CN103951593B - Warm clean fracturing fluid viscosifying agent synthetic method and application thereof in one - Google Patents
Warm clean fracturing fluid viscosifying agent synthetic method and application thereof in one Download PDFInfo
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- CN103951593B CN103951593B CN201410201382.4A CN201410201382A CN103951593B CN 103951593 B CN103951593 B CN 103951593B CN 201410201382 A CN201410201382 A CN 201410201382A CN 103951593 B CN103951593 B CN 103951593B
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Abstract
Warm clean fracturing fluid viscosifying agent synthetic method and application thereof in one, relate to technical field of oil production engineering, under oxygen free condition, sodium hydroxide or sodium methoxide catalyzed condition, longer chain fatty acid is carried out amidation, by the aminate of longer chain fatty acid that obtains and hydroperoxidation, obtained clean fracturing fluid viscosifying agent.Clean fracturing fluid viscosifying agent and NaCl, NaOH, water are mixed and made into clean fracturing fluid, the viscosifying agent used and the amount of NaCl, NaOH all less, concentration is low, and amine oxide aqueous solution is at pH & gt; When 7, main in non-ionic surface active character, little to fracturing fracture injury, biological degradability is good, little to environmental influence.
Description
Technical field
The present invention relates to technical field of oil production engineering, the of the fracturing fluid blending technology particularly in hydraulic fracturing technology field.
Background technology
Hydraulic fracturing technology is the technical way of hyposmosis, extra-low permeability oil reservoirs volume increase.At present, this technology mainly uses polymer class fracturing liquid, comprises vegetable jelly class fracturing liquid and artificial-synthetic copolymer's class fracturing liquids such as hydroxypropyl guanidine that glue, your glue of carboxy-methyl hydroxy propyl guanidine.Owing to forming the polymer fragment that size does not wait after polymer class fracturing liquid rubber-breaking aquation, wherein, overwhelming majority polymer fragment particle diameter ratio low permeability reservoir pore radius is much bigger, therefore in fracturing process, due to leak-off effect, a large amount of residue concentrates in sand packed fracture, and in supporting crack, concentrated guanidine that glue reduces fracture pore; Because low-permeability oil deposit pore throat radius is little, in fracturing liquid, admittedly form infringement containing easy formation; In production process, fracturing fluid residue backflows and blocks propping agent packing layer, reduces fracture flow capacity.Your glue HPG(first grade of current hydroxypropyl guanidine) residue content at about 300mg/L, your glue of carboxy-methyl hydroxy propyl guanidine GHPG(first grade) and the residue content of low-molecular(weight)polymer viscosifying agent at about 100mg/L, inject 10PV polymer class fracturing liquid rubber-breaking liquid and can make fracture flow capacity and low-permeability sandstone core permeability injury 90%, especially outstanding for low pressure, your glue class fracturing liquid injury problem of ultra-permeable reservior guanidine.
Domesticly in clean fracturing fluid, do a large amount of work, have studied positively charged ion, negatively charged ion, amphoterics clean fracturing fluid, these fracturing fluid systems have without residue, to the feature such as fracturing fracture, formation damage be little, but these fracturing fluid systems use sodium-chlor (Repone K) concentration higher, be generally 2% ~ 6%, sodium hydroxide (potassium hydroxide) 1% ~ 6%, dosing difficulty, and cats product biodegradability is poor, anion surfactant working concentration is high, and zwitterionics working conditions is harsh.
Summary of the invention
The present invention seeks in order to overcome existing polymer fracturing fluid to hypotonic, ultra-permeable reservior and Damage to Fractures large, the shortcomings such as existing clean fracturing fluid preparation difficulty, working conditions are harsh, propose a kind of composition simple, prepare clean fracturing fluid viscosifying agent easily.
The present invention includes following steps:
1) under anaerobic, under sodium hydroxide or sodium methoxide catalyzed condition, longer chain fatty acid is carried out amidation, obtain the aminate of longer chain fatty acid;
2) by the aminate of longer chain fatty acid and hydroperoxidation, obtained clean fracturing fluid viscosifying agent.
Namely can be made under normal pressure of the present invention, manufacture craft is simple, be coordinate-covalent bond between nitrogen oxygen in amine oxide molecule, there is larger moment of dipole, polarity is large, and thickening capabilities is strong, the product made under equal temperature more conventional clean fracturing fluid tensio-active agent and additive working concentration low, prepare easy, cost is low.
In addition, because dimethylaminopropylamine is along with the increase of consumption, transformation efficiency improves not clearly, considers again dimethylaminopropylamine price, consumption should not increase again, so the molar ratio of longer chain fatty acid of the present invention and dimethylaminopropylamine is 1 ︰ 1.05 ~ 1.1.
When the temperature condition of amidate action of the present invention is 165 ~ 175 DEG C, the transformation efficiency of longer chain fatty acid can improve greatly, need not purify, and directly carries out second step reaction, is beneficial to suitability for industrialized production.
Described peroxidation is carried out under 1,2-PD, sodium bicarbonate and ethylenediamine tetraacetic acid (EDTA) exist, and the temperature condition of peroxidation is 55 ± 2 DEG C.During owing to exceeding this temperature, viscosity number declines, so the preferred said temperature condition of the present invention.
Because 1,2-PD quantity of solvent is very few, product easily forms gel, and too much effective concentration reduces; Sodium bicarbonate makes catalyzer, effective within the scope of this, too much can separate out; Ethylenediamine tetraacetic acid (EDTA) is complexing of metal ion agent, prevents heavy metal ion catalytic decomposition hydrogen peroxide, can affect rheological when dosage is many.So the present invention is seasonable at described peroxidation, the mass ratio that feeds intake of the aminate of longer chain fatty acid, 1,2-PD, sodium bicarbonate, ethylenediamine tetraacetic acid (EDTA) and hydrogen peroxide is 100 ︰ 84 ︰ 1.90 ~ 2.52 ︰ 0.05 ︰ 10.5.
Seasonable at described peroxidation, after first the mixing of the aminate of longer chain fatty acid, 1,2-PD, sodium bicarbonate and ethylenediamine tetraacetic acid (EDTA) being warming up to 45 ~ 50 DEG C, then drip aqueous hydrogen peroxide solution, can prevent hydrogen peroxide from crossing thermolysis.
Another object of the present invention proposes the application of above clean fracturing fluid viscosifying agent in clean fracturing fluid.
Middle temperature clean fracturing fluid viscosifying agent and NaCl, NaOH, water are mixed and made into clean fracturing fluid, and in described clean fracturing fluid, warm clean fracturing fluid viscosifying agent and NaCl, NaOH account for 2.0% ~ 3.0%, 0.75% ~ 1% and 0.2% of clean fracturing fluid total mass respectively.
The viscosifying agent used in this application method and the amount of NaCl, NaOH all less, concentration is low, and amine oxide aqueous solution is when pH>7, main in non-ionic surface active character, little to fracturing fracture injury, biological degradability is good, little to environmental influence.
Accompanying drawing explanation
Fig. 1 is viscosity and temperature, the graph of a relation of time of clean fracturing fluid.
Fig. 2 is another viscosity and temperature, the graph of a relation of time of clean fracturing fluid.
Fig. 3 is the injury rate graph of a relation of clean fracturing fluid to flow conductivity.
Embodiment
One, clean fracturing fluid viscosifying agent (JSCF-100) synthesis
1, surfactivity viscosifying agent synthesis ultimate principle:
Using longer chain fatty acid and other two kinds of industrial chemicals as the initial feed of synthetic surfactant, through two step chemical reactions, synthesize viscoelastic surfactant fatty acid amide dimethyl amine (JSCF-100).Longer chain fatty acid can be main carbochain be more than 14 saturated and unsaturated fatty acids.
As follows for oleic acid reaction equation:
2, surfactivity viscosifying agent synthesis step:
The first step (amidation): in a reservoir, adds oleic acid 1mol, heating and melting, logical nitrogen deoxygenation 5min.Add 1.05 ~ 1.1mol dimethylaminopropylamine, add catalyzer 1.5g sodium hydroxide or 1.97g sodium methylate, react 5.5 hours at 165 ~ 175 DEG C, obtain intermediate---the amidate of oleic acid.
Second step (peroxidation): in another container, add above-mentioned intermediate 100g, 84mL1,2-propylene glycol, 1.90 ~ 2.52g sodium bicarbonate, 0.05gEDTA(ethylenediamine tetraacetic acid (EDTA)), heat up, the hydrogen peroxide 35.0g that concentration is 30% is dripped at about 45 DEG C, 55 DEG C of reactions 4 hours, obtain clean fracturing fluid viscosifying agent (JSCF-100).
Two, apply:
1, middle temperature clean fracturing fluid viscosifying agent, NaCl, NaOH and water are mixed and made into clean fracturing fluid.
Wherein in clean fracturing fluid, warm clean fracturing fluid viscosifying agent and NaCl, NaOH account for 2.0% ~ 3.0%, 0.75% ~ 1% and 0.2% of clean fracturing fluid total mass respectively.
2, effect:
1. working concentration is low, and prepare easy, cost is low.
Under equal temperature more conventional clean fracturing fluid tensio-active agent and additive working concentration low, prepare easy, cost is low.
Fig. 1 shows the clean fracturing fluid containing 2.0%JSCF-100,1%NaCl and 0.2%NaOH, at 30 DEG C ~ 80 DEG C, 170s
-1the result of rheological experiment is done, as can be seen from Figure 1: after shearing 1h, viscosity still can reach about 90mPas under condition.
2. the clean fracturing fluid heatproof of 3.0%JSCF-100 preparation is used can to reach 100 DEG C.
Be coordinate-covalent bond between nitrogen oxygen in amine oxide molecule, have larger moment of dipole, polarity is large, and thickening capabilities is strong.
Fig. 2 shows the clean fracturing fluid containing 3.0%JSCF-100,0.75%NaCl and 0.2%NaOH, at 30 DEG C-100 DEG C, 170s
-1do the result of rheological experiment under condition, Fig. 2 can find out, after shearing 1h, viscosity still can reach about 25mPas.
3. the injury of fracture flow conductivity is little
As the pH>7 of amine oxide aqueous solution, main in non-ionic surface active character, little to fracturing fracture injury.
By industry standard SY/T6302-1997, take 64.5g20/40 order haydite, 64.5/1.8*40%=14.33mL is a volume of voids, and under 10MPa, logical breaking glue solution, surveys flow conductivity injury rate.
As seen from Figure 3, the injury rate of 2.0% clean fracturing fluid to flow conductivity is 13%, and the injury rate of polymer class fracturing liquid to flow conductivity is more than 90%.
The injury rate of visible clean fracturing fluid of the present invention is well below polymer class fracturing liquid.
4. biological degradability is good, little to environmental influence.
Owing to containing amido linkage and nitrogen oxygen coordinate-covalent bond in synthetic surfactant JSCF-100, readily biodegradable, little to environmental hazard.
The injury rate of your fracturing fluid of hydroxypropyl guanidine to flow conductivity is more than 90%, and the injury rate of clean fracturing fluid is well below hydroxypropyl guanidine that fracturing fluid.
Embodiment: Jiangsu oilfield C6 block C6-4A well E
1f
2 3sandstone reservoir 7# layer well section 2119.9-2122.9m, porosity is 10.1%, and rate of permeation is 2.8 × 10
-3μm
2, belong to low hole-ultra-permeable reservior.Formation temperature 81 DEG C.This well uses the clean fracturing fluid 50m of 2.0%JSCF-100 in January, 2012
3carry out pressure break, after pressure break, daily oil production rises to 6.8t/d by 1t/d before pressure break, and the oily 2655t of accumulative increasing, achieves good effect of increasing production.
Claims (2)
1. a synthetic method for warm fracturing fluid gelatinizer in, comprises the following steps:
1) under anaerobic, longer chain fatty acid and dimethylaminopropylamine are carried out amidate action, obtains the aminate of longer chain fatty acid;
2) aminate of longer chain fatty acid and hydrogen peroxide are carried out peroxidation, obtained clean fracturing fluid viscosifying agent;
Described amidate action carries out under sodium hydroxide or sodium methoxide catalyzed condition, and the temperature condition of amidate action is 165 ~ 175 DEG C; Described peroxidation is carried out under 1,2-PD, sodium bicarbonate and ethylenediamine tetraacetic acid (EDTA) exist, and the temperature condition of peroxidation is 55 ± 2 DEG C;
It is characterized in that the molar ratio of described longer chain fatty acid and dimethylaminopropylamine is 1 ︰ 1.05 ~ 1.1;
Described peroxidation is seasonable, and the mass ratio that feeds intake of the aminate of longer chain fatty acid, 1,2-PD, sodium bicarbonate, ethylenediamine tetraacetic acid (EDTA) and hydrogen peroxide is 100 ︰ 84 ︰ 1.90 ~ 2.52 ︰ 0.05 ︰ 10.5.
2. synthetic method according to claim 1, is characterized in that described peroxidation is seasonable, after first the mixing of the aminate of longer chain fatty acid, 1,2-PD, sodium bicarbonate and ethylenediamine tetraacetic acid (EDTA) being warming up to 45 ~ 50 DEG C, then drips aqueous hydrogen peroxide solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103438837B (en) * | 2013-09-05 | 2016-02-03 | 东南大学 | A kind of bidirectional deflection pointer of micro electro mechanical system |
| CN105348441A (en) * | 2015-12-10 | 2016-02-24 | 李准 | Production process of ultralow-concentration clean thickening agent fracturing fluid for petroleum oil-gas well |
| CN112342008B (en) * | 2020-11-06 | 2023-03-17 | 成都明亚科技有限公司 | Ammonium oxide surfactant fracturing fluid |
Citations (4)
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| US4093711A (en) * | 1976-08-13 | 1978-06-06 | Noxell Corporation | Oral hygiene |
| JPS6225197A (en) * | 1985-07-24 | 1987-02-03 | 川研ファインケミカル株式会社 | Liquid detergent composition |
| GB2405421A (en) * | 2003-07-18 | 2005-03-02 | Bj Services Co | Method of acidizing a subterranean formation with diverting foam or fluid |
| CN102851017A (en) * | 2012-08-16 | 2013-01-02 | 四川西普化工股份有限公司 | Viscous-elastic clean fracturing fluid containing erucic acid betaines |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887861A (en) * | 2005-06-29 | 2007-01-03 | 上海高维化学有限公司 | Prepn of alkyl amidopropyldimethyl amine oxide surfactant |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4093711A (en) * | 1976-08-13 | 1978-06-06 | Noxell Corporation | Oral hygiene |
| JPS6225197A (en) * | 1985-07-24 | 1987-02-03 | 川研ファインケミカル株式会社 | Liquid detergent composition |
| GB2405421A (en) * | 2003-07-18 | 2005-03-02 | Bj Services Co | Method of acidizing a subterranean formation with diverting foam or fluid |
| CN102851017A (en) * | 2012-08-16 | 2013-01-02 | 四川西普化工股份有限公司 | Viscous-elastic clean fracturing fluid containing erucic acid betaines |
Non-Patent Citations (4)
| Title |
|---|
| Solution Behavior of Long-alkyi-chain Amide Amine Oxide Surfactants Having Multiple Hydrogen-bonding Sites;Rie Kakehashi et al;《Chem.Lett》;20121231;第41卷;1050-1051 * |
| 一种压裂用黏弹性表面活性剂的合成及其应用性能研究;戚建平等;《精细石油化工》;20120731;第29卷(第3期);12-16 * |
| 脂肪酰胺丙基二甲基氧化胺的合成及其在酸性体系中的增稠研究;刘庆刚等;《日用化学品科学》;20120531;第35卷(第5期);28-31 * |
| 脂肪酰胺丙基二甲基氧化胺的合成及性能;方云，夏咏梅，周建东，邱峰;《日用化学工业》;19960220(第01期);4-6 * |
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