethylene oxide finishes, be that 150 ℃ slowly pass into 870 grams of (15 moles) propylene oxide, control pressure≤0.50MPa.After reaction finishes, use nitrogen purging system, cooling rear neutralization, dehydration, obtain 1141.7 grams of lauryl alcohol polyoxyethylene poly-oxygen propylene aethers (m=3, n=15), molar yield 96.1%.
(b) chloro lauryl alcohol polyoxyethylene poly-oxygen propylene aether (m=3, n=15) is synthetic
By the lauryl alcohol polyoxyethylene poly-oxygen propylene aether (m=3 of step (a) synthesized, n=15) 1141.7 grams (0.961 mole), 75.9 grams of (0.961 mole) pyridines are placed in backflow are housed, stir, in 2000 milliliters of there-necked flasks of gas absorbing device, under agitation slowly drip 171.5 grams of sulfur oxychlorides (1.442 moles), 80 ℃ of reactions 6 hours, reaction finishes the excessive thionyl chloride of rear pressure reducing and steaming, residuum is cooling, stratification, upper strata is neutralized to neutrality with 30% sodium hydroxide solution, divide and remove inorganic salt, organic layer washes with water 3～4 times again, vacuum-drying obtains chloro lauryl alcohol polyoxyethylene poly-oxygen propylene aether (m=3, n=15) 1035.4 grams, molar yield 89.3%.
(c) lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=3, n=15) is synthetic
By the chloro lauryl alcohol polyoxyethylene poly-oxygen propylene aether (m=3 of step (b) synthesized, n=15) 1035.4 grams (0.858 moles) are placed in autoclave, add 62.1 gram 1, ammediol, 124.3 grams of water, 156.3 grams of S-WATs (1.240 moles) and 31.7 grams of sodium bisulfites (0.305 mole), at 120 ℃ of temperature, react 6 hours, reaction finishes rear underpressure distillation and boils off most of moisture, in mixture, add appropriate Virahol standing over night, the inorganic salt that filtering is precipitated out. solvent is removed in decompression, cooling, neutralization, add again the further filtering inorganic salt of appropriate methylene dichloride, obtain lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=3, n=15) 914.2 grams, molar yield is 85.1%.
(d) lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl calcium sulphonate (m=3, n=15) is synthetic
To being furnished with the lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=3 that adds respectively step (c) synthesized in churned mechanically high-pressure reactor, n=15) 914.2 grams (0.730 mole), 20.4 grams of (0.365 mole) CaO (Average Particle Diameters is 40 μ m) and 3738.4 grams of water, be heated to 70 ℃, it is to react 2.5 hours under 0.60MPa gauge pressure condition that logical nitrogen makes system pressure, after reaction finishes, cooling, branch vibration layer, product is dried, obtain 909.4 grams of lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl calcium sulphonate (m=3, n=15).
To synthetic lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl calcium sulphonate (m=3, n=15), application U.S. Nicolet-5700 infrared spectrometer, adopts pressed disc method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), there is the characteristic peak shown in Fig. 2.
(e) by percentage to the quality, get synthetic lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl calcium sulphonate (m=3, n=15) 3 parts, this 85 1 parts, dish, 0.5 part of sodium lauryl sulphate, 0.5 part and 30 parts whiterusss of water add in reaction flask successively, being warming up to 60 ℃ stirs 3 hours, obtain required composite oil base emulsifying agent oil solution, wherein compound emulsion agent content is 12.9% by percentage to the quality.
[embodiment 2]
(a) hexadecanol polyoxyethylene poly-oxygen propylene aether (m=2, n=6) is synthetic
To being equipped with in the reactor of condensing works, whipping appts and gas distributor, add 242 grams of (1 mole) hexadecanols, 4.5 grams of calcium oxide and 3.0 grams of barium oxide, when logical nitrogen limit, limit is heated to 135 ℃, add 20 grams of water, stirring reaction 1 hour.Remove after moisture content, be cooled to 80 ℃, the sulfuric acid (20wt%) that slowly drips catalyst neutralisation theoretical amount makes high reactivity, the Compositional type calcium barium bimetallic catalyst reaction solution system of highly selective, system temperature is heated to 80～90 ℃, open vacuum system, under high vacuum, dewater 2 hours, then use nitrogen purging 3～4 times, system temperature of reaction is adjusted to 140 ℃ and slowly passes into 88 grams of (2 moles) oxyethane, control pressure≤0.40MPa, after reacting ethylene oxide finishes, be that 160 ℃ slowly pass into 348 grams of (6 moles) propylene oxide, control pressure≤0.60MPa.After reaction finishes, use nitrogen purging system, cooling rear neutralization, dehydration, obtain 659.0 grams of hexadecanol polyoxyethylene poly-oxygen propylene aethers (m=2, n=6), molar yield 97.2 %.
(b) chloro hexadecanol polyoxyethylene poly-oxygen propylene aether (m=2, n=6) is synthetic
By the hexadecanol polyoxyethylene poly-oxygen propylene aether (m=2 of step (a) synthesized, n=6) 659.0 grams (0.972 mole), 115.2 grams of (1.458 moles) pyridines are placed in 2000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed, under agitation slowly drip 231.3 grams of sulfur oxychlorides (1.944 moles), 75 ℃ of reactions 8 hours, reaction finishes aftertreatment with [embodiment 1] (b), obtain chloro hexadecanol polyoxyethylene poly-oxygen propylene aether (m=2, n=6) 586.3 grams, molar yield 86.6%.
(c) hexadecanol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=2, n=6) is synthetic
By the chloro hexadecanol polyoxyethylene poly-oxygen propylene aether (m=2 of step (b) synthesized, n=6) 586.3 grams (0.842 moles) are placed in autoclave, add 46.9 gram 1, ammediol, 87.9 grams of water, 170.1 grams of S-WATs (1.350 moles) and 34.5 grams of sodium bisulfites (0.332 mole), at 130 ℃ of temperature, react 7 hours, all the other operations with [embodiment 1] (c), obtain hexadecanol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=2, n=6) 529.8 grams, molar yield is 84.8%.
(d) hexadecanol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid zinc (m=2, n=6) is synthetic
To being furnished with the hexadecanol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=2 that adds respectively step (c) synthesized in churned mechanically high-pressure reactor, n=6) 529.8 grams (0.714 mole), 32.3 grams of (0.397 mole) CaO (Average Particle Diameters is 500nm) and 3185.2 grams of water, be heated to 65 ℃, it is to react 3 hours under 0.60MPa gauge pressure condition that logical nitrogen makes system pressure, after reaction finishes, cooling, branch vibration layer, product is dried, obtain 542.6 grams, hexadecanol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid zinc (m=2, n=6).
To synthetic hexadecanol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid zinc (m=2, n=6), application U.S. Nicolet-5700 infrared spectrometer, adopts pressed disc method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), there is the characteristic peak shown in Fig. 2.
(e) by percentage to the quality, get synthetic hexadecanol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid zinc (m=2, n=6) 3 parts, 0.5 part of polysorbate40,0.5 part of hexadecyl benzene sulfonic acid sodium salt, 0.3 part and 30 parts whiterusss of water add in reaction flask successively, being warming up to 70 ℃ stirs 2 hours, obtain required composite oil base emulsifying agent oil solution, wherein compound emulsion agent content is 11.7% by percentage to the quality.
[embodiment 3]
(a) octanol polyoxyethylene poly-oxygen propylene aether (m=1, n=35) is synthetic
To being equipped with in the reactor of condensing works, whipping appts and gas distributor, add 130 grams of (1 mole) octanols, 3.7 grams of calcium oxide and 3.0 grams of barium oxide, when logical nitrogen limit, limit is heated to 135 ℃, add 25 grams of water, stirring reaction 1 hour.Remove after moisture content, be cooled to 80 ℃, the sulfuric acid (20wt%) that slowly drips catalyst neutralisation theoretical amount makes the calcium barium bimetallic catalyst reaction solution system of high reactivity, highly selective, system temperature is heated to 80～90 ℃, open vacuum system, under high vacuum, dewater 2 hours, then use nitrogen purging 3～4 times, system temperature of reaction is adjusted to 120 ℃ and slowly passes into 44 grams of (1 mole) oxyethane, control pressure≤0.40MPa, after reacting ethylene oxide finishes, be that 150 ℃ slowly pass into 2030 grams of (35 moles) propylene oxide, control pressure≤0.50MPa.After reaction finishes, use nitrogen purging system, cooling rear neutralization, dehydration, obtain 2126.9 grams of octanol polyoxyethylene poly-oxygen propylene aethers (m=1, n=35), molar yield 96.5%.
(b) chloro octanol polyoxyethylene poly-oxygen propylene aether (m=1, n=35) is synthetic
By the octanol polyoxyethylene poly-oxygen propylene aether (m=1 of step (a) synthesized, n=35) 1102.0 grams (0.5 mole), 71.1 grams of (0.9 mole) pyridines are placed in 2000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed, under agitation slowly drip 119.0 grams of sulfur oxychlorides (1.0 moles), 85 ℃ of reactions 4 hours, reaction finishes aftertreatment with [embodiment 1] (b), obtain chloro octanol polyoxyethylene poly-oxygen propylene aether (m=1, n=35) 891.2 grams, molar yield 80.2%.
(c) octanol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=1, n=35) is synthetic
By the chloro octanol polyoxyethylene poly-oxygen propylene aether (m=1 of step (b) synthesized, n=35) 891.2 grams (0.4 moles) are placed in autoclave, add 44.6 gram 1, ammediol, 89.1 grams of water, 60.6 grams of S-WATs (0.481 mole) and 12.3 grams of sodium bisulfites (0.118 mole), at 140 ℃ of temperature, react 4 hours, all the other operations with [embodiment 1] (c), obtain octanol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=1, n=35) 730.3 grams, molar yield is 80.5%.
To synthetic octanol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=1, n=35), application U.S. Nicolet-5700 infrared spectrometer, adopts liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), there is the characteristic peak shown in Fig. 1.
(e) by percentage to the quality, get synthetic octanol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=1, n=35) 1 part, this 40 4 parts, dish, 0.5 part of sodium lauryl sulphate, 0.5 part and 10 parts whiterusss of water add in reaction flask successively, being warming up to 50 ℃ stirs 2 hours, obtain required composite oil base emulsifying agent oil solution, wherein compound emulsion agent content is 34.4% by percentage to the quality.
[embodiment 4]
(a) octodecyl alcohol polyoxyethylene polyethenoxy ether (m=5, n=8) is synthetic
To being equipped with in the reactor of condensing works, whipping appts and gas distributor, add 270 grams of (1 mole) stearyl alcohol, 5.0 grams of calcium oxide and 3.1 grams of barium oxide, when logical nitrogen limit, limit is heated to 135 ℃, add 25 grams of water, stirring reaction 1 hour.Remove after moisture content, be cooled to 80 ℃, the sulfuric acid (20wt%) that slowly drips catalyst neutralisation theoretical amount makes the calcium barium bimetallic catalyst reaction solution system of high reactivity, highly selective, system temperature is heated to 80～90 ℃, open vacuum system, under high vacuum, dewater 2 hours, then use nitrogen purging 3～4 times, system temperature of reaction is adjusted to 130 ℃ and slowly passes into 220 grams of (5 moles) oxyethane, control pressure≤0.40MPa, after reacting ethylene oxide finishes, be that 150 ℃ slowly pass into 464 grams of (8 moles) propylene oxide, control pressure≤0.50MPa.After reaction finishes, use nitrogen purging system, cooling rear neutralization, dehydration, obtain 937.8 grams of octodecyl alcohol polyoxyethylene polyethenoxy ethers (m=5, n=8), molar yield 98.3%.
(b) chloro octodecyl alcohol polyoxyethylene polyethenoxy ether (m=5, n=8) is synthetic
By the octodecyl alcohol polyoxyethylene polyethenoxy ether (m=5 of step (a) synthesized, n=8) 937.8 grams (0.983 mole), 93.2 grams of (1.180 moles) pyridines are placed in 2000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed, under agitation slowly drip 175.5 grams of sulfur oxychlorides (1.475 moles), 90 ℃ of reactions 5 hours, reaction finishes aftertreatment with [embodiment 1] (b), obtain chloro octodecyl alcohol polyoxyethylene polyethenoxy ether (m=5, n=8) 865.2 grams, molar yield 90.5%.
(c) octodecyl alcohol polyoxyethylene polyethenoxy ether isopropyl sulfonic acid (m=5, n=8) is synthetic
By the chloro octodecyl alcohol polyoxyethylene polyethenoxy ether (m=5 of step (b) synthesized, n=8) 865.2 grams (0.890 moles) are placed in autoclave, add 69.2 gram 1, ammediol, 121.1 grams of water, 143.9 grams of S-WATs (1.143 moles) and 29.2 grams of sodium bisulfites (0.281 mole), at 110 ℃ of temperature, react 8 hours, all the other operations with [embodiment 1] (c), obtain octodecyl alcohol polyoxyethylene polyethenoxy ether isopropyl sulfonic acid (m=5, n=8) 760.2 grams, molar yield is 83.9%.
(d) octodecyl alcohol polyoxyethylene polyethenoxy ether isopropyl calcium sulphonate (m=5, n=8) is synthetic
To being furnished with octodecyl alcohol polyoxyethylene polyethenoxy ether isopropyl sulfonic acid (m=5, n=8) 760.2 grams of (0.747 mole), 24.1 grams of (0.325 mole) Ca (OH) that add respectively step (c) synthesized in churned mechanically high-pressure reactor
2(Average Particle Diameters is 80 μ m) and 1830.0 grams of water, be heated to 85 ℃, it is to react 1.5 hours under 0.60MPa gauge pressure condition that logical nitrogen makes system pressure, after reaction finishes, cooling, branch vibration layer, product is dried, obtain 762.9 grams of octodecyl alcohol polyoxyethylene polyethenoxy ether isopropyl calcium sulphonate (m=5, n=8).
To synthetic octodecyl alcohol polyoxyethylene polyethenoxy ether isopropyl calcium sulphonate (m=5, n=8), application U.S. Nicolet-5700 infrared spectrometer, adopts pressed disc method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), there is the characteristic peak shown in Fig. 2.
(e) by percentage to the quality, get synthetic octodecyl alcohol polyoxyethylene polyethenoxy ether isopropyl calcium sulphonate (m=5, n=8) 1 part, this 60 3 parts, dish, 1 part of sodium lauryl sulphate, 0.8 part and 40 parts whiterusss of water add in reaction flask successively, being warming up to 60 ℃ stirs 3 hours, obtain required composite oil base emulsifying agent oil solution, wherein compound emulsion agent content is 10.9% by percentage to the quality.
[embodiment 5]
(a) lauryl alcohol polyoxyethylene poly-oxygen propylene aether (m=3, n=30) is synthetic
To being equipped with in the reactor of condensing works, whipping appts and gas distributor, add 186 grams of (1 mole) lauryl alcohols, 5.7 grams of calcium oxide and 3.6 grams of barium oxide, when logical nitrogen limit, limit is heated to 135 ℃, add 30 grams of water, stirring reaction 1 hour.Remove after moisture content, be cooled to 80 ℃, the sulfuric acid (20wt%) that slowly drips catalyst neutralisation theoretical amount makes the calcium barium bimetallic catalyst reaction solution system of high reactivity, highly selective, system temperature is heated to 80～90 ℃, open vacuum system, under high vacuum, dewater 2 hours, then use nitrogen purging 3～4 times, system temperature of reaction is adjusted to 130 ℃ and slowly passes into 132 grams of (3 moles) oxyethane, control pressure≤0.40MPa, after reacting ethylene oxide finishes, be that 160 ℃ slowly pass into 1740 grams of (30 moles) propylene oxide, control pressure≤0.60MPa.After reaction finishes, use nitrogen purging system, cooling rear neutralization, dehydration, obtain 1938.6 grams of lauryl alcohol polyoxyethylene poly-oxygen propylene aethers (m=3, n=30), molar yield 94.2%.
(b) chloro lauryl alcohol polyoxyethylene poly-oxygen propylene aether (m=3, n=30) is synthetic
By the lauryl alcohol polyoxyethylene poly-oxygen propylene aether (m=3 of step (a) synthesized, n=30) 1029.0 grams (0.5 mole), 79.0 grams of (1.0 moles) pyridines are placed in 2000 milliliters of there-necked flasks that backflow, stirring, gas absorbing device are housed, under agitation slowly drip 148.8 grams of sulfur oxychlorides (1.25 moles), 75 ℃ of reactions 7 hours, reaction finishes aftertreatment with [embodiment 1] (b), obtain chloro lauryl alcohol polyoxyethylene poly-oxygen propylene aether (m=3, n=30) 850.3 grams, molar yield 81.9%.
(c) lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=3, n=30) is synthetic
By the chloro lauryl alcohol polyoxyethylene poly-oxygen propylene aether (m=3 of step (b) synthesized, n=30) 850.3 grams (0.409 moles) are placed in autoclave, add 59.5 gram 1, ammediol, 127.5 grams of water, 74.4 grams of S-WATs (0.591 mole) and 15.1 grams of sodium bisulfites (0.145 mole), at 120 ℃ of temperature, react 7 hours, all the other operations with [embodiment 1] (c), obtain lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=3, n=30) 683.0 grams, molar yield is 78.7%.
To synthetic lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=3, n=30), application U.S. Nicolet-5700 infrared spectrometer, adopts liquid-film method to carry out Infrared spectroscopy (sweep limit 4000～400cm
-1), there is the characteristic peak shown in Fig. 1.
(d) by percentage to the quality, get synthetic lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl sulfonic acid (m=3, n=30) 4 parts, 0.5 part of lauroyl diethanolamine, 0.5 part of Sodium palmityl sulfate, 0.3 part and 10 parts whiterusss of water add in reaction flask successively, being warming up to 40 ℃ stirs 2 hours, obtain required composite oil base emulsifying agent oil solution, wherein compound emulsion agent content is 32.7% by percentage to the quality.
[embodiment 6]
With [embodiment 1], difference substitutes 1 part of this dish 85 with 1 part of hard acyl diethanolamine, and all the other are identical, obtain required composite oil base emulsifying agent oil solution.
[embodiment 7]
With [embodiment 1], the usage quantity of lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl calcium sulphonate (m=3, n=15) is 4 parts, and difference substitutes 1 part of this dish 85 with 0.5 part of polysorbate85, and all the other are identical, obtain required composite oil base emulsifying agent oil solution.
[embodiment 8～14]
With [embodiment 1～7] synthetic composite oil base emulsifying agent preparation oil base drilling fluid system, the water oil ratio of employing is 70:30, and basic recipe is 210mL oil+90mL 20wt%CaCl
2wt % cis-1,4-polybutadiene rubber+ 1, wt % organophilic clay+1wt % organic amine modified humic acid+1, the aqueous solution+3wt % compound emulsifying agent+3 wt % CaO powder.Wherein, white oil total amount comprises the white oil amount in composite emulsifier oil solution, and the add-on of composite emulsifier is with the mass percent conversion of composite emulsifier oil solution.
Accurately take a certain amount of white oil and mix (total amount of white oil is 210mL) with 3 wt % emulsifying agents, high-speed stirring 10min, add successively again 3 wt % organophilic clays, 1wt % organic amine modified humic acid, 1 wt % ethylene-propylene rubber(EPR) and 1 wt % CaO powder, continue high-speed stirring 20min, finally add 90mL 20wt%CaCl
2the aqueous solution, then high-speed stirring 10min, obtain stable water-in-oil-type drilling fluid system.Measure respectively rheological parameter, emulsion-breaking voltage and the API filtration of this water-in-oil-type drilling fluid system.Wherein rheological parameter adopts the fast rotary viscosity design determining of ZNN-D6 type six of sea, Qingdao sensible instrumentation factory, and calculates apparent viscosity (μ according to formula (1) and (2)
a) and plastic viscosity (μ
p), emulsion-breaking voltage is measured by the DWY-2 type drilling fluid elctrical stability determinator of Qingdao sensible instrumentation factory, and API filtration is measured by the multi-joint filtration device of SD type, and calculates filter loss (FL) according to formula (3).
Formula (1)
(mPa.s)
Formula (2)
(mPa.s)
Formula (3)
(mL)
The above-mentioned water-in-oil-type drilling fluid preparing is put into XGRL-4 type high temp roller process furnace, 180 ℃ of high temperature ageings 24 hours, measure respectively rheological parameter, emulsion-breaking voltage and the API filtration of this water-in-oil-type drilling fluid system, instrument and process are with before aging, and result is as shown in table 1,2.
Oil base drilling fluid system performance before table 1 aged at room temperature
180 ℃, table 2 is oil base drilling fluid system performance after aging 24 hours
[comparative example 1]
With [embodiment 8], it is emulsifying agent that difference is used 3 wt % calcium stearates to substitute the composite oil base emulsifying agent of 3 wt % of [embodiment 1] preparing, all the other are identical, have measured rheological parameter, emulsion-breaking voltage and the API filtration of water-in-oil-type drilling fluid system, and result is as shown in table 3.
Table 3
Claims (8)
1. the composite oil base emulsifying agent of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate, comprises following component in mass fraction:
The aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate of (1) 0.5～6 part;
The nonionogenic tenside of (2) 0.5～5 parts;
The anion surfactant of (3) 0.1～3 parts;
The oil of (4) 5～50 parts;
The water of (5) 0.1～1 parts;
Wherein the general molecular formula of (1) component is:
In formula: M is any one ion being selected from hydrogen, calcium, magnesium, barium, zinc, aluminium or iron, and R is C
8～C
30alkyl, m is the adduction number of ethoxy group EO, its span is any one integer in 1～10, n is the adduction number of the PO of propoxy-group, its span is any one integer in 1～40, x span is any one integer in 1～3.
2. the composite oil base emulsifying agent of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate according to claim 1, is characterized in that described ion is hydrogen, calcium, magnesium or zinc; R is C
8～C
20alkyl; M is any one integer in 1～6;
N is any one integer in 3～35; X is 1 or 2.
3. the composite oil base emulsifying agent of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate according to claim 1, is characterized in that described nonionogenic tenside is selected from this dish or tween or higher fatty acid amide.
4. the composite oil base emulsifying agent of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate according to claim 3, is characterized in that this described dish series of surfactants is selected from least one in this dish 20, this dish 40, this dish 60, span 80 or this dish 85; Tween series of surfactants is selected from least one in polysorbas20, polysorbate40, polysorbate60, tween 80 or polysorbate85; Higher fatty acid amide series of surfactants is selected from least one in lauroyl diethanolamine, cocounut oil acyl diethanolamine, myristoyl diethanolamine, palmitoleoyl diethanolamine, oleoyl diethanolamine or hard acyl diethanolamine.
5. the composite oil base emulsifying agent of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate according to claim 1, is characterized in that described anion surfactant is chain alkyl sulfuric acid or long-chain alkyl benzene sulfonate.
6. the composite oil base emulsifying agent of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate according to claim 5, is characterized in that described chain alkyl sulfuric acid is selected from carbon chain length C
12～C
18sodium sulfate; Long-chain alkyl benzene sulfonate is selected from carbon chain length C
12～C
24benzene sulfonic acid sodium salt; Described grease separation is from white oil or whiteruss; Described wet concentration is from deionized water.
7. the preparation method of the composite oil base emulsifying agent of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate claimed in claim 1, comprises the following steps:
(a) preparation of aliphatic alcohol polyethenoxy polyethenoxy ether:
By fatty alcohol and oxyethane, propylene oxide, by required proportioning, in temperature of reaction, be 85～160 ℃, pressure is less than under 0.80MPa gauge pressure condition, and calcium barium bimetal compound is catalyzer, reacts to obtain aliphatic alcohol polyethenoxy polyethenoxy ether; Wherein the mol ratio of fatty alcohol and oxyethane, propylene oxide is 1: 1～15: 1～50, and catalyst levels is 1.0～8.0 % of fatty alcohol quality;
(b) preparation of chloro fat alcohol polyoxyethylene poly-oxygen propylene aether:
The aliphatic alcohol polyethenoxy polyethenoxy ether of step (a) synthesized is reacted 3～10 hours at 70～100 ℃ by required proportioning with thionyl chloride, pyridine by required proportioning, excessive thionyl chloride is extracted in decompression out, in and layering remove inorganic salt, vacuum-drying obtains chloro fat alcohol polyoxyethylene poly-oxygen propylene aether; Wherein, the mol ratio of aliphatic alcohol polyethenoxy polyethenoxy ether, thionyl chloride and pyridine is 1: 1～3: 0.5～2.5;
(c) preparation of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonic acid (x=1)
The chloro fat alcohol polyoxyethylene poly-oxygen propylene aether of step (b) synthesized is placed in to reactor, the solvent 1 that adds required proportioning, mixture and the water of ammediol, sulphonating agent S-WAT or S-WAT and sodium bisulfite, at 90～150 ℃, react 3～9 hours, then through steaming water, aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonic acid (x=1) neutralizes, desalts and to obtain;
Wherein, sulfonated reagent is the mixture of S-WAT or S-WAT and sodium bisulfite, and the mol ratio of chloro fat alcohol polyoxyethylene poly-oxygen propylene aether and sulfonated reagent is 1: 1.5～2.5,1, ammediol consumption is 4～10% of reactant quality, and water consumption is 5～20% of reactant quality;
(d) preparation of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate (x=2 or 3)
By the aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonic acid of step (c) synthesized by required proportioning and water, M (OH)
xor MO (M
2o
3) add respectively in autoclave, in temperature of reaction, be 50～120 ℃, the reaction times is 0.5～5 hour, under 0.60MPa gauge pressure condition, reacts to obtain aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate; Wherein the mol ratio of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonic acid and oxyhydroxide or oxide compound is 1.5～3: 1, and the mass percent that water accounts for the total material of reaction is 60～90%, M (OH)
xor MO (M
2o
3) Average Particle Diameters be 200nm～200 μ m;
(e) aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate, nonionogenic tenside, anion surfactant, base oil and the water of aequum are added in reaction flask successively, be warming up to 30～80 ℃ and stir 1～4 hour, obtain required composite oil base emulsifying agent; In mass fraction, the proportioning of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate, nonionogenic tenside, anion surfactant, oil and water is 0.5～6 part: 0.5～5 part: 0.1～3 part: 5～50 parts: 0.5～3 part.
8. the preparation method of the composite oil base emulsifying agent of fatty alcohol polyoxyethylene poly-oxygen propylene aether sulfonate according to claim 7, is characterized in that the range of reaction temperature in (a) step is 120～160 ℃, and pressure range is 0.30～0.60MPa gauge pressure; The mol ratio of fatty alcohol and oxyethane, propylene oxide is 1: 1～5: 5～35, and catalyst levels is 2.5～5.0% of fatty alcohol quality; (b) in step, the mol ratio of aliphatic alcohol polyethenoxy polyethenoxy ether, thionyl chloride and pyridine is 1: 1.5～2.5: 1～2, and temperature of reaction is 75～90 ℃, and the reaction times is 4～8 hours; (c) in step, the mol ratio of chloro fat alcohol polyoxyethylene poly-oxygen propylene aether and sulfonated reagent is 1: 1.5～2,1,3-PD consumption is preferably 5～8% of reactant quality, and water consumption is 10～15% of reactant quality, temperature of reaction is 110～140 ℃, and the reaction times is 4～8 hours; (d) aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonic acid and M (OH) in step
xor MO (M
2o
3) mol ratio be 1.8～2.5: 1, water account for reaction total material mass percent be 70～85%, M (OH)
xor MO (M
2o
3) Average Particle Diameters be 400nm～100 μ m, temperature of reaction is 60～90 ℃, the reaction times is 1～3 hour; (e) in mass fraction, the amount ranges of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate is 1～4 part, the amount ranges of nonionogenic tenside is 1～4 part, the amount ranges of anion surfactant is 0.5～1 part, the amount ranges of oil is 10～40 parts, the amount ranges of water is 0.3～0.7 part, and temperature of reaction is 40～70 ℃, and churning time is 2～3 hours.
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| CN111088025B (en) * | 2018-10-23 | 2022-05-24 | 中国石油化工股份有限公司 | Efficient oil washing agent for improving carbon dioxide oil displacement efficiency and preparation method and application thereof |
| CN115975619A (en) * | 2022-12-13 | 2023-04-18 | 中国日用化学研究院有限公司 | Surfactant compound, preparation method thereof and application thereof in tertiary oil recovery |
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