CN102559168A - Acid-sensitive variable-viscosity mixed surfactant - Google Patents
Acid-sensitive variable-viscosity mixed surfactant Download PDFInfo
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- CN102559168A CN102559168A CN2012100028629A CN201210002862A CN102559168A CN 102559168 A CN102559168 A CN 102559168A CN 2012100028629 A CN2012100028629 A CN 2012100028629A CN 201210002862 A CN201210002862 A CN 201210002862A CN 102559168 A CN102559168 A CN 102559168A
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Abstract
The invention provides an acid-sensitive variable-viscosity mixed surfactant, formed by mixing sulphonate Gemini surfactant and alkyl glucoside non-ionic surfactant in mass ratio of (1-4): (4-1). Viscosity of a mixed system is high, after acid is added into the system, the viscosity is rapidly reduced. In an acid-containing acid-sensitive mixed surfactant system, viscosity of solution is improved by consuming acid, and the acid-containing acid-sensitive mixed surfactant system has low-permeability interval automatic finding characteristic during oil reservoir acidification, has automatic steering function, can realize uniform acidification and can obtain good acidification effect. The acid-containing acid-sensitive mixed surfactant has high viscosity after being acidified, the viscosity can be automatically reduced after the acid-containing acid-sensitive mixed surfactant is contacted with crude oil or hydrocarbon substance, the viscosity is close to the viscosity of water, and the acid-containing acid-sensitive mixed surfactant is easy to flow back.
Description
Technical field:
The present invention relates to a kind of acid sensitivity mixed surfactant that becomes sticky, specifically, the become sticky viscosity of mixed surfactant system of acid sensitivity increases with the reduction of acid strength, has from turning to function, can be used as acidifying and uses from diversion agent.
Background technology:
Acidifying is one of method of intensified oil reduction (EOR), is well production increment, an otherwise effective technique measure of injecting the well augmented injection.Its principle is through dissolving and the corrosion of acid solution to tamper in rock cementing matter or formation pore, the crack etc., recovers or improves formation pore and fissured perviousness.Acidifying can be divided into pickling, matrix acidifying and acid fracturing (also claiming acid fracturing) according to the technology difference.Pickling is that a small amount of acid solution is injected in the pit shaft, removes solubility in acid particle and drilling cuttings and dirt etc. in the pit shaft eyelet, and the mediation perf.Matrix acidifying is the stratum to be injected in acid being lower than under the rock burst pressure, rely on the corrosion of acid solution recover or improve near the pit shaft in a big way in the perviousness of oil reservoir.Acid fracturing is the stratum to be injected in acid being higher than under the rock burst pressure, in the stratum, forms the crack, the inhomogeneous corrosion of sides of fracture face material is formed the crack of high flow conductivity through acid solution.Acidizing treatment use such as
Cementing truck,
Pump truckOne type Construction traffic, with acidic aqueous solution (example hydrochloric acid,
Hydrofluoric acid,
Organic acid) inject
The stratumThe acid solution of injecting can be dissolved the stratum
RockOr
Cementing matterThereby, increase zone permeability, make the output of oil gas, displacement water inject convenient.
Because formation heterogeneity, the feasible fresh acid solution of injecting be intake resistance interval minimum, that rate of permeation is high at first, in these intervals; Acid fluid dissolves carbonate or sandstone mineral; And produced the highly conc passage, made these intervals have higher injectability, the result who finally causes is that most of acid solutions flow into same interval; And other target interval does not advance acid, can not obtain acidifying.Therefore, need carry out the acid solution diversion treatments, guarantee that whole stratum all obtains acidification, so that obtain the rate of permeation of homogeneous.The effect of diversion agent is that the balance acid solution flows, so that the stratum of different rate of permeation all can reach acidifying.According to the mechanism of action, acidifying turns to technology can be divided into mechanical steering and chemistry turns to etc.
Mechanical steering mainly contains pkr and turns to particle and turn to, but mechanical skill is heavy, needs on-the-spot appliance arrangement, and not only time-consuming but also expensive, its validity receives the influence of eyelet circularity and slickness and perforation quantity; Particle turns to the diversion agent of use also to be difficult to discharge, and causes formation damage easily.
The acidifying mode that chemistry turns to has the turning to certainly of OSR suspension-s, polymer class, surfactant-based turning to certainly with foam to turn to etc.
On the borehole wall, stick with paste after OSR suspension-s pours down, extraction crude oil in stratum returns its dissolving and ejects, and its advantage is that resin can be out of shape; Heatproof is also good, and plugging effect is good, but expensive; External soluble solids with the pore throat size match commonly used is done, but at home, the one, seldom do the analysis of pore throat data during design; The 2nd, be difficult to find industrialized known particle diameter material, the effect of therefore always doing is bad.
The polymer class diversion agent is formed the viscosity that improves acid solution by solubility in acid polymkeric substance or solubility in acid polymkeric substance and linking agent; Such diversion agent viscosity under the low situation of pH value is higher; And when the pH value raises viscosity degradation, or under the effect of depolymerizing agent, guarantee crosslinked disintegration fully.Acid liquid viscosity reduces, and is easier to shift out from the stratum.But remain in the superpolymer in the interval, will damage the perviousness of reservoir, therefore reduce the validity of acidification.Show that according to the relevant systems analysis of returning discharge opeing in the acidification process, 30% to 45% injection superpolymer returns row at oil well and obtains in the stage reclaiming, considerable polymkeric substance is still stayed in the stratum.In order to increase the effect of clear operation, once attempted a series of measure, yet produced little effect.
Surfactant-based turn to main employing viscoelastic surfactant certainly, when viscoelastic surfactant self-steering acid penetration was gone into the carbonate rock, along with the carrying out of sour rock reaction, acid concentration constantly descended, the pH value and the CaCl of solution
2, MgCl
2Concentration increase; The rising of the appearance of salt and pH value is transformed into the elongated rod shape micella in the viscoelastic fluid and twines the vermiculate glues of knitting together each other; High viscosity fluid has served as temporary transient barrier action; Turn to fluid to remaining low permeability processing layer, after processing finishes, run into the hydrocarbon polymer in the reservoir or break glue in advance during (back) treatment solution automatically based on the acid solution barrier of viscoelastic surfactant.The viscoelastic surfactant that report is used mainly contains betaine type (Zheng Yunchuan; Zhao Liqiang; Liu Pingli. the acidizing fluid research [J] that becomes sticky of mustard seed amido propyl betaine. oilfield chemistry; 2005,4:302-306) and big type of quaternary (Bernhard Lungwitz.Diversion and clean up studies of viscoelastic surfactant-based self-diverting acid [C] .SPE 86504:9-11) two.
It is with the acid solution that has added pore forming material and nitrogen thorough mixing in the frothing machine of ground that foam turns to acidifying, forms stable foam and injects into well immediately, improves the stratum production capacity.Because of the gas in the foamed acid helps row's effect, the foamed acid acidifying is specially adapted to the reservoir reconstruction of low pressure and low permeability discharge opeing difficulty, old well production potential tapping and low pressure well stimulation, the operation that also can effectively solve exceptional wells such as discharge opeing difficulty, sensitive reservoir.
In the application that turns to, surfactant-based turns to spot effect best certainly at above-mentioned chemistry, but the viscoelastic surfactant concentration of using is higher, and general concentration is greater than 4%, thereby cost is higher, and its application is restricted.
Summary of the invention:
The objective of the invention is to utilize the mixed surfactant system soltion viscosity with the characteristics that acid concentration changes, a kind of acid sensitivity mixed surfactant that becomes sticky is provided.
For reaching above technical purpose, the present invention proposes following technical scheme.
The acid sensitivity mixed surfactant that becomes sticky is to mix in 4: 1～1: 4 to form by sulphonate Gemini surfactant and APG nonionogenic tenside by mass ratio, wherein,
The structural formula of sulphonate Gemini surfactant is following:
In the formula, n=2,4,6,8,
Hydrophobic group R group is:
The molecular weight of sulphonate Gemini surfactant is 642～726.
The structural formula of APG nonionogenic tenside is following:
In the formula, m=8～16, n=1.2～1.8,
The molecular weight of APG nonionogenic tenside is 304.6～550.4.
Sulphonate Gemini surfactant has better chemical stability, temperature tolerance and salt tolerance; The low 1-2 one magnitude of the conventional single linked list surface-active agent of active height and ratio of the (Zhao Xiutai etc. connect the influence [J] of the IT and the lathering property of basic p-sulfonic acid salt type Gemini surface active agent. petroleum journal (refining of petroleum), 2011 27 2 phases of volume).
APG (Alkyl Polyglycoside, APG for short) belongs to novel nonionogenic tenside by the pure and mild glucose synthetic of renewable resources natural fat, is a kind of compound that in water, is not dissociated into the amphiphilic structure of ionic condition.APG has four outstanding advantages: (1) surface tension is low, can with various surfactant compounds, have the characteristics of synergistic effect; (2) toxicity is little, and is little to skin irritation; (3) biological degradation is complete, meets environmental protection concept; (4) belong to renewable resources, can solve the various drawbacks that oil crisis is brought.Thereby APG is called as world-class green surfactant of 21 century.
The mass ratio of sulphonate Gemini surfactant and APG nonionogenic tenside is 4: 1～1: 4 in the mixed surfactant system.When the tensio-active agent total mass concentration was 2% in the mixed surfactant system, system viscosity was higher; And in system, slowly adding hydrochloric acid, system viscosity reduces.In mass concentration is that to add mass concentration in 2% the mixed surfactant system be 5% hydrochloric acid, and again toward wherein adding lime carbonate, along with the carrying out of reaction, acid strength reduces, and system viscosity raises.
The invention has the beneficial effects as follows: acidiferous acid sensitivity becomes sticky that mixed surfactant has that viscosity descends along with acid strength and the characteristics that raise, the acid solution diversion agent of can be with it using during as the oil reservoir acidifying.At the acidifying initial stage, fresh acid solution gets into the most permeable zone section, and along with the carrying out of sour rock reaction, acid strength descends, and system viscosity raises, and acid solution and reaction rates with rocks certainly will be slowed down; System viscosity increases simultaneously, and resistance to flow increases, and makes follow-up fresh acid solution get into the relatively low interval of rate of permeation; Acid rock reaction back system viscosity raises, and makes follow-up acid solution get into other low permeability interval again, and that goes round and begins again like this carries out acidifying; Acid solution is sought the low relatively interval of rate of permeation automatically; Cause the high interval of rate of permeation to be unlikely to excessive acidifying, therefore, adopt the acidiferous acid sensitivity mixed surfactant system that becomes sticky to obtain the uniform acidizing effect of rate of permeation.
Embodiment:
Further specify the present invention through embodiment below.
Embodiment 1: according to the mass ratio of sulphonate Gemini surfactant and APG nonionogenic tenside is that to prepare the tensio-active agent total mass concentration in 4: 1,3: 1,2: 1,1: 1,1: 2,1: 3 and 1: 4 respectively be 2% mixed surfactant system; In each system, add mass concentration then respectively and be 2% Calcium Chloride Powder Anhydrous; In the viscosity of measuring under 60 ℃ the condition under the different shear rate, the result sees table 1.Under 1: 4～4: 1 mass ratio, mixed surfactant has higher viscosity, and viscosity is far longer than the viscosity of single surfactant soln, and when mass ratio is 2: 1, the tackify best results of mixed surfactant.
Table 1 acid sensitivity mixed surfactant system viscosity
Embodiment 2: preparation hydrochloric acid mass concentration is respectively 1%, 0.5%, 0.1%, 0.05%, 0.01%, 0.005% and 0% sulphonate Gemini surfactant and the mass ratio of APG nonionogenic tenside is 2: 1 mixed surfactants solutions systems; The total surfactant mass concentration of this system is 1.5%; In each system, add mass concentration then respectively and be 2% Calcium Chloride Powder Anhydrous; In the viscosity of measuring under 60 ℃ the condition under the different shear rate, see table 2.The viscosity of mixed surfactant system raises along with the reduction of sour mass concentration.
Table 2 acid concentration is to the influence of acid sensitivity mixed surfactant system viscosity
Embodiment 3: the preparation mass concentration is 1.5%, the mass ratio of sulphonate Gemini surfactant and APG nonionogenic tenside is that 2: 1 mixed surfactants solutions system and mass concentration is 2% anhydrous chlorides of rase calcium solution; It is very big to obtain solution system viscosity; Add volume ratio again and be 3% kerosene; Stir back solution system viscosity and obviously reduce, add volume ratio again and be 3% kerosene, solution system viscosity is near the viscosity of water.
Embodiment 4: preparation acidifying acid solution solution; Wherein contain mass concentration and be 5% hydrochloric acid; Mass concentration is 2.0%, the mass ratio of sulphonate Gemini surfactant and APG nonionogenic tenside is 2: 1 mixed surfactants solutions system, and mass concentration is that 2% Calcium Chloride Powder Anhydrous and mass concentration are 0.2% octyne alcohol; Acidifying acid solution solution is injected the bigger rock core of rate of permeation extreme difference, and along with the carrying out of sour rock reaction, injection pressure progressively raises; After reaction is accomplished, removal of core, a bit of inlet section that contacts with acid solution of intercepting; Examine under a microscope, find that pore size is even basically.
Compared with prior art, the present invention has the following advantages:
(1) acid sensitivity mixed surfactant system viscosity provided by the invention is very responsive to the variation of acid concentration, and system viscosity significantly raises with the reduction of acid concentration;
When (2) acid sensitivity mixed surfactant system provided by the invention can be used as acidifying acid solution from diversion agent, have the function of automatic searching low permeability interval;
(3) acidiferous fresh acid sensitivity mixed surfactant system viscosity is lower, has the advantages that to be prone to injection;
(4) acid sensitivity mixed surfactant system provided by the invention viscosity after acidifying is higher, when its with can automatic viscosity reduction after crude oil or hydrocarbons contact, viscosity approaches the viscosity of water, the row of returning easily;
(5) working concentration of acid sensitivity mixed surfactant system provided by the invention is lower than the viscoelastic surfactant diversion agent of report, applies for it and has created favourable condition.
Claims (2)
1. acid sensitivity mixed surfactant that becomes sticky; It is characterized in that mixing in 1: 4～4: 1 by mass ratio by sulphonate Gemini surfactant and APG nonionogenic tenside; The molecular weight of described sulphonate Gemini surfactant is 642～726, and its structural formula is following:
Wherein, n=2,4,6,8,
Hydrophobic group R group is:
The molecular weight of described APG nonionogenic tenside is 304.6～550.4, and its structural formula is following:
Wherein, m=8～16, n=1.2～1.8.
2. acid sensitivity according to claim 1 become sticky mixed surfactant during as acidifying acid solution from diversion agent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106281296A (en) * | 2016-08-08 | 2017-01-04 | 安徽炎胜新材料科技有限公司 | A kind of become sticky acid from broken glue surfactant |
| CN106590575A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant low-tension foaming agent composition as well as preparation method and application thereof |
| CN113004883A (en) * | 2021-03-22 | 2021-06-22 | 郑州市新郑梅久实业有限公司 | Cleanup additive for fracturing and preparation method thereof |
| CN113884425A (en) * | 2021-06-21 | 2022-01-04 | 中海油田服务股份有限公司 | Quantitative acid liquid slug combined selection method for carbonate rock |
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| WO2006055549A2 (en) * | 2004-11-15 | 2006-05-26 | Rhodia Inc. | Viscoelastic surfactant fluids having enhanced shear recovery, rheology and stability performance |
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| WO2006055549A2 (en) * | 2004-11-15 | 2006-05-26 | Rhodia Inc. | Viscoelastic surfactant fluids having enhanced shear recovery, rheology and stability performance |
| WO2007056392A2 (en) * | 2005-11-07 | 2007-05-18 | Stepan Company | Polycationic viscoelastic compositions |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106590575A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Temperature-resistant salt-resistant low-tension foaming agent composition as well as preparation method and application thereof |
| CN106281296A (en) * | 2016-08-08 | 2017-01-04 | 安徽炎胜新材料科技有限公司 | A kind of become sticky acid from broken glue surfactant |
| CN113004883A (en) * | 2021-03-22 | 2021-06-22 | 郑州市新郑梅久实业有限公司 | Cleanup additive for fracturing and preparation method thereof |
| CN113884425A (en) * | 2021-06-21 | 2022-01-04 | 中海油田服务股份有限公司 | Quantitative acid liquid slug combined selection method for carbonate rock |
| CN113884425B (en) * | 2021-06-21 | 2023-12-15 | 中海油田服务股份有限公司 | Quantitative acid liquid slug combination selection method for carbonate rock |
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Application publication date: 20120711 |