CN108456513A - A kind of fracturing fluid organic aluminum crosslinker, preparation method and application - Google Patents
A kind of fracturing fluid organic aluminum crosslinker, preparation method and application Download PDFInfo
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- CN108456513A CN108456513A CN201710088789.4A CN201710088789A CN108456513A CN 108456513 A CN108456513 A CN 108456513A CN 201710088789 A CN201710088789 A CN 201710088789A CN 108456513 A CN108456513 A CN 108456513A
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- fracturing fluid
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
Abstract
The invention discloses a kind of organic aluminium cross-linked, preparation method and applications of fracturing fluid.The crosslinking agent includes：Each component is counted in parts by weight, 100 parts by weight of distilled water；7~25 parts by weight of aluminium chloride；Polyacid/12~25 parts by weight of polynary hydrochlorate；5~15 parts by weight of organic amine；85~125 parts by weight of polyalcohol.Organic aluminum crosslinker preparation method prepared by the present invention is simple, the cost of raw material is cheap, organic aluminum crosslinker can cross-linked polyacrylamide or the polyacrylamide polymer of partial hydrolysis in neutral conditions, pH adjusting agent need not be added and adjust polymer solution pH value, the excellent fracturing fluid of forming properties, the pressing crack construction that 60~120 DEG C of stratum can be met, is with a wide range of applications.
Description
Technical field
The present invention relates to drilling applications, further say, are to be related to a kind of fracturing fluid organic aluminum crosslinker, preparation method
And application.
Background technology
Aqueous fracturing fluid is the most commonly used fracturing fluid system, typically organo-metallic crosslinker is utilized to be crosslinked natural polymer
Son or synthesis polyacrylamide polymer form the gel rubber system with prop-carrying capacity with certain viscosity.It is crosslinked guanidine glue class
The common crosslinking agent of polymer is organic boron, organic zirconium etc., and cross-linked polyacrylamide polymer is mainly crosslinked using organic zirconium
Agent, however above-mentioned cross-linking agents will be crosslinked within the scope of certain pH value, when practical application, need to adjust cross-linking system pH value,
Site operation complex steps are caused, situation about not being crosslinked or cross-linking effect is bad often occur.
Patent 201310250908.3 discloses a kind of tartaric acid aluminium crosslinking agent for polymer water-based fracturing, prepares
Method is complicated.Patent 201410649366.1 discloses a kind of aluminium citrate water blockoff crosslinking agent of oil recovery, and preparation method is complicated,
It is mainly used for water blockoff field.
Invention content
To solve the problem in the prior art, the present invention provides a kind of fracturing fluid organic aluminum crosslinker, preparations
Method and application.This crosslinking agent can cross-linked polyacrylamide or the poly- propionamide of partial hydrolysis in neutral conditions, need not adjust
Section polymer solution pH value (general organic zirconium crosslinker will adjust pH value to acid, Site Detection and complicated for operation), not only
Scene can be simplified and match liquid stream journey, moreover it is possible to reduce site operation risk.The fracturing fluid system being cross-linked to form is functional, can meet
The pressing crack construction on 60~120 DEG C of stratum.
An object of the present invention is to provide a kind of organic aluminum crosslinker of fracturing fluid.
Each component is counted in parts by weight,
Preferred amount ranges：
It is preferred that：
The polyacid/polynary hydrochlorate is selected from least one of citric acid, sodium citrate, tartaric acid, sodium tartrate；
The polyalcohol is selected from least one of ethylene glycol, glycerine, sorbierite；
The organic amine is triethanolamine, at least one of diethanol amine, monoethanolamine.
Aluminium chloride provides the active ingredient of organic aluminum crosslinker, and chlorion, crosslinking agent is by discharging aluminium ion and polypropylene
Amino and carboxyl coordination in amide form crosslinked gel structure；Polyacid/polynary hydrochlorate controls aluminium ion mainly as ligand
Release plays delay crosslinking, improves fracturing fluid temperature tolerance；Polyalcohol plays delay crosslinking and prevents from handing over as ligand and solvent
The effect that connection agent is precipitated in aqueous solution；Organic amine improves organo-aluminium crosslinked fracturing fluid as pH adjusting agent and temperature stability agent
Stability, while may be implemented effectively to be crosslinked in neutral conditions.
The second object of the present invention is to provide a kind of preparation method of the organic aluminum crosslinker of fracturing fluid.
Including：
Step 1) is dissolved in distilled water at room temperature, by aluminium chloride, and stirring is cooled to room temperature to being completely dissolved；
Step 2) is dissolved in distilled water at room temperature, by citric acid, stirs to being completely dissolved, is cooled to room temperature；
Aluminium chloride dissolved drip is added in aqueous citric acid solution by step 3), and polyalcohol is added after dripping；
Organic amine is added dropwise in the solution of step 3) in step 4), and the pH value for adjusting solution is 5~7；
Step 5) is stirred obtained organic aluminum crosslinker, obtains organic aluminum crosslinker preferably at 50~80 DEG C,
Stir 3~5h.
The third object of the present invention be to provide a kind of fracturing fluid with organic aluminum crosslinker answering in oil drilling
With.
Organic aluminum crosslinker preparation method prepared by the present invention is simple, and the cost of raw material is cheap, and organic aluminum crosslinker can be with
Cross-linked polyacrylamide or the polyacrylamide polymer of partial hydrolysis in neutral conditions, need not add pH adjusting agent tune
Polymer solution pH value is saved, the excellent fracturing fluid of forming properties can meet the pressing crack construction on 60~120 DEG C of stratum, have extensive
Application prospect.
Specific implementation mode
With reference to embodiment, further illustrate the present invention.
Embodiment described below is only the preferred embodiment of the invention, to those of ordinary skill in the art,
Under the premise of not departing from inventive principle, several modifications and modification can also be made to technical scheme of the present invention, it is relevant to change
Into with modification also in protection scope of the present invention.
Experimental raw source
Polyacrylamide polymer：It makes by oneself in laboratory；
Aluminium chloride hexahydrate：Chinese medicines group chemical reagent, analysis are pure；
Ethylene glycol, glycerine：Fine chemistry industry research institute is recovered in Tianjin, and analysis is pure；
Citric acid, tartaric acid：Beijing Chemical Plant, analysis are pure；
Ethanol amine：Beijing Chemical Plant, analysis are pure.
Embodiment 1
Present embodiments provide the organic aluminum crosslinker of fracturing fluid and its crosslinked polyacrylamide frozen glue.
Fracturing fluid provided in this embodiment includes following components in terms of weight fraction with organic aluminum crosslinker：
12 parts of Aluminium chloride hexahydrates；
15 parts of citric acids；
7 parts of triethanolamines；
90 parts of ethylene glycol；
100 parts of distilled water.
The preparation process of the crosslinking agent is as follows：
At room temperature, Aluminium chloride hexahydrate is dissolved in a certain amount of distilled water, stirring and dissolving is cooled to room temperature；Citric acid is molten
In a certain amount of distilled water, stirring and dissolving is cooled to room temperature；Above-mentioned Aluminium chloride hexahydrate is added dropwise to aqueous citric acid solution
In, ethylene glycol is added after dripping；Then triethanolamine is added dropwise dropwise, the pH value for adjusting solution is 5；By above-mentioned mixed solution
At 50 DEG C, 3h is stirred, organic aluminum crosslinker of the present invention is obtained.
The organo-aluminium cross-linked polyacrylamide aqueous solutions of polymers is recycled, fracturing fluid gel is obtained.The pressure
Liquid frozen glue is split, based on mass fraction, including following components：
99.8 parts of polyacrylamide polymers aqueous solution；
0.2 part of organic aluminum crosslinker.
The method of organo-aluminium cross-linked polyacrylamide frozen glue in the present embodiment includes the following steps：
According to water：Polyacrylamide polymers are 99.6:0.4 weight ratio is slowly added to polypropylene under agitation
Amide polymer obtains 0.4% polyacrylamide polymers aqueous solution after stirring 30min.
It is static under the conditions of 30 DEG C to place 2 hours, organic aluminum crosslinker is added, is uniformly mixed to obtain organic
Aluminium cross-linked polyacrylamide polymers frozen glue.
Embodiment 2
Present embodiments provide the organic aluminum crosslinker of fracturing fluid and its crosslinked polyacrylamide frozen glue.
Fracturing fluid provided in this embodiment includes following components in terms of weight fraction with organic aluminum crosslinker：
16 parts of Aluminium chloride hexahydrates；
17 parts of sodium tartrates；
8 parts of diethanol amine；
105 parts of glycerine；
100 parts of distilled water.
The preparation process of the crosslinking agent is as follows：
At room temperature, Aluminium chloride hexahydrate is dissolved in a certain amount of distilled water, stirring and dissolving is cooled to room temperature；By sodium tartrate
It is dissolved in a certain amount of distilled water, stirring and dissolving is cooled to room temperature；Above-mentioned Aluminium chloride hexahydrate is added dropwise to sodium tartrate water
In solution, glycerine is added after dripping；Then diethanolamine solution is added dropwise dropwise, the pH value for adjusting solution is 6；It will be above-mentioned
Mixed solution stirs 4h, obtains organic aluminum crosslinker of the present invention at 70 DEG C.
The organo-aluminium cross-linked polyacrylamide aqueous solutions of polymers is recycled, fracturing fluid gel is obtained.The pressure
Liquid frozen glue is split, based on mass fraction, including following components：
99.8 parts of polyacrylamide polymers aqueous solution；
0.2 part of organic aluminum crosslinker.
The method of organo-aluminium cross-linked polyacrylamide frozen glue in the present embodiment includes the following steps：
According to water：Polyacrylamide polymers are 99.6:0.4 weight ratio is slowly added to polypropylene under agitation
Amide polymer obtains 0.4% polyacrylamide polymers aqueous solution after stirring 30min.
It is static under the conditions of 30 DEG C to place 2 hours, organic aluminum crosslinker is added, is uniformly mixed to obtain organic
Aluminium cross-linked polyacrylamide polymers frozen glue.
Embodiment 3
Present embodiments provide the organic aluminum crosslinker of fracturing fluid and its crosslinked polyacrylamide frozen glue.
Fracturing fluid provided in this embodiment includes following components in terms of weight fraction with organic aluminum crosslinker：
20 parts of Aluminium chloride hexahydrates；
20 parts of tartaric acid；
10 parts of monoethanolamine；
105 parts of glycerine；
100 parts of distilled water.
The preparation process of the crosslinking agent is as follows：
At room temperature, Aluminium chloride hexahydrate is dissolved in a certain amount of distilled water, stirring and dissolving is cooled to room temperature；Tartaric acid is molten
In a certain amount of distilled water, stirring and dissolving is cooled to room temperature；Above-mentioned Aluminium chloride hexahydrate is added dropwise to aqueous tartaric acid solution
In, glycerine is added after dripping；Then monoethanolamine solution is added dropwise dropwise, the pH value for adjusting solution is 7；By above-mentioned mixing
Solution stirs 8h, obtains organic aluminum crosslinker of the present invention at 80 DEG C.
The organo-aluminium cross-linked polyacrylamide aqueous solutions of polymers is recycled, fracturing fluid gel is obtained.The pressure
Liquid frozen glue is split, based on mass fraction, including following components：
99.8 parts of polyacrylamide polymers aqueous solution；
0.2 part of organic aluminum crosslinker.
The method of organo-aluminium cross-linked polyacrylamide frozen glue in the present embodiment includes the following steps：
According to water：Polyacrylamide polymers are 99.6:0.4 weight ratio is slowly added to polypropylene under agitation
Amide polymer obtains 0.4% polyacrylamide polymers aqueous solution after stirring 30min.
It is static under the conditions of 30 DEG C to place 2 hours, organic aluminum crosslinker is added, is uniformly mixed to obtain organic
Aluminium cross-linked polyacrylamide polymers frozen glue.
Performance detection
According to China National Petroleum professional standard SY/T 6216-1996《Pressure break crosslinking agent performance test method》With
SY/T 5107—2005《Aqueous fracturing fluid method of evaluating performance》Carry out performance measurement.
1 cross-linking properties of table
As it can be seen from table 1 changing with organic aluminum crosslinker formula, the performance of organic aluminum crosslinker and crosslinked gel is
Variation, crosslinked gel can be hung, and had preferable viscoelasticity, can be met the fracturing fluid application of different temperatures.The present invention carries
The organic aluminum crosslinker supplied can meet the pressing crack construction on 60~120 DEG C of stratum, have live liquid of matching simple, easy to use excellent
Point.
Claims (8)
1. a kind of organic aluminum crosslinker of fracturing fluid, it is characterised in that the crosslinking agent includes：
Each component is counted in parts by weight,
2. the organic aluminum crosslinker of fracturing fluid as described in claim 1, it is characterised in that：
3. the organic aluminum crosslinker of fracturing fluid as described in claim 1, it is characterised in that：
The polyacid/polynary hydrochlorate is selected from least one of citric acid, sodium citrate, tartaric acid, sodium tartrate.
4. the organic aluminum crosslinker of fracturing fluid as claimed in claim 3, it is characterised in that：
The polyalcohol is selected from least one of ethylene glycol, glycerine, sorbierite.
5. the organic aluminum crosslinker of fracturing fluid as claimed in claim 4, it is characterised in that：
The organic amine is triethanolamine, at least one of diethanol amine, monoethanolamine.
6. a kind of fracturing fluid as described in one of Claims 1 to 5 preparation method of organic aluminum crosslinker, it is characterised in that institute
The method of stating includes：
Step 1) is dissolved in distilled water at room temperature, by aluminium chloride, and stirring is cooled to room temperature to being completely dissolved；
Step 2) is dissolved in distilled water at room temperature, by citric acid, stirs to being completely dissolved, is cooled to room temperature；
Liquor alumini chloridi is added drop-wise in aqueous citric acid solution by step 3), and polyalcohol is added after dripping；
Organic amine is added dropwise in the solution of step 3) in step 4), and the pH value for adjusting solution is 5~7；
Step 5) is stirred obtained organic aluminum crosslinker.
7. preparation method as claimed in claim 6, it is characterised in that：
Step 5) stirs 3~5h at 50~80 DEG C.
8. a kind of application of fracturing fluid as described in one of Claims 1 to 5 with organic aluminum crosslinker in oil drilling.
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| CN201710088789.4A CN108456513B (en) | 2017-02-20 | 2017-02-20 | Organic aluminum crosslinking agent for fracturing fluid, preparation method and application |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171797A (en) * | 2018-11-13 | 2020-05-19 | 中国石油化工股份有限公司 | Cross-linking agent and preparation method thereof |
| CN111171800A (en) * | 2018-11-13 | 2020-05-19 | 中国石油化工股份有限公司 | Preparation method of crosslinked acid |
| CN112375555A (en) * | 2020-11-10 | 2021-02-19 | 中石化石油工程技术服务有限公司 | Preparation method of organic aluminum crosslinking agent capable of crosslinking with W/O inverse emulsion type drag reducer |
| CN115287054A (en) * | 2022-08-23 | 2022-11-04 | 洲际海峡能源科技有限公司 | Organic aluminum crosslinking agent, preparation method thereof and application thereof in continuous mixed fracturing fluid |
| CN115678532A (en) * | 2021-07-30 | 2023-02-03 | 中国石油化工股份有限公司 | Crosslinking agent and preparation method and application thereof |
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| CN111171797A (en) * | 2018-11-13 | 2020-05-19 | 中国石油化工股份有限公司 | Cross-linking agent and preparation method thereof |
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| CN112375555A (en) * | 2020-11-10 | 2021-02-19 | 中石化石油工程技术服务有限公司 | Preparation method of organic aluminum crosslinking agent capable of crosslinking with W/O inverse emulsion type drag reducer |
| CN115678532A (en) * | 2021-07-30 | 2023-02-03 | 中国石油化工股份有限公司 | Crosslinking agent and preparation method and application thereof |
| CN115287054A (en) * | 2022-08-23 | 2022-11-04 | 洲际海峡能源科技有限公司 | Organic aluminum crosslinking agent, preparation method thereof and application thereof in continuous mixed fracturing fluid |
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