CN103665367A - Fatty alcohol polyoxyethylene polyoxypropylene ether sulfonate and preparation method thereof - Google Patents
Fatty alcohol polyoxyethylene polyoxypropylene ether sulfonate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to fatty alcohol polyoxyethylene polyoxypropylene ether sulfonate and a preparation method thereof, and is mainly used for solving the problems that an oil-based drilling fluid emulsion in the prior art is poor in stability performance, weak in salt resistance and weak in temperature tolerance. The problems are well solved by adopting the technical scheme of the fatty alcohol polyoxyethylene polyoxypropylene ether sulfonate containing a general molecular formula shown in the specification and the preparation method thereof, wherein in the general molecular formula, M is selected from any ion of hydrogen, calcium, magnesium, barium, zinc, aluminum or iron; R is C8-C30 alkyl; m is an adduct number of an ethoxy group EO and is any integer in 1-10; n is an adduct number of a propoxy group PO and is any integer in 1-40; x is any integer in 1-3. The fatty alcohol polyoxyethylene polyoxypropylene ether sulfonate can be applied to special drilling operations such as strong water-sensitivity and high-temperature stratum, exceptional wells requiring drilling a large displacement, an offshore horizontal well and the like.
Description
Technical field
The present invention relates to a kind of aliphatic alcohol polyethenoxy polyoxypropylene ether 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 at 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 aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate oil base emulsifying agent that stability and high efficiency oil base drilling fluid uses and preparation method thereof.
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 aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate is provided.Take this aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate is that the oil base drilling fluid of oil base emulsifying agent preparation 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 aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate 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: a kind of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate, and its general molecular formula is:
Wherein: 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.Described R preferred version is C
8～C
20alkyl.Described m preferred version is any one integer in 1～6.Described n preferred version is any one integer in 3～35.Described x preferred version is 1 or 2.
For solve the problems of the technologies described above two, the technical solution adopted in the present invention is as follows: a kind of preparation method of aliphatic alcohol polyethenoxy polyoxypropylene ether 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.
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 polyethenoxy ether carboxylic 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.
Aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate prepared by the present invention, owing to containing polyoxyethylene, polyoxypropylene non-ionic group and azochlorosulfonate acid anion group in its molecular structure simultaneously, make the salt tolerant advantage of its heat resistance that has anion surfactant concurrently and nonionogenic tenside, in its molecule, do not contain aromatic ring structure in addition, being easier to biological degradation, is a kind of oil base drilling fluid emulsifying agent that is suitable for high temperature and high salt stratum.
The aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate that adopts the present invention to prepare is the oil base drilling fluid that emulsifying agent forms, and 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 tackifier, 2～5 parts of fluid loss agents, 0.5～3 part of pH adjusting agent.This oil base drilling fluid heatproof reaches emulsion-breaking voltage >=800V after 180 ℃, API filtration≤3ml, high temperature ageing, 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.
[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 compound 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.
[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.
[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.
[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.
[embodiment 6]
[embodiment 1] the synthetic lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl calcium sulphonate (m=3, n=15) of take is emulsifying agent, preparation oil base drilling fluid system, and the basic recipe of employing is 210mL white oil+90mL 20wt%CaCl
2wt % organophilic clay+1wt % ethylene-propylene rubber(EPR)+1wt % modified humic acid+1, the aqueous solution+3wt % emulsifying agent+3 wt % CaO powder.
Specific experiment process is: accurately measure 210mL white oil and mix with 3 wt % emulsifying agents, high-speed stirring 10min, add successively again 3 wt % organophilic clays, 1wt % modified humic acid, 1wt % 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 ageing 24h, 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.
Table 1
[comparative example 1]
With [embodiment 6], difference substitutes 3 wt % lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl calcium sulphonate (m=3 with 3 wt % calcium stearates, n=15) be emulsifying agent, all the other are identical, rheological parameter, emulsion-breaking voltage and the API filtration of having measured water-in-oil-type drilling fluid system, result is as shown in table 2.
Table 2
[comparative example 2]
With [embodiment 6], difference substitutes 3 wt % lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl calcium sulphonate (m=3 with 3 wt % lauryl alcohol polyethenoxy ethers (n=15), n=15) be emulsifying agent, all the other are identical, rheological parameter, emulsion-breaking voltage and the API filtration of having measured water-in-oil-type drilling fluid system, result is as shown in table 3.
Table 3
[comparative example 3]
With [embodiment 6], difference is with 2 wt % lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl calcium sulphonate (m=3, n=15) add 1wt % Sodium dodecylbenzene sulfonate mixture and substitute 3 wt % lauryl alcohol polyoxyethylene poly-oxygen propylene aether isopropyl calcium sulphonate (m=3, n=15) be emulsifying agent, all the other are identical, rheological parameter, emulsion-breaking voltage and the API filtration of having measured water-in-oil-type drilling fluid system, result is as shown in table 4.
Table 4
Claims (8)
1. an aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate, its general molecular formula is:
Wherein: 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. aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate according to claim 1, is characterized in that described ion is hydrogen, calcium, magnesium or zinc.
3. aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate according to claim 1, is characterized in that described R is C
8～C
20alkyl.
4. aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate according to claim 1, is characterized in that described m is any one integer in 1～6.
5. aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate according to claim 1, is characterized in that described n is any one integer in 3～35.
6. aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate according to claim 1, is characterized in that described x is 1 or 2.
7. the preparation method of aliphatic alcohol polyethenoxy polyoxypropylene ether 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.
8. the preparation method of aliphatic alcohol polyethenoxy polyoxypropylene ether sulfonate according to claim 1, 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 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 polyethenoxy ether carboxylic 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.
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