CN104388074B - A kind of carboxymethyl guanidine rubber cross linker and its preparation method and application - Google Patents
A kind of carboxymethyl guanidine rubber cross linker and its preparation method and application Download PDFInfo
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- CN104388074B CN104388074B CN201410590856.9A CN201410590856A CN104388074B CN 104388074 B CN104388074 B CN 104388074B CN 201410590856 A CN201410590856 A CN 201410590856A CN 104388074 B CN104388074 B CN 104388074B
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- rubber cross
- carboxymethyl guanidine
- cross linker
- carboxymethyl
- water
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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
- C09K8/84—Compositions based on water or polar solvents
- C09K8/845—Compositions based on water or polar solvents containing inorganic compounds
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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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of carboxymethyl guanidine rubber cross linkers and its preparation method and application.A kind of technical solution of the present invention main points are as follows: carboxymethyl guanidine rubber cross linker, it is made of the raw material that following weight percent matches: crystal aluminum chloride 8%-12%, additive 20%-22%, remaining is water, the mixture that wherein additive is in formaldehyde, glyoxal, ethylene glycol, glycerine and glacial acetic acid at least two or more.The invention also discloses the preparation method of the carboxymethyl guanidine rubber cross linker and its applications in carboxymethyl guanidine gum fracturing fluid system.Carboxymethyl guanidine rubber cross linker produced by the present invention has broad applicability, and cross-linking properties is good, and overall cost is cheap, it is added in carboxymethyl guanidine gum fracturing fluid system, system is weakly acidic, pH=3-4, migration is expanded caused by the elecrtonegativity because of surface of clay can be effectively suppressed, plays the role of clay stabilization.
Description
Technical field
The invention belongs to oilfield chemistry carboxymethyl guanidine gum fracturing fluid technical fields, and in particular to a kind of carboxymethyl guanidine glue crosslinking
Agent and its preparation method and application.
Background technique
Due to oil and gas reservoir complex lithology, physical property condition is poor, shale content, high reservoir permeability are low, using conventional water base
Fracturing fluid such as guar gum or hydropropyl guar fracturing fluid are transformed reservoir, and there is thickener dosage height, water are insoluble
The disadvantages of object is more, breaking glue solution residue content is high, larger to reservoir and fracture condudtiviy damage, have seriously affected fracturing reform effect
Fruit.To further increase reservoir fracturing improvement effect, development and application carboxymethyl guar fracturing fluid technology, with conventional Guar
Glue or hydropropyl guar fracturing fluid the carboxymethyl guar gum thickener that compares have that the mass fraction that uses is lower, fracturing fluid
Residue content is less and injures more low plurality of advantages to reservoir permeability.
Currently, domestic common guanidine glue class fracturing fluid system crosslinking agent, inorganic or organic boron, organic is generallyd use
It based on zirconium, organic titanium, these crosslinking agents or is crosslinked under alkaline condition, such as borate crosslinker, is easy blocking channel, cause serious
Secondary injury；Have the characteristics that crosslinking is at high cost, such as organic zirconium, organic titanium.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of proportions rationally, overall cost is cheap and cross-linking properties is good
Carboxymethyl guanidine rubber cross linker.
Another technical problem that the present invention solves uses low-cost crystal aluminum chloride for raw material there is provided a kind of
And the preparation method of the carboxymethyl guanidine rubber cross linker of additional other additives.
The technical issues of present invention also solves is the carboxymethyl guanidine rubber cross linker in carboxymethyl guanidine gum fracturing fluid system
Using.
The technical solution of the present invention is as follows: a kind of carboxymethyl guanidine rubber cross linker, it is characterised in that matched by following weight percent
The raw material composition of ratio: crystal aluminum chloride 8%-12%, additive 20%-22%, remaining is water, and wherein additive is formaldehyde, second two
At least two or more mixture in aldehyde, ethylene glycol, glycerine and glacial acetic acid.
What carboxymethyl guanidine rubber cross linker of the present invention was made of the raw material that following weight percent matches: crystallization chlorination
Aluminium 12%, formaldehyde 8%, glyoxal 2%, glacial acetic acid 3%, ethylene glycol 8% and water 67%.
What carboxymethyl guanidine rubber cross linker of the present invention was made of the raw material that following weight percent matches: crystallization chlorination
Aluminium 10%, formaldehyde 6%, glacial acetic acid 5%, ethylene glycol 7%, glycerine 4% and water 68%.
What carboxymethyl guanidine rubber cross linker of the present invention was made of the raw material that following weight percent matches: crystallization chlorination
Aluminium 8%, formaldehyde 8%, glacial acetic acid 2%, ethylene glycol 8%, glycerine 2% and water 72%.
The preparation method of carboxymethyl guanidine rubber cross linker of the present invention, it is characterised in that specific steps are as follows: according to above-mentioned
Weight percent proportion weighs raw material respectively, and weighed crystal aluminum chloride is put into reaction vessel, and water dissolution is added, is then added
The additive being made of in formaldehyde, glyoxal, ethylene glycol, glycerine and glacial acetic acid at least two or more mixture, stirring is simultaneously
It is heated to 60-70 DEG C of reaction and obtains carboxymethyl guanidine rubber cross linker.
The preparation method of carboxymethyl guanidine rubber cross linker of the present invention, specific steps are as follows: match according to following weight percent
Than weighing raw material respectively, crystal aluminum chloride 12%, formaldehyde 8%, glyoxal 2%, glacial acetic acid 3%, ethylene glycol 8% and water 67% will be weighed
Crystal aluminum chloride be put into reaction vessel, be added water dissolution, be then added by formaldehyde, glyoxal, glacial acetic acid and ethylene glycol
The additive of mixture composition, is stirred and heated to 60-70 DEG C of reaction and obtains carboxymethyl guanidine rubber cross linker.
The preparation method of carboxymethyl guanidine rubber cross linker of the present invention, specific steps are as follows: match according to following weight percent
Than weighing raw material respectively, crystal aluminum chloride 10%, formaldehyde 6%, glacial acetic acid 5%, ethylene glycol 7%, glycerine 4% and water 68% will be weighed
Crystal aluminum chloride be put into reaction vessel, be added water dissolution, be then added by formaldehyde, glacial acetic acid, ethylene glycol and glycerine
The additive of mixture composition, is stirred and heated to 60-70 DEG C of reaction and obtains carboxymethyl guanidine rubber cross linker.
The preparation method of carboxymethyl guanidine rubber cross linker of the present invention, specific steps are as follows: match according to following weight percent
Than weighing raw material respectively, crystal aluminum chloride 8%, formaldehyde 8%, glacial acetic acid 2%, ethylene glycol 8%, glycerine 2% and water 72% will be weighed
Crystal aluminum chloride is put into reaction vessel, and water dissolution is added, is then added by the mixed of formaldehyde, glacial acetic acid, glycerine and ethylene glycol
The additive for closing object composition, is stirred and heated to 60-70 DEG C of reaction and obtains carboxymethyl guanidine rubber cross linker.
Application of the carboxymethyl guanidine rubber cross linker of the present invention in carboxymethyl guanidine gum fracturing fluid system, wherein carboxymethyl
Mass percentage of the guanidine rubber cross linker in carboxymethyl guanidine gum fracturing fluid is 0.3%-1%.
Compared with the prior art, the present invention has the following advantages having broad applicability, cross-linking properties is good, and overall cost is low
It is honest and clean, it is added in carboxymethyl guanidine gum fracturing fluid system, system is weakly acidic, pH=3-4, and bearing because of surface of clay can be effectively suppressed
Expansion migration, plays the role of clay stabilization caused by electrically.The present invention and fracturing fluid others clay stabilizer, temperature are stablized
The additives compatibility such as agent, cleanup additive, gel breaker is good, is easy to extemporaneous preparation construction, is suitable for high temperature formation breakdown.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment
It weighs respectively according to the following ratio raw material (kilogram):
Crystal aluminum chloride 12, formaldehyde 8, glyoxal 2, glacial acetic acid 3, ethylene glycol 8 and water 67；
Crystal aluminum chloride 10, formaldehyde 6, glacial acetic acid 5, ethylene glycol 7, glycerine 4 and water 68；
Crystal aluminum chloride 8, formaldehyde 8, glacial acetic acid 2, ethylene glycol 8, glycerine 2 and water 72.
Preparation method:
Raw material is weighed respectively according to above-mentioned weight percent proportion, and weighed crystal aluminum chloride is put into reaction vessel, is added
Enter water dissolution, is then added by formaldehyde, glyoxal, ethylene glycol, glycerine and glacial acetic acid at least two or more mixture group
At additive, be stirred and heated to 60-70 DEG C of reaction and obtain carboxymethyl guanidine rubber cross linker.
Obtained carboxymethyl guanidine rubber cross linker is detected, examining report is as follows, meets every skill of pressure break crosslinking agent
Art index.
| Detection project | As a result |
| Appearance | Colourless uniform liquid |
| It is water-soluble | It is miscible with water |
| pH | 2 |
| Cross-linking properties | It can hang |
| Delay time | 0.5-5min is adjustable |
The carboxymethyl guanidine rubber cross linker can form frozen glue with carboxymethyl guanidine glue, wherein the carboxymethyl for being 0.4% with mass concentration
The frozen glue heatproof that guanidine glue is formed can have preferable heat resistance up to 80 DEG C or more.
Application method:
In use process, quality percentage of the carboxymethyl guanidine rubber cross linker obtained in carboxymethyl guanidine gum fracturing fluid system adds
Dosage is 0.3%-1%, and related crosslinking agent is added in fracturing fluid system, system is weakly acidic, can be effectively suppressed in acidity
Because surface of clay elecrtonegativity caused by expand migration, play the role of clay stabilization, can be glued with other in fracturing fluid system
The additives compatibility such as soil stabilizer, temperature stability agent, cleanup additive, gel breaker is good, is easy to extemporaneous preparation construction, is suitable for
High-temperature stratum pressure break.
Basic principle of the invention, main feature and advantage has been shown and described above, do not depart from spirit of that invention and
Under the premise of range, there are also various changes and modifications, these changes and improvements to both fall within claimed invention by the present invention
Range.
Claims (1)
1. a kind of carboxymethyl guanidine rubber cross linker, it is characterised in that be made of the raw material that following weight percent matches: crystallization chlorine
Change aluminium 12%, formaldehyde 8%, glyoxal 2%, glacial acetic acid 3%, ethylene glycol 8% and water 67%；Alternatively, crystal aluminum chloride 10%, formaldehyde 6%, ice
Acetic acid 5%, ethylene glycol 7%, glycerine 4% and water 68%；Alternatively, crystal aluminum chloride 8%, formaldehyde 8%, glacial acetic acid 2%, ethylene glycol 8%, third
Triol 2% and water 72%, the carboxymethyl guanidine rubber cross linker weigh original the preparation method comprises the following steps: matching according to above-mentioned weight percent respectively
Material, weighed crystal aluminum chloride is put into reaction vessel, and water dissolution is added, then adds the remaining raw materials, is stirred and heated to
60-70 DEG C of reaction obtains carboxymethyl guanidine rubber cross linker, and wherein carboxymethyl guanidine rubber cross linker is in carboxymethyl guanidine gum fracturing fluid
Mass percentage is 0.3%-1%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410590856.9A CN104388074B (en) | 2014-10-29 | 2014-10-29 | A kind of carboxymethyl guanidine rubber cross linker and its preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410590856.9A CN104388074B (en) | 2014-10-29 | 2014-10-29 | A kind of carboxymethyl guanidine rubber cross linker and its preparation method and application |
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| CN104388074A CN104388074A (en) | 2015-03-04 |
| CN104388074B true CN104388074B (en) | 2019-03-01 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102102014A (en) * | 2009-12-16 | 2011-06-22 | 中国石油天然气股份有限公司 | Carboxymethyl guar gum acid fracturing fluid |
| CN102329606A (en) * | 2011-08-03 | 2012-01-25 | 西安长庆化工集团有限公司 | Cross-linking agent for carboxymethyl guar gum acidic fracturing fluid and preparation method thereof |
| CN102417814A (en) * | 2011-11-16 | 2012-04-18 | 北京国海能源技术研究院 | Seawater-based fracturing fluid and preparation method thereof |
| CN102618249A (en) * | 2012-03-05 | 2012-08-01 | 中国海洋石油总公司 | Seawater base fracturing fluid and preparation method thereof |
| CN103275690A (en) * | 2013-05-23 | 2013-09-04 | 中国石油天然气股份有限公司 | Cross-linking agent for polymer fracturing fluid and preparation and application thereof |
-
2014
- 2014-10-29 CN CN201410590856.9A patent/CN104388074B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102102014A (en) * | 2009-12-16 | 2011-06-22 | 中国石油天然气股份有限公司 | Carboxymethyl guar gum acid fracturing fluid |
| CN102329606A (en) * | 2011-08-03 | 2012-01-25 | 西安长庆化工集团有限公司 | Cross-linking agent for carboxymethyl guar gum acidic fracturing fluid and preparation method thereof |
| CN102417814A (en) * | 2011-11-16 | 2012-04-18 | 北京国海能源技术研究院 | Seawater-based fracturing fluid and preparation method thereof |
| CN102618249A (en) * | 2012-03-05 | 2012-08-01 | 中国海洋石油总公司 | Seawater base fracturing fluid and preparation method thereof |
| CN103275690A (en) * | 2013-05-23 | 2013-09-04 | 中国石油天然气股份有限公司 | Cross-linking agent for polymer fracturing fluid and preparation and application thereof |
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| CN104388074A (en) | 2015-03-04 |
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