CN101081976A - Fire-resistant non-injury fracturing fluid thickening agent and preparation method and usage thereof - Google Patents
Fire-resistant non-injury fracturing fluid thickening agent and preparation method and usage thereof Download PDFInfo
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Abstract
The present invention is thickener for heat resistant no-harm fracturing fluid and its preparation process and use. The thickener in the general expression of R1-X-(EO)m(PO)n-Y, where, R1 is long chain hydrophobic group, EO is ethoxy group, PO is 2-oxidized propyl group, m and n are average addition molar numbers, X is linking group ether bond, ester bond or amido bond, Y is hydrophilic group quaternary ammonium group, carboxyl group, sulfuric group or sulfonic group, is prepared through esterification or addition and further reaction. When the thickener is applied, the thickener in 1-3 weight portions and high temperature stabilizer in 0.05-0.4 weight portion are added into base fluid compounded with halogen salt in 2-3 weight portions and water in 100 weight portions to obtain heat resistant no-harm fracturing fluid for increasing yield of oil-gas field.
Description
Technical field:
The invention belongs to oil-gas field fracturing liquid technical field, be specifically related to surfactant thickened dose of small molecules that fire-resistant non-injury fracturing fluid uses and preparation method thereof.
Background technology:
U.S.'s " international petroleum IEEE will " 1998 the 43rd page (article SPE39785) once reported, widely used plant gum fracturing fluid returns the vegetable jelly deficiency that drains into ground and pumps into 40% of stratum in the oil-gas field fracturing volume increase after construction finishes, a large amount of " the non-propping agent solid substance " that remain in inside, stratum can stop up artificial water conservancy diversion crack and stratum, make stratum infiltration situation to be significantly improved, seriously reduced the recovery ratio of crude oil.
United States Patent (USP) U.S.P.5,551, the 516 a kind of clean fracturing fluids based on the small molecules tensio-active agent that propose are regulated its viscosity by the type of regulating small molecules tensio-active agent self-assembled structures, do not use any polymer, successfully solved the residue problem of plant gum fracturing fluid on the stratum.But since its adopt mainly contain effective constituent erucyl dihydroxy ethyl ammonium chloride need be under high temperature, condition of high voltage the selective catalytic hydrogenation preparation, not only technological process more complicated danger, and cost an arm and a leg, cost is common plant gum fracturing fluid more than 20 times, be difficult to obtain to apply on a large scale.
What Chinese patent CN1439691 and CN1621484 proposed is that the small molecules tensio-active agent fracturing liquid of major ingredient reduces significantly than external clean fracturing fluid cost to grow alkyl chain length trimethyl quaternary ammonium salt and oleic acid, be about about three times of plant gum fracturing fluid cost, but because its tensio-active agent hydrophobic chain that adopts is shorter, intermolecular hydrophobic interaction intensity a little less than, in hot environment, can't form stable vermiform aggregate, be only applicable to the waterfrac treatment operation that temperature is lower than 80 ℃ low temperature formation.
China's net " about the suggestion of China's hydrocarbon resources development strategy problem " (Chen Zhouqi,
Www.china.org.cn, 2002/3/5) literary composition points out, the land a lot of main forces of China oil field has entered development phase middle and later periods, buried depth surpasses reservoirs such as 3500 meters hyposmosis or the hydrocarbon-bearing pool of extra-low permeability rate, and to account for whole workable reserve over half, the inexorable trend that maturing field was faced during oil was adopted deeply and just become, existing fracturing liquid has been difficult to satisfy the needs of China's energy extraction, it is good to develop a kind of heat resistance, and the moderate non-injury fracturing fluid of cost is a urgent task.
Summary of the invention:
The purpose of this invention is to provide a kind of fire-resistant non-injury fracturing fluid thickening agent and preparation method thereof, and with the fire-resistant non-injury fracturing fluid of this thickening material preparation, to overcome the above-mentioned defective of prior art.
Fire-resistant non-injury fracturing fluid thickening agent of the present invention is characterised in that it is a general formula R
1-X-(EO)
m(PO)
nThe tensio-active agent of-Y; In the formula, R
1Long-chain hydrophobic grouping for the saturated or unsaturated alkyl that is selected from carbonatoms 20 to 26; EO is an oxyethyl group, and PO is a 2-oxidation propyl group, and m, n are respectively the average addition mole number of EO and PO, and 0≤m≤10,0≤n≤10,0≤m+n≤10 are preferably 1≤m+n≤6; X is alkyl and hydrotropy segment (EO)
m(PO)
nBetween linking group, comprise ehter bond, ester bond or amido linkage; Y is an ionic hydrophilic group group, comprises quaternary ammonium group, carboxyl, sulfate or sulfonic group.
The preparation method of fire-resistant non-injury fracturing fluid thickening agent of the present invention, it is characterized in that: adopt lipid acid and low-molecular-weight polyoxyethylene glycol or poly(propylene oxide) esterification method earlier, or under the catalysis of level Four salt, Lewis acid or Lewis base, make oxyethane or/and the method for propylene oxide and long chain aliphatic alcohol, lipid acid or aliphatic amide generation addition reaction realizes that the long-chain hydrophobic group is connected with the hydrotropy segmental; Then hydrotropy segmental terminal hydroxyl is converted into halogen atom, further obtain quaternary ammonium salt cationic surfactant with excessive reactive tertiary amine, or hydrotropy segmental terminal hydroxyl and sulfonated reagent thionamic acid or chlorsulfonic acid reaction produced sulfonic acid or sulfuric acid type anion surfactant, or hydrotropy segmental terminal hydroxyl reacted with sodium chloroacetate produce the carboxylic acid type anion surfactant; Above-mentioned preparation process can be expressed as with general formula:
In the formula, R
1Straight chained alkyl, alkenyl or carboxyl groups for carbonatoms 20～26, can be selected from the longer chain fatty acid or derivatives thereof that refines in the natural animal-plant grease, comprise: linolic acid, linolenic acid, arachidonic acid, eicosanoic acid, mountain Yu acid, erucyl acid, wooden pyro acid, behenyl alcohol, V-1326, Tetracosyl alcohol, n-Hexacosanol, amine hydroxybenzene, stearic amide, mountain Yu acid acid amides, erucyl acid acid amides, mountain Yu base amine or erucyl amine; R
2, R
3And R
4Be respectively the alkyl or the hydroxyethyl groups of carbonatoms 1～3.
Contain impurity such as inorganic salt and non-polar organic solvent in the rough sample, can adopt the method for washing, distillation or recrystallization to remove, so that active ingredient content is no less than 90% in the finished product.
Fire-resistant non-injury fracturing fluid of the present invention is will to be made into base fluid in 100 parts of water of halogen adding of 2～3 parts by weight; It is characterized in that: in base fluid, add 1～3 part thickening material and 0.05～0.4 part high-temperature stabiliser; Described thickening material is that general formula of the present invention is R
1-X-(EO)
m(PO)
nThe fire-resistant non-injury fracturing fluid thickening agent of-Y; Described high-temperature stabiliser is and the long-chain tensio-active agent of selected thickening material band counter ion group that preferred general formula of the present invention is R
1-X-(EO)
m(PO)
nThe fire-resistant non-injury fracturing fluid thickening agent of-Y.
Described halogen comprises that Repone K, sodium-chlor, ammonium chloride, Potassium Bromide, Sodium Bromide are or/and brometo de amonio is preferably sodium-chlor or/and Repone K.
Fire-resistant non-injury fracturing fluid thickening agent of the present invention, strengthen hydrophobic interaction intensity between surfactant molecule owing to take to prolong significantly the length of the hydrophobic chain of surfactant molecule, thereby improved the resistance to elevated temperatures of the vermiform aggregate that its self aggregation forms effectively; And because hydrophobic chain length increases the problem of the water-soluble reduction of tensio-active agent that is brought, then be to solve by the hydrotropy segment that between hydrophobic grouping and ionic hydrophilic group group, adds appropriate length, the hydrotropy segmental insert to adopt common esterification or etherification reaction to realize, this reaction can avoid using the severe condition, safer and be easy to realize suitability for industrialized production of High Temperature High Pressure.
Fire-resistant non-injury fracturing fluid of the present invention, by selecting for use long-chain tensio-active agent with thickening material band counter ion group as high-temperature stabiliser, can make between the inner surfactant molecule of vermiform aggregate and produce very strong synergy, this synergy has further strengthened intermolecular non-covalent interaction intensity, has improved the heat resistance of non-injury fracturing fluid effectively; High-temperature stabiliser is preferably 0.05～0.4: 1～3 with the ratio of thickening material weight, the high-temperature stabiliser consumption is low excessively, then between the surfactant molecule a little less than the non covalent bond effect too, resulting fracturing liquid heat resistance is poor, the high-temperature stabiliser consumption is too high, then the non covalent bond effect is too strong between the surfactant molecule, easily forms throw out, is difficult to obtain the fracturing liquid of homogeneous.
The non-injury fracturing fluid that adopts small molecules thickening material of the present invention and compound method thereof to obtain has stable viscosity under the high temperature, fully propping agent suspends and transports performance and stratum and propping agent packing layer are not caused the distinguishing feature of any injury.
Compare with the clean fracturing fluid of domestic big Khanh Hoa Dagang Oilfield development, non-injury fracturing fluid heat resistance of the present invention significantly improves, and reaches 150 degrees centigrade, approximately exceed domesticly now to use more than 70 degree centigrade of clean fracturing fluid, and cost only increases about 1/3rd; Compare with the clean fracturing fluid that aforementioned Britain Schlumberger company develops, non-injury fracturing fluid advantage of the present invention is that the major ingredient that uses is to be feedstock production with the first oil crops Semen Brassicae campestris that China extensively plants, cost reduces significantly, only be its about 1/5th, simultaneously high temperature tolerance has also improved more than 20 degree centigrade than its 130 degrees centigrade, can satisfy the needs of China's deep stratum hyposmosis or extra-low permeability rate hydrocarbon-bearing pool fracturing yield increasing.
Embodiment:
Embodiment 1: prepare cationic thickening material polyethylene oxide list behenate methyl dihydroxy ethyl brometo de amonio (DHAB-2)
Take by weighing mountain Yu acid 2040g (6 moles), tetramethyl ammonium chloride 17g, add volume and be in 5 liters the autoclave, be warming up to 125 ℃, under the pressure condition of 0.45MPa, make it reaction, carry out 5 hours slaking with oxyethane 721g (16.4 moles).Open reducing valve, slowly emptying in 75 ℃ again.Adopt 10% salt solution 2Kg washing,, obtain polyethylene oxide list behenate 2510g through dehydration, filtration.
According to the content of the methods analyst oxyethyl group of standard GB7385-1987, the average addition mole number of oxyethane is 2.2.With the lipid acid of reacting ethylene oxide, also can substitute in this step reaction with carbon chain lengths suitable Fatty Alcohol(C12-C14 and C12-C18) or aliphatic amide.Catalyzer in this reaction also can adopt Lewis acid or Lewis base except that level Four salt.
Take by weighing 210g (0.5 mole) polyethylene oxide list behenate, measure 5 milliliters of triethylamine catalyzer and 200ml toluene, add in the three-necked flask of 1000ml, mixing, slowly drip 23.7 milliliters of (about 0.25 mole) phosphorus tribromides under the room temperature, after dropwising, be warmed up to 50 ℃ of reactions 4 hours, organic phase is used saturated sodium bicarbonate aqueous solution successively, the tap water washing is to neutral, toluene is removed in underpressure distillation, gained yellow liquid volume ratio be 90: 10 sherwood oil (boiling range is 60～90 ℃) and methylene dichloride mixed solvent through 100 purpose silicagel column wash-outs, remove impurity, further distillation removes and desolvates, and gets the transparent liquid of 204g achromaticity and clarification; The IR spectrum shows that this liquid is at v=1208cm
-1There is a strong vibration peak at the place, shows CH
2The existence of-Br shows that product is a bromo polyethylene oxide list behenate, and its structural formula is: C
21H
43CO (OCH
2CH
2)
2.2Br, yield are 82%.
Get 124g (0.25 mole) bromo polyethylene oxide list behenate, 44.68g (0.37 mole) N methyldiethanol amine and 200 milliliters of acetone, add in 500 milliliters of three-necked flasks, nitrogen filled protection, heat up, refluxed six hours, can observe white solid in the reaction process and separate out, sampling is also adopted tlc (TLC) analysis, finds that bromoalkane has transformed substantially in the reaction solution, with reaction solution cooling, filtration, oven dry, obtain 152g white paste solid; This paste solid adopts the tetrabromophenol sulfonphthalein two-phase titration to record wherein, and the content of cats product is 95%.So far successfully prepared cationic thickening material polyethylene oxide list behenate methyl dihydroxy ethyl brometo de amonio (DHAB-2).
Get this DHAB-2 crude samples 1g, add in 50 ml waters, stir (about 30 minutes) to sample and dissolve fully, the aqueous solution has bigger viscosity, with Brookfield PVS type rheometer record at normal temperatures, shearing rate is 4S
-1The time viscosity be 66cp, show that this sample has thickening properties preferably.
In the present embodiment in the tensio-active agent long-chain hydrophobic group be connected with the hydrotropy segmental that the method that be to adopt lipid acid and oxyethane that addition reaction takes place realizes under the catalysis of level Four salt; This step also can adopt lipid acid and low-molecular-weight polyoxyethylene glycol or poly(propylene oxide) esterification method to realize, because the reactivity of propylene oxide, wetting ability and bad oxidative ethane are comparatively approaching, and can some or all of displaced loop oxidative ethane.
Synthetic cationic surfactant in the present embodiment, what the substituting group on the water-wet side nitrogen-atoms was selected for use is hydroxyethyl groups, it is that 1～3 alkyl substitutes that this hydroxyethyl groups also can partly or entirely adopt the approaching carbonatoms of hydrophilicity.
Embodiment 2: the thickening material polyethylene oxide list behenate sodium sulfate (DSN-2) of preparation anionic
Take by weighing the polyethylene oxide list behenate 100g (0.25 mole) of preparation among the embodiment 1, place the three-necked flask of 250mL, be heated to 115～120 ℃, under constantly stirring, in 10～15 minutes, add 25.5g (0.37 mole) thionamic acid,, be cooled to room temperature 120～125 ℃ of stirring reactions 2 hours, add the sodium hydroxide neutralization, reach 7.5～8.5 to the pH value.The crude product volume ratio is 75: 25 an acetoneand ethyl acetate mixed solvent recrystallization, again in 60 ℃ of oven dry down, at last purified micro-yellow powder 89g, record wherein according to the method for standard GB/T5173-1995 that the content of anion surfactant is 96.3%, yield 77.4%.
Embodiment 3: with cationic thickening material DHAB-2 preparation high temperature non-injury fracturing fluid
Get three capacity and be 500 milliliters beaker, the potassium chloride solution that all adds 200 milliliter 2% (weight fraction) in each beaker, in three beakers, add synthetic DHAB-2 among 2g, 4g and the 6g embodiment 1 respectively, be stirred well to dissolving fully, promptly get non-injury fracturing fluid;
Adopt this of the fracturing fluid viscosity under the Brookfield PVS type rheometer measurement differing temps, the results are shown in following table:
| Temperature (℃) | 60 | 80 | 100 | 110 | 120 | 130 | |
| Viscosity (cp) @170S -1 | 1％DHAB-2 | 115 | 63 | 28 | - | - | - |
| 2％DHAB-2 | 162 | 124 | 106 | 74 | 22 | - | |
| 3％DHAB-2 | 308 | 246 | 1 84 | 120 | 72 | 48 | |
As seen from the above table, of the fracturing fluid heat resistance improves along with the increase of thickening material DHAB-2 consumption; But, under the situation that does not add any high-temperature stabiliser, concentration is that 3% the shear viscosity of fracturing liquid when temperature rises to 130 ℃ has been reduced to 48 centipoises, and less than successfully taking the desired MV minium viscosity 50cp of sand, the frac job that still can not satisfied temperature surpasses oil gas a surname of 130 ℃ needs; As only relying on the consumption that increases thickening material to improve of the fracturing fluid heat resistance, of the fracturing fluid cost will rise significantly, and moderate for guaranteeing of the fracturing fluid cost, the weight concentration of thickening material of the present invention should be 1%～3%.
In above-mentioned 200 ml concns that prepare are 2% and 3% DHAB-2 fracturing liquid, add synthetic DSN-2 anion surfactant among 0.4g, the 0.2g embodiment 2 respectively, be stirred to dissolving fully, promptly get fire-resistant non-injury fracturing fluid.Measure this of the fracturing fluid shear viscosity with the variation of temperature situation, the result is as follows:
| Temperature (℃) | 60 | 80 | 100 | 120 | 140 | 150 |
| Viscosity (cp) @170S -1The 2%DHAB-2+0.4% high-temperature stabiliser | 141 | 185 | 162 | 117 | 72 | 34 |
| Viscosity (cp) @170S -1The 3%DHAB-2+0.2% high-temperature stabiliser | 221 | 258 | 287 | 150 | 103 | 77 |
Select for use cationic surfactant D HAB-2 as thickening material in the present embodiment, having selected water-wet side simultaneously for use is that anionic DSN-2 tensio-active agent is made high-temperature stabiliser, as seen from the above table, the adding of DSN-2 has improved the shear viscosity of DHAB-2 fracturing liquid when temperature surpasses 120 degrees centigrade greatly, concentration is that 2% the shear viscosity of DHAB-2 fracturing liquid in the time of 140 ℃ reaches 72 centipoises, has surpassed and has carried desired MV minium viscosity 50 centipoises of propping agent; Concentration is that 3% the shear viscosity of DHAB-2 fracturing liquid in the time of 150 ℃ reaches 77 centipoises, has surpassed and has carried desired MV minium viscosity 50 centipoises of propping agent, shows that its heat resistance has surpassed 150 ℃.This is that zwitterion is right closely because the water-wet side of DSN-2 and DHAB-2 surfactant molecule forms, again because both hydrophobic end hydrophobic chain length is suitable, consistency is better, improve the non covalent bond action intensity between the aggregate interior molecules greatly, thereby improved the heat resistance of DHAB-2 aggregate.
According to the method described above, preparing three parts of 100g weight concentrations is the 2%DHAB-2 non-injury fracturing fluid, in this fracturing liquid, add DSN-2 high-temperature stabiliser 0.1g, 0.2g and 0.5g more respectively, the weight concentration of corresponding high-temperature stabiliser is respectively 0.1%, 0.2% and 0.5%, be stirred to fully dissolving, leaving standstill the back, to find that the high-temperature stabiliser consumption is that 0.5% fracturing liquid becomes muddy, do not become the fluid of homogeneous, show that the high-temperature stabiliser consumption is too high, can't make high temperature fracture liquid on the contrary; Measure all the other two of the fracturing fluid shear viscosities according to the method described above with the variation of temperature situation, the high-temperature stabiliser consumption is that 0.1%, 0.2% fracturing liquid is when temperature rises to 120 ℃, 134 ℃ respectively, shear viscosity is reduced to 50cp, show that the high-temperature stabiliser consumption is too low, of the fracturing fluid viscosity with temperature rise and fall are too fast.
By above-mentioned experiment comparative result as can be known, when the thickening material consumption was 2%, the consumption of high-temperature stabiliser generally should be 0.2%～0.4%.
Embodiment 4: with the thickening material DSN-2 preparation high temperature non-injury fracturing fluid of anionic
Adopt with embodiment 3 in identical method, in the potassium chloride solution of 200 milliliter 2% (weight fraction), add synthetic aniorfic surfactant DSN-2 among the 4g embodiment 2, and the DHAB-2 of adding 0.8g is as high-temperature stabiliser, be stirred well to dissolving fully, use Brookfield PVS type rheometer measurement at 170S
-1This fracturing liquid is in the shear viscosity of differing temps under the shearing rate, result such as following table:
| Temperature (℃) | 120 | 125 | 130 | 135 | 140 | 145 |
| Viscosity (cp) @170S -1The 2%DHAB-2+0.4% high-temperature stabiliser | 99 | 113 | 106 | 87 | 63 | 46 |
By last table data as seen, the surfactant D SN-2 that selects anionic in the present embodiment for use is as thickening material, select the cationic DHAB-2 tensio-active agent high temperature fracture liquid that preparation obtains as high-temperature stabiliser for use simultaneously, in the time of 140 ℃, shear viscosity still has 63cp, surpassed that to take the high temperature fracture liquid performance of being prepared among needed MV minium viscosity 50cp of sand and the embodiment 3 suitable.
The raising of the heat resistance of high-temperature thickening agent of the present invention mainly is because selected the hydrophobic grouping of long-chain, and select the long-chain tensio-active agent of suitable band counter ion group to make high-temperature stabiliser according to thickening material, little with the kind relation of the water-wet side ionic type of tensio-active agent, common hydrophilic radical such as carboxyl, sulfate, sulfonic group or quaternary ammonium group can be as the hydrophilic radicals of tensio-active agent of the present invention.
Comparative example 5: the thickening properties of different lengths hydrophobic chain, hydrotropy segment thickening material relatively
The comparison of the thickening properties of different lengths hydrophobic chain thickening material:
According to the method among the embodiment 1, produce the average addition mole number of oxyethane respectively between 2.0～2.3 polyethylene oxide monopalmitate, polyoxyethylene monostearate and polyethylene oxide list hexacosane acid esters, further carry out quaterisation and obtain corresponding quaternary ammonium salt C
16HAB, C
18HAB and C
26HAB.
Take by weighing C
16HAB, C
18HAB and C
26Each 1g of HAB crude samples, adding fills in three beakers of 50 ml waters respectively, and normal temperature stirs down, C
16HAB and C
18HAB stirs less than just dissolving fully in 10 minutes, and C
26HAB has stirred just dissolving fully in 1 hour, and recording three sample solutions is 4S in 25 ℃ of temperature, shearing rate
-1The time shear viscosity be respectively 12cp, 25cp and 83cp.DHAB-2 viscosity in aqueous solution data can be found among the comparative example 1: thickening material hydrotropy chain length is fixedly the time, the hydrophobic chain length of thickening material is long more, the viscosity of solution is big more, the thickening capabilities that shows thickening material thus is along with the corresponding enhancing of the growth of hydrophobic chain length, but it is that the water-soluble of thickening material reduces greatly that hydrophobic chain increases a unfavorable factor that produces, if and shorten the length of thickening material hydrophobic chain, its thickening capabilities can significantly reduce again.Therefore, desire to make the synthetic tensio-active agent both to have the feature of high-temperature thickening agent, has better water solubility again, should select the hydrophobic chain carbonatoms is 20～26 hydrophobic grouping, optional using from the longer chain fatty acid or derivatives thereof that refines in the natural animal-plant grease comprises linolic acid, linolenic acid, arachidonic acid, eicosanoic acid, mountain Yu acid, erucyl acid, wooden pyro acid, behenyl alcohol, V-1326, Tetracosyl alcohol, n-Hexacosanol, amine hydroxybenzene, stearic amide, mountain Yu acid acid amides, erucyl acid acid amides, mountain Yu base amine or erucyl amine.
The comparison of the thickening properties of different lengths hydrotropy segment thickening material:
According to the method among the embodiment 1, produce the average addition mole number of oxyethane respectively and be 0,4.5,5.8 and 6.3 polyethylene oxide list behenate methyl dihydroxy ethyl brometo de amonio, and called after DHAB-0, DHAB-4, DHAB-5 and DHAB-6 respectively.
Take by weighing four kinds of each 1g of sample of above-mentioned synthetic, add respectively and fill in four beakers of 50 ml waters, stirred 30 minutes, sample DHAB-4, DHAB-5 and DHAB-6 can dissolve fully, and recording these three sample solutions with Brookfield PVS type rheometer is 4S at 25 ℃, shearing rate
-1The time viscosity be respectively 50cp, 38cp and 8cp, above data show, when one timing of thickening material hydrophobic chain length, along with its hydrotropy segmental is elongated, the viscosity of solution reduces significantly, and this is because the hydrotropy segment is oversize, hydrophilic-lipophilic balance that will the failure surface active agent molecule, be unfavorable for that its self aggregation forms vermiculate glues, thickening capabilities significantly reduces.
Sample DHAB-0 stirs the paste that still is white in color after 30 minutes and is suspended in the water, there is not the dissolved sign, this aqueous solution is heated to 60 ℃, continue to stir 20 minutes, sample has a little dissolving, cooling back solid is separated out again, shows that not introduce hydrotropy segmental long-chain tensio-active agent water-soluble very poor, can not be used as the high-temperature thickening agent.
Therefore, be 22 tensio-active agent for carbonatoms in the hydrophobic chain, the average addition mole number of oxyethane is preferably 2～4 in the hydrotropy segment; When selecting longer hydrophobic chain, have hydrophilic-lipophilic balance preferably for ensureing the synthetic tensio-active agent, the hydrotropy segment is answered corresponding prolongation; Equally, when hydrophobic chain length reduced, the hydrotropy segment should corresponding shortening.So, be 20～26 tensio-active agent for carbonatoms in the hydrophobic chain of the present invention, the average addition mole number of oxyethane is preferably 1～6 in the hydrotropy segment.
The hydrotropy segment is an ester group with the base that is connected of hydrophobic grouping in the embodiment of the invention, the group size of the group of other type such as ether, amide group, the polarity of group are suitable with ester group with wetting ability, and therefore substituting ester group becomes and connect the hydrophilic-lipophilic balance that base can not change tensio-active agent.
Claims (8)
1, a kind of fire-resistant non-injury fracturing fluid thickening agent is characterised in that it is a general formula R
1-X-(EO)
m(PO)
nThe tensio-active agent of-Y; In the formula, R
1Long-chain hydrophobic grouping for the saturated or unsaturated alkyl that is selected from carbonatoms 20 to 26; EO is an oxyethyl group, and PO is a 2-oxidation propyl group, and m, n are respectively the average addition mole number of EO and PO, 0≤m≤10,0≤n≤10,0≤m+n≤10; X is alkyl and hydrotropy segment (EO)
m(PO)
nBetween linking group, comprise ehter bond, ester bond or amido linkage; Y is an ionic hydrophilic group group, comprises quaternary ammonium group, carboxyl, sulfate or sulfonic group.
2, fire-resistant non-injury fracturing fluid thickening agent as claimed in claim 1 is characterised in that wherein 1≤m+n≤6.
3, the preparation method of claim 1 fire-resistant non-injury fracturing fluid thickening agent, it is characterized in that: adopt lipid acid and low-molecular-weight polyoxyethylene glycol or poly(propylene oxide) esterification method earlier, or under the catalysis of level Four salt, Lewis acid or Lewis base, make oxyethane or/and the method for propylene oxide and long chain aliphatic alcohol, lipid acid or aliphatic amide generation addition reaction realizes that the long-chain hydrophobic group is connected with the hydrotropy segmental; Then hydrotropy segmental terminal hydroxyl is converted into halogen atom, further obtain quaternary ammonium salt cationic surfactant with excessive reactive tertiary amine, or hydrotropy segmental terminal hydroxyl and sulfonated reagent thionamic acid or chlorsulfonic acid reaction produced sulfonic acid or sulfuric acid type anion surfactant, or hydrotropy segmental terminal hydroxyl reacted with sodium chloroacetate produce the carboxylic acid type anion surfactant; Above-mentioned preparation process can be expressed as with general formula:
In the formula, R
1Straight chained alkyl, alkenyl or carboxyl groups for carbonatoms 20～26; R
2, R
3And R
4Be respectively the alkyl or the hydroxyethyl groups of carbonatoms 1～3.
4, the preparation method of fire-resistant non-injury fracturing fluid thickening agent as claimed in claim 3 is characterised in that: R wherein
1Be selected from the longer chain fatty acid or derivatives thereof that refines in the natural animal-plant grease, comprise: linolic acid, linolenic acid, arachidonic acid, eicosanoic acid, mountain Yu acid, erucyl acid, wooden pyro acid, behenyl alcohol, V-1326, Tetracosyl alcohol, n-Hexacosanol, amine hydroxybenzene, stearic amide, mountain Yu acid acid amides, erucyl acid acid amides, mountain Yu base amine or erucyl amine.
5, a kind of fire-resistant non-injury fracturing fluid is will to be made into base fluid in 100 parts of water of halogen adding of 2～3 parts by weight; It is characterized in that: in base fluid, add 1～3 part thickening material and 0.05～0.4 part high-temperature stabiliser; It is R that described thickening material adopts the general formula of claim 1
1-X-(EO)
m(PO)
nThe fire-resistant non-injury fracturing fluid thickening agent of-Y; Described high-temperature stabiliser is the long-chain tensio-active agent with selected thickening material band counter ion group.
6, fire-resistant non-injury fracturing fluid as claimed in claim 5 is characterised in that it is R that described high-temperature stabiliser adopts the general formula with selected thickening material band counter ion group
1-X-(EO)
m(PO)
nThe fire-resistant non-injury fracturing fluid thickening agent of-Y.
7, fire-resistant non-injury fracturing fluid as claimed in claim 5 is characterised in that described halogen comprises that Repone K, sodium-chlor, ammonium chloride, Potassium Bromide, Sodium Bromide are or/and brometo de amonio.
8, fire-resistant non-injury fracturing fluid as claimed in claim 5 is characterised in that described halogen is that sodium-chlor is or/and Repone K.
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| CN101845301A (en) * | 2010-05-05 | 2010-09-29 | 广汉沃瑞信化工有限公司 | Clean fracturing fluid thickener and preparation method thereof |
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| CN102311722A (en) * | 2010-06-29 | 2012-01-11 | 哈尔滨杰力沃石油科技有限公司 | Aliphatic acid lubricant for petroleum drilling fluid |
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| US4861499A (en) * | 1987-10-13 | 1989-08-29 | American Cyanamid Company | Water-dispersible hydrophobic thickening agent |
| CN1073194A (en) * | 1991-12-10 | 1993-06-16 | 山东省东明县田菁胶厂 | Fracturing fluid thickener |
| US5551516A (en) * | 1995-02-17 | 1996-09-03 | Dowell, A Division Of Schlumberger Technology Corporation | Hydraulic fracturing process and compositions |
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