CN103951593A - Synthesis method and application of medium-temperature clean fracturing fluid thickening agent - Google Patents
Synthesis method and application of medium-temperature clean fracturing fluid thickening agent Download PDFInfo
- Publication number
- CN103951593A CN103951593A CN201410201382.4A CN201410201382A CN103951593A CN 103951593 A CN103951593 A CN 103951593A CN 201410201382 A CN201410201382 A CN 201410201382A CN 103951593 A CN103951593 A CN 103951593A
- Authority
- CN
- China
- Prior art keywords
- fracturing fluid
- clean fracturing
- fatty acid
- chain fatty
- longer chain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a synthesis method and application of a medium-temperature clean fracturing fluid thickening agent, relating to the technical field of oil production engineering. The synthesis method comprises the steps of amidating long-chain fatty acid under an anaerobic condition or a sodium hydrate catalysis condition or a sodium methoxide catalysis condition; enabling the obtained amide of the long-chain fatty acid to react with hydrogen peroxide to prepare the clean fracturing fluid thickening agent. The clean fracturing fluid thickening agent is mixed with NaCl, NaOH and water to prepare a clean fracturing fluid; the used thickening agent, NaCl and NaOH are small in quantity and low in concentration; when the pH value of an amide oxide water solution is larger than 7, the amide oxide water solution mainly has nonionic surface activity and is little in fracture damage, good in biodegradability and little in environment influence.
Description
Technical field
The present invention relates to technical field of oil production engineering, particularly the of the fracturing fluid blending technology 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 is mainly used 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 not polymer fragment of grade of size 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 residues concentrate in sand packed fracture, and in supporting crack, concentrated your glue of guanidine reduces fracture pore; Because low-permeability oil deposit pore throat radius is little, solid containing easily stratum being formed to infringement in fracturing liquid; In production process, fracturing fluid residue backflows and stops up propping agent packing layer, has reduced fracture flow capacity.Current hydroxypropyl guanidine that glue HPG(first grade) residue content is in 300mg/L left and right, your glue of carboxy-methyl hydroxy propyl guanidine GHPG(first grade) and the residue content of low-molecular(weight)polymer viscosifying agent in 100mg/L left and right, 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 special low permeability reservoir guanidine.
Domesticly aspect clean fracturing fluid, done a large amount of work, positively charged ion, negatively charged ion, amphoterics clean fracturing fluid have been studied, these fracturing fluid systems have without residue, to the feature such as fracturing fracture, formation damage be little, but these fracturing fluid systems are used 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, zwitterionics working conditions harshness etc.
Summary of the invention
The present invention seeks in order to overcome existing polymer fracturing fluid large to the injury of hypotonic, special low permeability reservoir and crack, the shortcoming 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 oxygen free condition, under sodium hydroxide or sodium methylate catalytic condition, longer chain fatty acid is carried out to amidation, obtain the aminate of longer chain fatty acid;
2), by the aminate of longer chain fatty acid and hydroperoxidation, make clean fracturing fluid viscosifying agent.
Under normal pressure of the present invention, can be made into, manufacture craft is simple, it in amine oxide molecule, between nitrogen oxygen, is coordinate-covalent bond, there is larger moment of dipole, polarity is large, and thickening capabilities is strong, the product of making under equal temperature more conventional clean fracturing fluid tensio-active agent and additive working concentration low, prepare easyly, cost is low.
In addition, due to the increase of dimethylaminopropylamine along with 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 ℃, 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 ℃.Owing to surpassing 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 is made 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, when dosage is many, can affect rheological.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, first the aminate of longer chain fatty acid, 1,2-PD, sodium bicarbonate and ethylenediamine tetraacetic acid (EDTA) are mixed and be warming up to after 45～50 ℃, then drip aqueous hydrogen peroxide solution, can prevent that hydrogen peroxide from crossing thermolysis.
Another object of the present invention is to propose 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 respectively 2.0%～3.0%, 0.75%～1% and 0.2% of clean fracturing fluid total mass.
The amount of the viscosifying agent using in this application method and NaCl, NaOH is all less, and concentration is low, and amine oxide aqueous solution is when pH>7, mainly be non-ionic surface active character, little to fracturing fracture injury, biological degradability is good, little to environmental influence.
Accompanying drawing explanation
Fig. 1 is the viscosity of clean fracturing fluid and temperature, the graph of a relation of time.
Fig. 2 is another viscosity of clean fracturing fluid and temperature, the graph of a relation of time.
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) is synthetic
1, the synthetic ultimate principle of surfactivity viscosifying agent:
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 oxidation amine (JSCF-100).Longer chain fatty acid can be that main carbochain is more than 14 saturated and unsaturated fatty acids.
Take oleic acid as example reaction equation as follows:
2, surfactivity viscosifying agent synthesis step:
The first step (amidation): in container, add 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, at 165～175 ℃, react 5.5 hours, obtain intermediate---the amidate of oleic acid.
Second step (peroxidation): in another container, add above-mentioned intermediate 100g, 84mL 1,2-propylene glycol, 1.90～2.52 g sodium bicarbonates, 0.05 g EDTA(ethylenediamine tetraacetic acid (EDTA)), heat up, at about 45 ℃, drip the hydrogen peroxide 35.0g that concentration is 30%, 55 ℃ of reactions 4 hours, obtain clean fracturing fluid viscosifying agent (JSCF-100).
Two, application:
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 respectively 2.0%～3.0%, 0.75%～1% and 0.2% of clean fracturing fluid total mass.
2, effect:
1. working concentration is low, prepares easyly, and cost is low.
Under equal temperature, more conventional clean fracturing fluid tensio-active agent and additive working concentration are low, prepare easyly, and cost is low.
Fig. 1 has shown and will contain the clean fracturing fluid of 2.0% JSCF-100,1% NaCl and 0.2% NaOH, at 30 ℃～80 ℃, 170s
-1under condition, do the result of rheological experiment, as can be seen from Figure 1: shear after 1h, viscosity still can reach 90 mPas left and right.
2. use the clean fracturing fluid heatproof of 3.0% JSCF-100 preparation can reach 100 ℃.
In amine oxide molecule, between nitrogen oxygen, be coordinate-covalent bond, have larger moment of dipole, polarity is large, and thickening capabilities is strong.
Fig. 2 has shown and will contain the clean fracturing fluid of 3.0% JSCF-100,0.75% NaCl and 0.2% NaOH, at 30 ℃-100 ℃, 170s
-1under condition, do the result of rheological experiment, Fig. 2 can find out, shears after 1h, and viscosity still can reach 25 mPas left and right.
3. the injury of fracture flow conductivity is little
When the pH>7 of amine oxide aqueous solution, be mainly non-ionic surface active character, little to fracturing fracture injury.
By industry standard SY/T6302-1997, take 64.5g 20/40 order haydite, 64.5/1.8*40%=14.33mL is a volume of voids, under 10MPa, logical breaking glue solution, surveys flow conductivity injury rate.
As seen from Figure 3,2.0% clean fracturing fluid is 13% to the injury rate of flow conductivity, and polymer class fracturing liquid is more than 90% to the injury rate of flow conductivity.
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 is little to environmental hazard.
Your fracturing fluid of hydroxypropyl guanidine is more than 90% to the injury rate of flow conductivity, and the injury rate of clean fracturing fluid is well below hydroxypropyl guanidine that fracturing fluid.
Embodiment: Jiangsu oilfield C6 piece C6-4A well E
1f
2 3sandstone reservoir 7# layer well section 2119.9-2122.9m, porosity is 10.1%, rate of permeation is 2.8 * 10
-3μ m
2, belong to low hole-Te low permeability reservoir.81 ℃ of formation temperature.This well is used the clean fracturing fluid 50m of 2.0% JSCF-100 in January, 2012
3carry out pressure break, after pressure break daily oil production by pressure break before 1t/d rise to 6.8t/d, totally increase oily 2655t, obtained good effect of increasing production.
Claims (7)
1. a synthetic method for warm clean fracturing fluid viscosifying agent in, is characterized in that comprising the following steps:
1) under oxygen free condition, under sodium hydroxide or sodium methylate catalytic condition, longer chain fatty acid and dimethylaminopropylamine are carried out to amidate action, obtain the aminate of longer chain fatty acid;
2) aminate of longer chain fatty acid and hydrogen peroxide are carried out to peroxidation, make clean fracturing fluid viscosifying agent.
2. synthetic method according to claim 1, the molar ratio that it is characterized in that described longer chain fatty acid and dimethylaminopropylamine is 1 ︰ 1.05～1.1.
3. synthetic method according to claim 1, the temperature condition that it is characterized in that described amidate action is 165～175 ℃.
4. synthetic method according to claim 1, is characterized in that described peroxidation carries out under 1,2-PD, sodium bicarbonate and ethylenediamine tetraacetic acid (EDTA) exist, and the temperature condition of peroxidation is 55 ± 2 ℃.
5. synthetic method according to claim 4, it is characterized in that described peroxidation is seasonable, 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.
6. according to synthetic method described in claim 4 or 5, it is characterized in that described peroxidation is seasonable, first the aminate of longer chain fatty acid, 1,2-PD, sodium bicarbonate and ethylenediamine tetraacetic acid (EDTA) are mixed and be warming up to after 45～50 ℃, then drip aqueous hydrogen peroxide solution.
7. the application of the middle temperature clean fracturing fluid viscosifying agent of making as claim 1 method in clean fracturing fluid, it is characterized in that middle temperature clean fracturing fluid viscosifying agent and NaCl, NaOH, water to be mixed and made into clean fracturing fluid, in described clean fracturing fluid, warm clean fracturing fluid viscosifying agent and NaCl, NaOH account for respectively 2.0%～3.0%, 0.75%～1% and 0.2% of clean fracturing fluid total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410201382.4A CN103951593B (en) | 2014-05-14 | 2014-05-14 | Warm clean fracturing fluid viscosifying agent synthetic method and application thereof in one |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410201382.4A CN103951593B (en) | 2014-05-14 | 2014-05-14 | Warm clean fracturing fluid viscosifying agent synthetic method and application thereof in one |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103951593A true CN103951593A (en) | 2014-07-30 |
| CN103951593B CN103951593B (en) | 2016-03-02 |
Family
ID=51328977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410201382.4A Active CN103951593B (en) | 2014-05-14 | 2014-05-14 | Warm clean fracturing fluid viscosifying agent synthetic method and application thereof in one |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103951593B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103438837A (en) * | 2013-09-05 | 2013-12-11 | 东南大学 | 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 |
| CN112342008A (en) * | 2020-11-06 | 2021-02-09 | 成都明亚科技有限公司 | Ammonium oxide surfactant fracturing fluid |
Citations (5)
| 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 |
| 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 |
| 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 |
-
2014
- 2014-05-14 CN CN201410201382.4A patent/CN103951593B/en active Active
Patent Citations (5)
| 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 |
| 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 |
| 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 (5)
| Title |
|---|
| RIE KAKEHASHI ET AL: "Solution Behavior of Long-alkyi-chain Amide Amine Oxide Surfactants Having Multiple Hydrogen-bonding Sites", 《CHEM.LETT》, vol. 41, 31 December 2012 (2012-12-31) * |
| 刘书秀: "氧化胺的制备、性质及应用", 《河北化工》, no. 4, 31 December 2004 (2004-12-31) * |
| 刘庆刚等: "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", 《日用化学品科学》, vol. 35, no. 5, 31 May 2012 (2012-05-31) * |
| 戚建平等: "一种压裂用黏弹性表面活性剂的合成及其应用性能研究", 《精细石油化工》, vol. 29, no. 3, 31 July 2012 (2012-07-31) * |
| 方云，夏咏梅，周建东，邱峰: "脂肪酰胺丙基二甲基氧化胺的合成及性能", 《日用化学工业》, no. 01, 20 February 1996 (1996-02-20) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103438837A (en) * | 2013-09-05 | 2013-12-11 | 东南大学 | Bidirectional deflection pointer of micro electro mechanical system |
| 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 |
| CN112342008A (en) * | 2020-11-06 | 2021-02-09 | 成都明亚科技有限公司 | Ammonium oxide surfactant fracturing fluid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103951593B (en) | 2016-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110218557A (en) | The preparation method of salt-resistant type Gemini zwitterionic viscoelastic surfactant and the water base clean fracturing fluid of high salinity | |
| CN104498014B (en) | Profile control agent based on breaking glue solution and preparation method thereof | |
| CN102851017A (en) | Viscous-elastic clean fracturing fluid containing erucic acid betaines | |
| CN103951593B (en) | Warm clean fracturing fluid viscosifying agent synthetic method and application thereof in one | |
| CN103275693B (en) | A kind of acid CO 2the efficient pore forming material of foam fracturing system | |
| RU2009106247A (en) | LAYOUT METHOD | |
| CN102952535A (en) | Self heat-generating and gas-generating clean fracturing fluid | |
| CN103911140B (en) | A kind of combined fracturing fluid enzyme gel breaker and using method thereof | |
| EP2139969A1 (en) | Method for treating subterranean formation | |
| CN104073235A (en) | Long-carbon-chain amide glycine betaine clean fracturing fluid and preparation method thereof | |
| CN101948684A (en) | Novel active water fracturing fluid for fracturing of coal bed gas well | |
| CN104371698A (en) | Clean high-temperature fracturing fluid containing erucylamidoammonium oxide | |
| CN101955441A (en) | Preparation method and application of fatty amide polyethylene polyamine amino acid for tertiary oil recovery | |
| AU2015389879A1 (en) | Crosslinked fluid treatment and methods for fracturing underground formations based on flowback, production water, seawater, fresh water, and mixtures of same | |
| CN107794030A (en) | A kind of imitative recyclable clean fracturing fluid of peptide type | |
| CN103951599B (en) | A kind of salt-free type clean fracturing fluid surface-active thickening agent synthetic method | |
| CN105086986A (en) | High-temperature-resistant recyclable clean fracturing fluid for gas wells | |
| CN104277818A (en) | Drag reducer for fracturing fluid and application thereof | |
| CN105820805B (en) | A kind of oil field clean fracturing fluid and preparation method thereof | |
| US20140338914A1 (en) | Method for enhancing the permeability of a geological formation | |
| CN102329396A (en) | Hydrophobic group and hydroxypropyl group-contained guar gum | |
| CN104277819A (en) | Drag reducer for fracturing fluid for shale gas reservoirs and preparation method thereof | |
| CN103305851B (en) | A kind of supramolecule composite corrosion inhibitor and preparation method | |
| CN105348441A (en) | Production process of ultralow-concentration clean thickening agent fracturing fluid for petroleum oil-gas well | |
| CN106118625A (en) | A kind of surfactant fracturing fluid system and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |