CN102618249A - Seawater base fracturing fluid and preparation method thereof - Google Patents
Seawater base fracturing fluid and preparation method thereof Download PDFInfo
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- CN102618249A CN102618249A CN2012100554361A CN201210055436A CN102618249A CN 102618249 A CN102618249 A CN 102618249A CN 2012100554361 A CN2012100554361 A CN 2012100554361A CN 201210055436 A CN201210055436 A CN 201210055436A CN 102618249 A CN102618249 A CN 102618249A
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Abstract
The invention relates to seawater base fracturing fluid, which is obtained by the steps of mixing 97-99 weight parts of seawater, 0.3-0.7 weight part of a thickening agent, 0.5-0.8 weight part of a surfactant, 0.05-0.2 weight part of a potential of hydrogen (pH) adjusting agent and 0.01-0.05 weight part of a gel breaker, and then performing cross-linking reaction with 0.3-0.7 weight part of a cross-linking agent. The thickening agent is a guar gum derivative formed by modifying hydroxyalkyl, carboxyl alkyl and sulfonic acid groups. The invention further relates to a preparation method of the seawater base fracturing fluid.
Description
Technical field
The present invention relates to a kind of seawater base fracturing liquid and preparation method thereof.
Background technology
Existing fracturing liquid all is the fresh water preparation, but for offshore oilfield, providing owing to receive influence of various factors such as space, transportation, cost of Freshwater resources is difficult to satisfy the needs that oil field compression fracture is transformed.For offshore oilfield, seawater is again a kind of ubiquity, the water resources of taking easily.But because seawater is the water system of a complicacy, the inside includes tens kinds of mineral elements, also has the existence of multiple organic matter, is the aqueous systems of a high salt, many compositions.Water-based fracturing fluid gelatinizer at present commonly used all more or less the influence that receives seawater component and be difficult to satisfy the requirement of pressing crack construction.
Therefore, need a kind of seawater water body that adapts to of exploitation to satisfy the fracturing liquid that pressure break requires simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of seawater base fracturing liquid.
Another object of the present invention provides the of the fracturing fluid method of a kind of preparation seawater base.
Seawater base fracturing liquid provided by the invention is the gel breaker mixing with the pH value regulator of the tensio-active agent of the viscosifying agent of the seawater of 97-99 weight part, 0.3-0.7 weight part, 0.5-0.8 weight part, 0.05-0.2 weight part, 0.01-0.05 weight part; Carry out crosslinking reaction with the 0.3-0.7 parts by weight of cross-linking agent then and promptly get, wherein said viscosifying agent is hydroxyalkyl, carboxyalkyl and sulfonic group modified guar derivative.
Viscosifying agent of the present invention; The preparation method who is hydroxyalkyl, carboxyalkyl and sulfonic group modified guar derivative can comprise by guar gum and oxyethane and/or propylene oxide; In the mixed solvent of alcohol-water, under the catalysis of Lewis acid or Lewis base, opening takes place in controlled temperature in 45-85 ℃ of scope; Reaction times 2-5 hour, filter, wash 2-4 time; Then, in the mixed solvent of alcohol-water, under the catalysis of basic cpd; Controlled temperature 50-90 ℃; React with carboxylated reagent and sulfonated reagent, reaction times 2-6 hour, filter, wash 2-4 time; Dry 4-10 hour, make and contain hydroxyalkyl, carboxyalkyl and/or sulfonic guar derivative.
Said Lewis acid is one or more in aluminum chloride, iron(ic)chloride, hydrochloric acid, sulfuric acid, the nitric acid; Said Lewis base is one or more in ammonia, Monomethylamine, sodium hydroxide, Pottasium Hydroxide, quicklime, the Natural manganese dioxide; Said pure water mixed solvent is formed (meter by volume) by the water of 0-50%, the alcohol of 50-100%; Said alcohol is methyl alcohol, ethanol, Virahol and composition thereof.Carboxylated reagent is selected from Mono Chloro Acetic Acid; Sulfonated reagent is selected from chlorsulfonic acid, the vitriol oil, sulphur trioxide, oleum, thionamic acid and sulphite.
Linking agent of the present invention is by the host of 5-15 weight part, the complexing agent of 10-20 weight part, the composite composition of water of 65-85 weight part.Host is selected from one or more in basic zirconium chloride, zirconate, zirconium tetrachloride, titanium tetrachloride, the titanic acid ester; Complexing agent is selected from one or more in polyvalent alcohol, polyprotonic acid, the alkanolamine; Polyvalent alcohol is selected from terepthaloyl moietie, USP Kosher, N.F,USP MANNITOL, Xylitol, sorbyl alcohol; Polyprotonic acid is selected from oxalic acid, tartrate, Hydrocerol A, propanedioic acid and Succinic Acid; Alkanolamine is selected from Monoethanolamine MEA BASF, diethylolamine and trolamine.
Tensio-active agent of the present invention is fluorocarbon surfactant, polyether surfactant, polyether carboxylation's type tensio-active agent and their mixtures; Polyethet surfactant is meant OP-7, OP-10, AEO-9, AE-1910, HD-3, SP169 etc., and polyether carboxylation's type tensio-active agent is meant AES, ABS, SBS etc.
Gel breaker of the present invention is selected from one or more in Potassium Persulphate, Sodium Persulfate, ammonium persulphate, potassium permanganate, potassium perchlorate, Potcrate, potassium periodate, Potassium Iodate and the ydrogen peroxide 50.
PH regulator according to the invention is selected from one or more in acetic acid, oxalic acid, formic acid, Hydrocerol A, hydrochloric acid, yellow soda ash, sodium hydrogencarbonate and the sodium hydroxide.
Seawater base of the present invention is of the fracturing fluid preparation method comprise the steps:
Viscosifying agent, tensio-active agent, gel breaker, pH value regulator sea water mixing are got base fluid, and then add linking agent and carry out crosslinking reaction and promptly get the seawater base fracturing liquid.
Seawater base fracturing liquid of the present invention is applicable to the seawater of China's different waters, and temperature resistant capability reaches 120 ℃.
Seawater base fracturing liquid of the present invention and seawater compatibleness are good, to the Ca in the seawater
2+, Mg
2+, Fe
3+Have tolerance and good complexing etc. multiple high price, variable valency metal ions.Can overcome and reduce the injury that secondary sedimentation causes.
Embodiment
Below in conjunction with embodiment the present invention is further specified, the material that adopts in following examples, except indicating, all the other are commercially available.
Embodiment 1:
At first prepare viscosifying agent: the guar gum flour of getting 50g adds in the mixing solutions of 100ml ethanol and 50ml water composition, adds the sodium hydroxide of 3g, and temperature control adds the oxyethane of 60ml to 50-55 ℃; Reacted 3 hours, and be cooled to room temperature, filter; Wash 2 times, add again in the mixing solutions of 100ml Virahol and 30ml water composition, add 2.5g sodium hydroxide; Temperature control 60-65 ℃, reaction 15min adds 5g Mono Chloro Acetic Acid and 1.5g chlorsulfonic acid reaction 4h; Be cooled to room temperature, filter, wash 3 times, drying and crushing is processed dry powder and is got hydroxyethyl-carboxymethyl sulfonic group guar gum.
Secondly the preparation of linking agent is got 10.0 gram basic zirconium chlorides and is added in the 70g water, and stirring and dissolving adds 6.8g oxalic acid, 2.3g Monoethanolamine MEA BASF, 4.7g trolamine more successively, and controlled temperature 45-50 ℃, reaction 3h makes alkanolamine zirconate-oxalic acid inner complex.
Measuring the 98.5ml seawater with graduated cylinder pours in the beaker that has magnetic stirring apparatus; Agitator also stirs with about 500rpm rotating speed; Under normal temperature condition, add the tensio-active agent (forming) of 0.5g, the ammonium persulphate of 0.04g then successively, slowly add the viscosifying agent of 0.5g at last again, treat swelling back (about 30 minutes) fully by 4g fluorocarbon surfactant, 25g AE1910,71g water; In beaker, adding 0.1g soda ash makes pH value in the scope of 7-9; Slowly add the above-mentioned organic zirconium linking agent of about 0.4g then, reaction continues to and makes the fracturing liquid that is mixed with have good visco-elasticity, can hang with glass stick and be advisable.
Performance evaluation:
According to SY/T 5107-2005 aqueous fracturing fluid method of evaluating performance fracturing liquid of the present invention is carried out performance evaluation.
Following table 1 has shown fracturing liquid and the performance index of fracturing liquid of the prior art in seawater that made by embodiment 1.
Fracturing liquid performance: adopt the RS-6000 rheometer, at 100 ℃, 170s
-1Shearing rate down cut 1h measures the fracturing liquid performance.Conventional fracturing liquid makes fracturing liquid according to the ordinary method of this area, and viscosifying agent concentration is identical with embodiment 1.
Table 1: conventional H PG fracturing liquid and fracturing liquid performance comparison of the present invention
Table 1 data presentation, it is big that fracturing liquid initial viscosity of the present invention and 1h shear the conventional fracturing liquid system of back viscosity ratio, shows that of the fracturing fluid heat-resisting property of the present invention, anti-shear performance are better than conventional fracturing liquid.And system status is described and is shown behind the broken glue, and fracturing liquid of the present invention prevents that to stablizing high-valency metal, variable valency metal the secondary sedimentation injury is better than conventional fracturing liquid, is more suitable for seawer system.
Embodiment 2:
At first prepare viscosifying agent: the guar gum flour of getting 50g adds in the mixing solutions of 100ml ethanol and 40ml water composition, adds the sodium hydroxide of 4.0g, and temperature control adds the oxyethane of 50ml to 50-55 ℃; Reacted 3 hours, and be cooled to room temperature, filter; Wash 2 times, add again in the mixing solutions of 100ml Virahol and 20ml water composition, add 2.0g sodium hydroxide; Temperature control 60-65 ℃, reaction 15min adds 4.0g Mono Chloro Acetic Acid and 2.0g chlorsulfonic acid reaction 4h; Be cooled to room temperature, filter, wash 3 times, drying and crushing is processed dry powder and is got hydroxyethyl-carboxymethyl sulfonic group guar gum.
Secondly the preparation of linking agent is got 9.0 gram basic zirconium chlorides and is added in the 77g water, and stirring and dissolving adds 6.8g oxalic acid, 7.2g trolamine more successively, and controlled temperature 50-55 ℃, reaction 4h makes triethanolamine zirconate-oxalic acid inner complex.
Measuring the 98.5ml seawater with graduated cylinder pours in the beaker that has magnetic stirring apparatus; Agitator also stirs with about 500rpm rotating speed; Under normal temperature condition, add the tensio-active agent (forming) of 0.5g, the ammonium persulphate of 0.04g then successively, slowly add the viscosifying agent of 0.5g at last again, treat swelling back (about 30 minutes) fully by 4g fluorocarbon surfactant, 25g AE1910,71g water; In beaker, adding 0.1g soda ash makes pH value in the scope of 7-9; Slowly add the above-mentioned organic zirconium linking agent of about 0.4g then, reaction continues to and makes the fracturing liquid that is mixed with have good visco-elasticity, can hang with glass stick and be advisable.
Performance evaluation:
According to SY/T 5107-2005 aqueous fracturing fluid method of evaluating performance fracturing liquid of the present invention is carried out performance evaluation.
Following table 2 has shown fracturing liquid and the performance index of fracturing liquid of the prior art in seawater that made by embodiment 2.
Fracturing liquid performance: adopt the RS-6000 rheometer, at 100 ℃, 170s
-1Shearing rate down cut 1h measures the fracturing liquid performance.Conventional fracturing liquid makes fracturing liquid according to the ordinary method of this area, and viscosifying agent concentration is identical with instance 2.
Table 2: conventional H PG fracturing liquid and fracturing liquid performance comparison of the present invention
The data presentation of table 2 goes out fracturing liquid initial viscosity of the present invention and 1h, and to shear the conventional fracturing liquid system of back viscosity ratio big, shows that of the fracturing fluid heat-resisting property of the present invention, anti-shear performance are better than conventional fracturing liquid.And system status is described and is shown behind the broken glue, and fracturing liquid of the present invention prevents that to stablizing high-valency metal, variable valency metal the secondary sedimentation injury is better than conventional fracturing liquid, is more suitable for seawer system.
The present invention can summarize with other the specific form without prejudice to spirit of the present invention or principal character.Therefore; No matter from which point; Above-mentioned embodiment of the present invention can only think that all claims have been pointed out scope of the present invention, therefore to exemplary illustration of the present invention rather than restriction the present invention; In implication suitable and any change in the scope, all think to be included in the scope of claims with claims of the present invention.
Claims (9)
1. seawater base fracturing liquid; It is the gel breaker mixing with the pH value regulator of the tensio-active agent of the viscosifying agent of the seawater of 97-99 weight part, 0.3-0.7 weight part, 0.5-0.8 weight part, 0.05-0.2 weight part, 0.01-0.05 weight part; Carry out crosslinking reaction with the 0.3-0.7 parts by weight of cross-linking agent then and promptly get, wherein said viscosifying agent is hydroxyalkyl, carboxyalkyl and sulfonic group modified guar derivative.
2. seawater base fracturing liquid as claimed in claim 1; Wherein said hydroxyalkyl, carboxyalkyl and sulfonic group modified guar derivative prepare through following step: by guar gum and oxyethane and/or propylene oxide; In the mixed solvent of alcohol-water, under the catalysis of Lewis acid or Lewis base, opening takes place in controlled temperature in 45-85 ℃ of scope; Reaction times 2-5 hour, filter, wash 2-4 time; Then, in the mixed solvent of alcohol-water, under the catalysis of basic cpd, controlled temperature 50-90 ℃, react with carboxylated reagent and sulfonated reagent, reaction times 2-6 hour, filter, wash 2-4 time, dry 4-10 hour, promptly get.
3. seawater base fracturing liquid as claimed in claim 2, said Lewis acid are one or more in aluminum chloride, iron(ic)chloride, hydrochloric acid, sulfuric acid, the nitric acid; Said Lewis base is one or more in ammonia, Monomethylamine, sodium hydroxide, Pottasium Hydroxide, quicklime, the Natural manganese dioxide; Said pure water mixed solvent is made up of the water of 0-50% and the alcohol of 50-100% by volume; Said alcohol is methyl alcohol, ethanol, Virahol and composition thereof; Said carboxylated reagent is selected from Mono Chloro Acetic Acid; Said sulfonated reagent is selected from chlorsulfonic acid, the vitriol oil, sulphur trioxide, oleum, thionamic acid and sulphite.
4. seawater base fracturing liquid as claimed in claim 1, wherein said linking agent is by the host of 5-15 weight part, the complexing agent of 10-20 weight part, the composite composition of water of 65-85 weight part.
5. seawater base fracturing liquid as claimed in claim 4, wherein said host is selected from one or more in basic zirconium chloride, zirconate, zirconium tetrachloride, titanium tetrachloride, the titanic acid ester; Complexing agent is selected from one or more in polyvalent alcohol, polyprotonic acid, the alkanolamine; Said polyvalent alcohol is selected from terepthaloyl moietie, USP Kosher, N.F,USP MANNITOL, Xylitol, sorbyl alcohol; Said polyprotonic acid is selected from oxalic acid, tartrate, Hydrocerol A, propanedioic acid and Succinic Acid; Said alkanolamine is selected from Monoethanolamine MEA BASF, diethylolamine and trolamine.
6. seawater base fracturing liquid as claimed in claim 1, wherein said tensio-active agent are selected from fluorocarbon surfactant, polyether surfactant, polyether carboxylation's type tensio-active agent and their mixtures.
7. seawater base fracturing liquid as claimed in claim 1, wherein said gel breaker is selected from one or more in Potassium Persulphate, Sodium Persulfate, ammonium persulphate, potassium permanganate, potassium perchlorate, Potcrate, potassium periodate, Potassium Iodate and the ydrogen peroxide 50.
8. seawater base fracturing liquid as claimed in claim 1, wherein said PH regulator is selected from one or more in acetic acid, oxalic acid, formic acid, Hydrocerol A, hydrochloric acid, yellow soda ash, sodium hydrogencarbonate, the sodium hydroxide.
9. one kind prepares the of the fracturing fluid method of seawater base as claimed in claim 1, and it comprises the steps:
Viscosifying agent, tensio-active agent, gel breaker, pH value regulator, sea water mixing are got base fluid, and then add linking agent and carry out crosslinking reaction and promptly get said seawater base fracturing liquid.
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Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: China Oilfield Services Limited Patentee after: China Offshore Oil Group Co., Ltd. Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee before: China Oilfield Services Limited Patentee before: China National Offshore Oil Corporation |