CN109280547A - A kind of organic borate cross-linker and guar gum fracturing fluid - Google Patents

A kind of organic borate cross-linker and guar gum fracturing fluid Download PDF

Info

Publication number
CN109280547A
CN109280547A CN201710597438.6A CN201710597438A CN109280547A CN 109280547 A CN109280547 A CN 109280547A CN 201710597438 A CN201710597438 A CN 201710597438A CN 109280547 A CN109280547 A CN 109280547A
Authority
CN
China
Prior art keywords
guar gum
fracturing fluid
linker
organic borate
borate cross
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.)
Pending
Application number
CN201710597438.6A
Other languages
Chinese (zh)
Inventor
陈凯
肖春金
黄波
左家强
宋李煜
杨峰
任占春
刘霜
陈培胜
陈磊
苏权生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Research Institute of Petroleum Engineering Shengli Co
Original Assignee
China Petroleum and Chemical Corp
Sinopec Research Institute of Petroleum Engineering Shengli Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Research Institute of Petroleum Engineering Shengli Co filed Critical China Petroleum and Chemical Corp
Priority to CN201710597438.6A priority Critical patent/CN109280547A/en
Publication of CN109280547A publication Critical patent/CN109280547A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/62Compositions for forming crevices or fractures
    • C09K8/66Compositions based on water or polar solvents
    • C09K8/68Compositions based on water or polar solvents containing organic compounds
    • C09K8/685Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/605Compositions for stimulating production by acting on the underground formation containing biocides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/12Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a kind of organic borate cross-linkers, it is to react to be prepared in anhydrous conditions with organic polyamine compound by boric acid, the organic polyamine compound is selected from diethylenetriamine, triethylene tetramine, tetraethylenepentamine, polyethylene polyamine or polyethyleneimine.The invention also discloses a kind of guar gum fracturing fluids: hydroxypropyl guar gum 0.2%~0.6%, and organic borate cross-linker 0.2%~0.6% described in claim 1, pH adjusting agent 0.01%~0.2%, temperature stability agent 0~0.5%, other additives 0.2%~2%, surplus is water.Organic borate cross-linker molecular volume of the invention is big, and the crosslinking points formed with low concentration guar gum aqueous solution are more, so improving the cross-linking properties and heat resistance of gelled fracturing fluid, while reducing dosage of crosslinking agent, reduces fracturing fluid system cost.Guar gum fracturing fluid of the invention has good cross-linking properties and heat resistance, and hydroxypropyl guar gum can be adjusted according to reservoir temperature and uses concentration, maximum operation (service) temperature is 150 DEG C.

Description

A kind of organic borate cross-linker and guar gum fracturing fluid
Technical field
The present invention relates to a kind of organic borate cross-linker and containing the guar gum fracturing fluid of the crosslinking agent, belong to oil field development technology neck Domain.
Background technique
Hydraulic fracturing is the Main Yield-increasing measure of hyposmosis/ultra-low penetration Reservoir Development, and principle is set using ground It is standby to generate high pressure, using fracturing fluid as main medium, hydraulic fracture is generated in the earth formation, and fracturing fluid is recycled to be entrained into proppant Enter in crack, form the supporting crack that there is certain flow conductivity to oil gas, improves well yield.
Fracturing fluid is one of the important materials in hydraulic fracturing construction, and main function is conducting pressure and carrying proppant Into stratum.Current most widely used fracturing fluid system is led to using guar gum and its derivative as the fracturing fluid system of thickener It crosses thickener and cross-linking agents forms frozen glue, carry proppant and enter man-made fracture.The system has at low cost, cross-linked stable The features such as property is good, crosslinking is controllable, temperature tolerance is good, site operation is simple, system support is improved.But there is also following shortcomings: Conventional guar gum fracturing fluid can be in crack in pressing crack construction process and crack wall surface remains a large amount of residues, and reservoir is caused to hurt Evil causes stratum filtration ability to reduce and declines with production capacity, directly affects fracturing effect.It reduces thickener dosage and will reduce and enter ground The solid phase substance content of layer can effectively reduce the injury of fracturing fluid filtrate and residue fracture and reservoir, but it is dense to reduce guar gum Degree can encounter again fracturing fluid plastic and heatproof, it is anti-shearing it is unstable cause the jelly system viscoelasticity to reduce, proppant sedimentation is asked Topic.
Guar gum is a kind of natural galacto mannosan, belongs to non-ionic macromolecule, relative molecular mass about 200 × 104。 Guar gum thickener currently used for pressure break is hydroxypropyl guar gum (HPG), using concentration generally 0.2%~0.8%.
The common crosslinking agent of hydroxypropyl melon fracturing fluid is boron class crosslinking agent, mainly includes borax, boric acid and boron and complexing The mixture etc. of agent composition is mainly characterized by being crosslinked reversible, resistance to high shear, and major defect is that temperature tolerance is poor (generally using temperature Degree is less than 130 DEG C), guar gum thickener is high using concentration in fracturing fluid.Concentration, drop are used to reduce guar gum thickener in fracturing fluid Injury of the low fracturing fluid breaking glue solution to supporting crack flow conductivity proposes the concept of low concentration guar gum fracturing fluid both at home and abroad, and Based on low concentration guar gum Borate Gelling Hydrofracturing Fluid.
US 5082579 proposes a kind of organic borate cross-linker with delayed cross-linking capacity energy, and the crosslinking agent is by borax, second two Aldehyde, sorbierite and inorganic base composition, the crosslinking agent and the cross-linking formation frozen glue of hydroxypropyl guar gum, it is adjustable by adjusting being formulated With the crosslinking time of guar gum aqueous solution, when hydroxypropyl guar gum dosage is 0.6%, 120 DEG C of frozen glue heatproof.
US 5266224 proposes the method for forming organic borate cross-linker with alpha-hydroxy carboxylic acid compounds and boron ion, and the crosslinking agent is main Including boric acid, alpha-hydroxy carboxylic acid compounds, alkali and polyalcohol, alpha-hydroxy carboxylic acid compounds are mainly sodium lactate and sodium citrate.
US 5827804 proposes the organic borate cross-linker used under a kind of cryogenic conditions, and the crosslinking agent is by boric acid, ethanol amine Or triethanolamine, ethylene glycol composition, the crosslinking agent can be stablized in -30 DEG C or more holdings.
US6060436 proposes a kind of high temperature Borate Gelling Hydrofracturing Fluid, and used crosslinking agent is by boric acid, sodium gluconate and alkali Composition, can be cross-linked to form frozen glue with hydroxypropyl guar gum, and system maximum operation (service) temperature is 150 DEG C.
CN 1524920A proposes a kind of preparation and application of organic boron delayed crosslinker, and the crosslinking agent is mainly by boron Sand, polyaldehyde, polyhydric alcohol amine, alkali and water composition can pass through the crosslinking time of change base fluid pH value adjustment and natural plant gum.
CN 102732244B proposes preparation and the user of a kind of super low concentration guar gum fracturing fluid organic borate cross-linker Method, the crosslinking agent mainly include water, acylate, boron compound, polyalcohol, sodium hydroxide composition, and acylate is usually Portugal Grape sodium saccharate, polyalcohol are sorbierite, xylitol etc..Using the crosslinking agent and the 0.3% cross-linking shape of hydroxypropyl melon glue solution At frozen glue, the heatproof resistant to shearing ability of frozen glue is 120 DEG C.
For low concentration guar gum fracturing fluid system, since guar gum uses concentration low, guar gum intermolecular force in aqueous solution Weakening, the mode to form crosslinking agent is acted on according to small molecule complexing agent and boron ion, cross-linking system intermolecular cross-linking degree is low, Cross-link intensity is low to will lead to cross-linking effect variation, and it is poor to hang performance.Therefore, it is necessary to research and develop a kind of crosslinked that crosslinking degree is high It is molecule.
Summary of the invention
For the above-mentioned prior art, the present invention provides a kind of organic borate cross-linkers, can hand over hydroxypropyl melon sol solution Connection forms low concentration guar gum fracturing fluid system.The present invention is reacted by boron compound with organic polyamine compound in anhydrous conditions The mode for forming organic borate cross-linker, increases the relative molecular mass of complexing agent, increases cross-linker molecules volume, increase The cross-linking properties of low concentration guar gum fracturing fluid system.
The present invention is achieved by the following technical solutions:
A kind of organic borate cross-linker is prepared using boric acid and organic polyamine compound as raw material, described organic more Amine compounds are selected from diethylenetriamine, triethylene tetramine, tetraethylenepentamine, polyethylene polyamine or polyethyleneimine, preparation side Method are as follows: boric acid is mixed with ethylene glycol, 60~70 DEG C are warming up under stirring, all after dissolution, n-butanol is added, under stirring in material 110~120 DEG C are warming up to, the water of reaction to abjection no longer changes (about 2 hours);Organic polyamine compound is added dropwise again, heats up To 120~140 DEG C, the n-butanol amount of reaction to abjection no longer changes (about 2 hours), is cooled to room temperature and hands over to get to organic boron Join agent;The boric acid, ethylene glycol, n-butanol, organic polyamine compound molar ratio be 1: (1.5~2): 1: (0.01~ 0.4)。
Further, react equipped with condenser pipe/water segregator, agitating paddle, addition funnel, thermometer four-hole boiling flask in into Row.
Organic borate cross-linker of the invention can be used for preparing low concentration guar gum fracturing fluid.
A kind of guar gum fracturing fluid is grouped as by the group of following parts by weight: each component percentage, hydroxypropyl melon Glue 0.2%~0.6%, organic borate cross-linker 0.2%~0.6%, pH adjusting agent 0.01%~0.2%, temperature stability agent 0~ 0.5%, other additives 0.2%~2%, surplus is water.
Preferably, the hydroxypropyl guar gum is selected from the Instant hydroxypropyl guar gum that Shengli Oil Field Chinese Academy of Engineering provides, trade name For SRG-1,0.6% aqueous solution apparent viscosity is 111mPas, water-insoluble 5.2%, moisture content 9.2%, 1min It dissolves percentage and is greater than 80%.
The pH adjusting agent is selected from sodium carbonate or/and sodium hydroxide.
The temperature stability agent be selected from sorbierite, xylitol, glucose, fructose, galactolipin, mannose, ribose, xylose, The combination of one or more of sodium gluconate.
Other additives are selected from one or both of expansion-resisting agent, cleanup additive, fungicide, non-emulsifier, gel breaker Above combination.
Preferably, the expansion-resisting agent is selected from the expansion-resisting agent that triumph underground circumference company provides, trade name FP-2.
Preferably, the cleanup additive is selected from the micro-emulsion type cleanup additive that Shengli Oil Field Chinese Academy of Engineering provides, trade name ME-2.
Preferably, the fungicide is selected from the fungicide that triumph underground circumference company provides, trade name SK-1.
Preferably, the non-emulsifier is the non-emulsifier that triumph underground circumference company provides, trade name SF-1.
Preferably, the gel breaker is the capsule breaker that Shengli Oil Field Chinese Academy of Engineering provides, trade name EB-1.
Preferably, the guar gum fracturing fluid is grouped as by the group of following parts by weight: hydroxypropyl guar gum, 0.3%;Have Machine borate crosslinker, 0.35%;Sodium gluconate, 0.1%;Expansion-resisting agent, 0.5%;Cleanup additive, 0.3%;Sodium carbonate, 0.1%;It kills Microbial inoculum, 0.1%;Non-emulsifier, 0.1%;Surplus is water.
Preferably, the guar gum fracturing fluid is grouped as by the group of following parts by weight: Instant hydroxypropyl guar gum, 0.3%;Organic borate cross-linker, 0.35%;Sodium gluconate, 0.1%;Expansion-resisting agent FP-1,0.5%;Cleanup additive ME-2,0.3%; Sodium carbonate, 0.1%;Fungicide SK-1,0.1%;Non-emulsifier SF-1,0.1%;Surplus is water.
Preferably, the guar gum fracturing fluid is grouped as by the group of following parts by weight: Instant hydroxypropyl guar gum, 0.3%;Organic borate cross-linker, 0.35%;Sodium gluconate, 0.1%;Expansion-resisting agent FP-1,0.5%;Cleanup additive ME-2,0.3%; Sodium carbonate, 0.1%;Fungicide SK-1,0.1%;Non-emulsifier SF-1,0.1%;Capsule breaker EB-1,0.02%;Surplus is Water.
Preferably, the guar gum fracturing fluid is grouped as by the group of following parts by weight: Instant hydroxypropyl guar gum, 0.55%;Organic borate cross-linker, 0.5%;Sodium gluconate, 0.2%;Expansion-resisting agent FP-1,0.5%;Cleanup additive ME-2,0.3%; Sodium hydroxide, 0.02%;Fungicide SK-1,0.1%;Non-emulsifier SF-1,0.1%;Surplus is water.
Preferably, the guar gum fracturing fluid is grouped as by the group of following parts by weight: Instant hydroxypropyl guar gum, 0.45%;Organic borate cross-linker, 0.4%;Sodium gluconate, 0.2%;Expansion-resisting agent FP-1,0.5%;Cleanup additive ME-2,0.3%; Sodium hydroxide, 0.02%;Fungicide SK-1,0.1%;Non-emulsifier SF-1,0.1%;Surplus is water.
The guar gum fracturing fluid the preparation method comprises the following steps: under stirring condition, hydroxypropyl guar gum is added to the water, stir 3min Afterwards, pH adjusting agent, temperature stability agent and other additives is added, is uniformly mixed to form base fluid;Base fluid standing 5min~ Organic borate cross-linker is added in 1h, is crosslinked 30~60s, forms adjustable extension frozen glue to get low concentration guar gum fracturing fluid.
Organic borate cross-linker prepared by the present invention, using organic polyamine compound as linking group, the system of reacting with boron compound The more borate cross-linking agents of machine are had, the crosslinking since the molecular volume of more boronic acid compounds is big, with the formation of low concentration guar gum aqueous solution Point is more, so improving the cross-linking properties and heat resistance of gelled fracturing fluid, while reducing dosage of crosslinking agent, reduces pressure break Liquid system cost.There is guar gum fracturing fluid of the invention good crosslinking to adjust and hang performance and heat resistance, can be according to reservoir temperature Adjust hydroxypropyl guar gum and use concentration: when hydroxypropyl melon gum concentration is 0.30%, frozen glue temperature resistant capability reaches 120 DEG C, works as hydroxyl When propyl guar gum concentration is 0.45%, frozen glue temperature resistant capability reaches 140 DEG C, and maximum operation (service) temperature is 150 DEG C.Melon of the invention The low concentration guar gum fracturing fluid that fracturing fluid can be used as high temperature low-permeability oil deposit pressure break uses.
Detailed description of the invention
Fig. 1: the heatproof resistant to shearing curve (120 DEG C) of fracturing fluid prepared by embodiment 3.
Fig. 2: the heatproof resistant to shearing curve (140 DEG C) of fracturing fluid prepared by embodiment 6.
Fig. 3: the heatproof resistant to shearing curve (150 DEG C) of fracturing fluid prepared by embodiment 9.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.
Instrument involved in following embodiments, reagent, material etc. are unless otherwise noted existing in the prior art Conventional instrument, reagent, material etc., can be obtained by regular commercial sources.Experimental method involved in following embodiments, inspection Survey method etc. is unless otherwise noted existing routine experiment method in the prior art, detection method etc..
Embodiment 1 prepares organic borate cross-linker
Equipped with condenser pipe/water segregator, agitating paddle, addition funnel, thermometer four-hole boiling flask in be added 31g boric acid, 120g ethylene glycol is warming up to 65 DEG C under stirring, after material all dissolution, add 37g n-butanol, be warming up to 115 under stirring DEG C, 2h is reacted, until the water of abjection no longer changes, divides water about 25g;19g tetraethylenepentamine is added dropwise in four-hole boiling flask again, rises Temperature reacts 2h to 130 DEG C, until the n-butanol amount of abjection no longer changes, n-butanol amount about 35g is finally cooled to room temperature and is produced Product.
2 preparing fracturing fluid base fluid of embodiment
493g water is added in device in mixed adjust, 1.50g Instant hydroxypropyl guar gum SRG-1 is added under stiring, dissolves 3min Afterwards, 0.5g sodium gluconate, 2.50g expansion-resisting agent FP-1,1.5g cleanup additive ME-2,0.5g sodium carbonate, 0.5g fungicide is added SK-1 and 0.5g non-emulsifier SF-1, stirring and dissolving 2min stand 1h, are configured to the pressure break liquid-based that guar gum concentration is 0.30% Liquid, fracturing fluid base fluid apparent viscosity 21mPas (170s-1), pH value 10.5.
3 fracturing fluid cross-linking properties of embodiment and temperature and shearing sustainability
The fracturing fluid base fluid 100mL that Example 2 is prepared is added organic borate cross-linker 0.35g prepared by embodiment 1, obtains To hydroxypropyl guar gum Borate Gelling Hydrofracturing Fluid, crosslinking time 1min, crosslinked gel can be hung with glass bar tune.Using SY/T 5107- Fracturing fluid heatproof resistant to shearing test method specified in 2005 " aqueous fracturing fluid method of evaluating performance ", with HAAKE MARS III The temperature and shearing sustainability of fracturing fluid under the conditions of high temperature rheometer tests 120 DEG C, as a result as described in Figure 1,120 DEG C, 170s-1 Under the conditions of shearing 90min system apparent viscosity be 142mPas.
4 fracturing liquid rubber-breaking performance of embodiment
0.02g capsule breaker EB-1 is added in fracturing fluid gel 100g prepared by Example 3, breaks in 90 DEG C of water-baths Glue, gel breaking time 90min, breaking glue solution viscosity 2.07mPas, residue content 112mg/L.
5 preparing fracturing fluid base fluid of embodiment
492g water is added in device in mixed adjust, 2.25g Instant hydroxypropyl guar gum SRG-1 is added under stiring, dissolves 3min Afterwards, 1g sodium gluconate, 2.50g expansion-resisting agent FP-1,1.5g cleanup additive ME-2,0.1g sodium hydroxide, 0.5g sterilization are sequentially added Agent SK-1 and 0.5g non-emulsifier SF-1, stirring and dissolving 2min stand 1h, are configured to the fracturing fluid that guar gum concentration is 0.45% Base fluid.Fracturing fluid base fluid apparent viscosity 70mPas (170s-1), pH value 11.
6 fracturing fluid cross-linking properties of embodiment and temperature and shearing sustainability
The fracturing fluid base fluid 100mL that Example 5 is prepared is added organic borate cross-linker 0.40g prepared by embodiment 1, obtains To hydroxypropyl guar gum Borate Gelling Hydrofracturing Fluid, crosslinking time 1min.Using " the aqueous fracturing fluid performance evaluation side SY/T 5107-2005 Method " specified in fracturing fluid heatproof resistant to shearing test method, test 140 DEG C of conditions with HAAKE MARS III high temperature rheometer The temperature and shearing sustainability of fracturing liquid, as a result as shown in Fig. 2, 140 DEG C, 170s-1Under the conditions of shear 90min system apparent viscosity For for 88mPas.
Embodiment 7 prepares organic borate cross-linker
Equipped with condenser pipe/water segregator, agitating paddle, addition funnel, thermometer four-hole boiling flask in be added 6.2g boric acid, 60g ethylene glycol is warming up to 65 DEG C under stirring, material all dissolves, and adds 3.7g n-butanol, 120 DEG C is warming up under stirring, instead 2h is answered, until the water of abjection no longer changes, divides water about 5.7g;50 DEG C are cooled to, 15g polyethylene is added dropwise in four-hole boiling flask Imines (relative molecular mass about 600, need to be dehydrated before use) is warming up to 140 DEG C, reacts 2h, until the n-butanol amount of abjection is no longer Variation, n-butanol amount about 4.1g are finally cooled to room temperature and obtain product.
8 preparing fracturing fluid base fluid of embodiment
492g water is added in device in mixed adjust, 2.75g Instant hydroxypropyl guar gum SRG-1 is added under stiring, dissolves 3min Afterwards, 1g sodium gluconate, 2.50g expansion-resisting agent FP-1,1.5g cleanup additive ME-2,0.1g sodium hydroxide, 0.5g sterilization are sequentially added Agent SK-1 and 0.5g non-emulsifier SF-1, stirring and dissolving 2min stand 1h, are configured to the fracturing fluid that guar gum concentration is 0.55% Base fluid.Fracturing fluid base fluid apparent viscosity 99mPas (170s-1), pH value 11.
9 fracturing fluid cross-linking properties of embodiment and temperature and shearing sustainability
The fracturing fluid base fluid 100mL that Example 8 is prepared is added organic borate cross-linker 0.50g prepared by embodiment 7, obtains To hydroxypropyl guar gum Borate Gelling Hydrofracturing Fluid, crosslinking time 40s.Using " the aqueous fracturing fluid performance evaluation side SY/T 5107-2005 Method " specified in fracturing fluid heatproof resistant to shearing test method, test 150 DEG C of conditions with HAAKE MARS III high temperature rheometer The temperature and shearing sustainability of fracturing liquid, as a result as shown in figure 3,150 DEG C, 170s-1Under the conditions of shear 90min system apparent viscosity For for 97mPas.
Application example
A bite that ancient 1** well is certain Mountain area upper palaeozoic is spent to evaluate well, in-place permeability (0.6~2) × 10-3μm2, hole Porosity 6%~10%, 2320~2390m of buried depth, are typical ultralow permeable reservoir, are mentioned using pressing crack construction by 110 DEG C of formation temperature High well yield.It adopts low concentration guar gum Borate Gelling Hydrofracturing Fluid prepared with embodiment 3 and carries out pressing crack construction, hydroxyl in fracturing fluid system Propyl guar gum concentration is 0.30%.
Live pressing crack construction is carried out in September, 2016, uses low concentration guar gum fracturing fluid 490m altogether3, Fracturing Pressure 52~65MPa, most high sand ratio 40% always add sand 50m3.The on-site crosslinked time 1min of fracturing fluid, crosslinking is all right, smoothly complete At pressing crack construction.Well day oil-producing 12t/d, fracturing effect are significant.
Above-mentioned, although specific embodiments of the present invention have been described in conjunction with the embodiments, not protects to the present invention The limitation of range, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art The various modifications or changes that can be made are not needed to make the creative labor still within protection scope of the present invention.

Claims (10)

1. a kind of organic borate cross-linker, it is characterised in that: be using boric acid and organic polyamine compound as raw material, by the following method It being prepared: boric acid is mixed with ethylene glycol, 60~70 DEG C are warming up under stirring, all after dissolution, n-butanol is added in material, 110~120 DEG C are warming up under stirring, the water of reaction to abjection no longer changes;Organic polyamine compound is added dropwise again, is warming up to 120~140 DEG C, the n-butanol amount of reaction to abjection no longer changes, and is cooled to room temperature to get organic borate cross-linker is arrived;It is described to have Machine polyamine compounds are selected from diethylenetriamine, triethylene tetramine, tetraethylenepentamine, polyethylene polyamine or polyethyleneimine.
2. organic borate cross-linker according to claim 1, it is characterised in that: the boric acid, ethylene glycol, n-butanol, organic The molar ratio of polyamine compounds is 1: (1.5~2): 1: (0.01~0.4).
3. organic borate cross-linker of any of claims 1 or 2 is preparing the application in guar gum fracturing fluid.
4. a kind of guar gum fracturing fluid, it is characterised in that: be grouped as by the group of following parts by weight: each component weight percent Meter, hydroxypropyl guar gum 0.2%~0.6%, organic borate cross-linker 0.2%~0.6% of any of claims 1 or 2, pH adjusting agent 0.01%~0.2%, temperature stability agent 0~0.5%, other additives 0.2%~2%, surplus is water.
5. guar gum fracturing fluid according to claim 4, it is characterised in that: the pH adjusting agent is selected from sodium carbonate or/and hydrogen Sodium oxide molybdena.
6. guar gum fracturing fluid according to claim 4, it is characterised in that: the temperature stability agent is selected from sorbierite, xylose The combination of one or more of alcohol, glucose, fructose, galactolipin, mannose, ribose, xylose, sodium gluconate.
7. guar gum fracturing fluid according to claim 4, it is characterised in that: other additives are selected from expansion-resisting agent, the row of helping The combination of one or more of agent, fungicide, non-emulsifier, gel breaker.
8. the guar gum fracturing fluid according to any one of claim 4~7, it is characterised in that: the guar gum fracturing fluid, be by What the group of following parts by weight was grouped as: hydroxypropyl guar gum, 0.3%;Organic borate cross-linker, 0.35%;Sodium gluconate, 0.1%; Expansion-resisting agent, 0.5%;Cleanup additive, 0.3%;Sodium carbonate, 0.1%;Fungicide, 0.1%;Non-emulsifier, 0.1%;Surplus is water.
9. the guar gum fracturing fluid according to any one of claim 4~7, it is characterised in that: the guar gum fracturing fluid, group It is grouped into following one:
1. Instant hydroxypropyl guar gum, 0.3%;Organic borate cross-linker, 0.35%;Sodium gluconate, 0.1%;Expansion-resisting agent FP-1, 0.5%;Cleanup additive ME-2,0.3%;Sodium carbonate, 0.1%;Fungicide SK-1,0.1%;Non-emulsifier SF-1,0.1%;Surplus For water;
2. Instant hydroxypropyl guar gum, 0.3%;Organic borate cross-linker, 0.35%;Sodium gluconate, 0.1%;Expansion-resisting agent FP-1, 0.5%;Cleanup additive ME-2,0.3%;Sodium carbonate, 0.1%;Fungicide SK-1,0.1%;Non-emulsifier SF-1,0.1%;Capsule Gel breaker EB-1,0.02%;Surplus is water;
3. Instant hydroxypropyl guar gum, 0.55%;Organic borate cross-linker, 0.5%;Sodium gluconate, 0.2%;Expansion-resisting agent FP-1, 0.5%;Cleanup additive ME-2,0.3%;Sodium hydroxide, 0.02%;Fungicide SK-1,0.1%;Non-emulsifier SF-1,0.1%;It is remaining Amount is water;
4. Instant hydroxypropyl guar gum, 0.45%;Organic borate cross-linker, 0.4%;Sodium gluconate, 0.2%;Expansion-resisting agent FP-1, 0.5%;Cleanup additive ME-2,0.3%;Sodium hydroxide, 0.02%;Fungicide SK-1,0.1%;Non-emulsifier SF-1,0.1%;It is remaining Amount is water.
10. the preparation method of guar gum fracturing fluid described in any one of claim 4~9, it is characterised in that: under stirring condition, Hydroxypropyl guar gum is added to the water, after stirring 3min, pH adjusting agent, temperature stability agent and other additives is added, is stirred Uniformly to formation base fluid;Base fluid stands 5min~1h, and organic borate cross-linker is added, and is crosslinked 30~60s to get low concentration guar gum pressure Split liquid.
CN201710597438.6A 2017-07-20 2017-07-20 A kind of organic borate cross-linker and guar gum fracturing fluid Pending CN109280547A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710597438.6A CN109280547A (en) 2017-07-20 2017-07-20 A kind of organic borate cross-linker and guar gum fracturing fluid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710597438.6A CN109280547A (en) 2017-07-20 2017-07-20 A kind of organic borate cross-linker and guar gum fracturing fluid

Publications (1)

Publication Number Publication Date
CN109280547A true CN109280547A (en) 2019-01-29

Family

ID=65185398

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710597438.6A Pending CN109280547A (en) 2017-07-20 2017-07-20 A kind of organic borate cross-linker and guar gum fracturing fluid

Country Status (1)

Country Link
CN (1) CN109280547A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110437815A (en) * 2019-07-26 2019-11-12 大港油田集团有限责任公司 Seawater-based fracturing fluid and preparation method thereof
CN112250703A (en) * 2020-10-16 2021-01-22 中国石油集团渤海钻探工程有限公司 Preparation method of borate crosslinking agent and product
CN113214336A (en) * 2021-05-24 2021-08-06 昆山京昆油田化学科技有限公司 Organic boron crosslinking agent based on allyl galactoside and preparation method and application thereof
CN113265236A (en) * 2021-06-11 2021-08-17 陕西丰登石化有限公司 Crosslinking agent for fracturing suitable for high-salinity water quality low-concentration guar gum system
CN113512413A (en) * 2021-06-17 2021-10-19 苏州福硼科技发展有限公司 Medicament for breaking boron crosslinking agent and preparation method thereof
CN114032083A (en) * 2021-12-21 2022-02-11 中石化石油工程技术服务有限公司 Crosslinking agent for reconstructing wellbore fracture and preparation method and application thereof
CN115433362A (en) * 2022-09-21 2022-12-06 河北工业大学 Preparation method of cross-linking agent for low-concentration temperature-resistant and shear-resistant guanidine gum
CN116120909A (en) * 2021-11-12 2023-05-16 中国石油天然气集团有限公司 Wettability-regulating crosslinking agent, fracturing fluid, and preparation and application methods thereof
CN116200182A (en) * 2021-11-30 2023-06-02 大庆油田有限责任公司 Crosslinking agent for ultralow-concentration vegetable gum fracturing fluid and synthesis process and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110214860A1 (en) * 2010-03-05 2011-09-08 Narongsak Tonmukayakul Clean Viscosified Treatment Fluids and Associated Methods
CN103694986A (en) * 2014-01-08 2014-04-02 四川川庆井下科技有限公司 Guar gum fracturing fluid
CN104910890A (en) * 2015-05-25 2015-09-16 中国石油集团渤海钻探工程有限公司 Organoboron-hydroxypropyl guanidine gum system crosslinking promoter, and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110214860A1 (en) * 2010-03-05 2011-09-08 Narongsak Tonmukayakul Clean Viscosified Treatment Fluids and Associated Methods
CN103694986A (en) * 2014-01-08 2014-04-02 四川川庆井下科技有限公司 Guar gum fracturing fluid
CN104910890A (en) * 2015-05-25 2015-09-16 中国石油集团渤海钻探工程有限公司 Organoboron-hydroxypropyl guanidine gum system crosslinking promoter, and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
白海涛等: ""有机胺硼交联剂AB-1的合成及应用"", 《精细化工》 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110437815A (en) * 2019-07-26 2019-11-12 大港油田集团有限责任公司 Seawater-based fracturing fluid and preparation method thereof
CN112250703A (en) * 2020-10-16 2021-01-22 中国石油集团渤海钻探工程有限公司 Preparation method of borate crosslinking agent and product
CN113214336A (en) * 2021-05-24 2021-08-06 昆山京昆油田化学科技有限公司 Organic boron crosslinking agent based on allyl galactoside and preparation method and application thereof
CN113214336B (en) * 2021-05-24 2022-12-02 昆山京昆油田化学科技有限公司 Organic boron crosslinking agent based on allyl galactoside and preparation method and application thereof
CN113265236A (en) * 2021-06-11 2021-08-17 陕西丰登石化有限公司 Crosslinking agent for fracturing suitable for high-salinity water quality low-concentration guar gum system
CN113512413A (en) * 2021-06-17 2021-10-19 苏州福硼科技发展有限公司 Medicament for breaking boron crosslinking agent and preparation method thereof
CN116120909A (en) * 2021-11-12 2023-05-16 中国石油天然气集团有限公司 Wettability-regulating crosslinking agent, fracturing fluid, and preparation and application methods thereof
CN116200182A (en) * 2021-11-30 2023-06-02 大庆油田有限责任公司 Crosslinking agent for ultralow-concentration vegetable gum fracturing fluid and synthesis process and application thereof
CN114032083A (en) * 2021-12-21 2022-02-11 中石化石油工程技术服务有限公司 Crosslinking agent for reconstructing wellbore fracture and preparation method and application thereof
CN115433362A (en) * 2022-09-21 2022-12-06 河北工业大学 Preparation method of cross-linking agent for low-concentration temperature-resistant and shear-resistant guanidine gum
CN115433362B (en) * 2022-09-21 2023-09-15 河北工业大学 Preparation method of cross-linking agent for low-concentration temperature-resistant shearing-resistant guanidine gum

Similar Documents

Publication Publication Date Title
CN109280547A (en) A kind of organic borate cross-linker and guar gum fracturing fluid
US6843841B2 (en) Preventing flow through subterranean zones
US7795190B2 (en) Process to prepare borozirconate solution and use as a cross-linker in hydraulic fracturing fluids
CN101675062B (en) Zirconium-based cross-linker compositions and their use in high pH oil field applications
CN101412905B (en) Preparation of composite fracturing fluid for hydraulic fracture
CN105368436B (en) A kind of small molecule clean fracturing fluid and the preparation method and application thereof
US8044001B2 (en) Solid zirconium-based cross-linking agent and use in oil field applications
CN105086985A (en) Synergistic-fiber vegetable-gel fracturing fluid and preparation method therefor
CN101945973A (en) Process to prepare zirconium-based cross-linker compositions and their use in oil field applications
CN102031102A (en) Preparation method and fracturing construction method of locally and continuously mixed clean fracturing fluid additive
CN106350048A (en) Oil washing agent for oil well fracturing as well as preparation method and application of oil washing agent
CN108018035A (en) A kind of resistant to shearing low concentration guar gum Zirconium gel fracturing fluid
US7790657B2 (en) Process to prepare borozirconate solution and use a cross-linker in hydraulic fracturing fluids
CN104312571B (en) A kind of modified xantham gum thickening and its application in fracturing fluid is prepared
CN105331348A (en) Homogeneous-phase microemulsion oil-displacing agent applied to low-permeation oil field and preparation method of homogeneous-phase microemulsion oil-displacing agent
US8544546B2 (en) Delivering water-soluble polysaccharides for well treatments
CN102643637B (en) Clear fracturing fluid
US7795189B2 (en) Zirconium-hydroxy alkylated amine-hydroxy carboxylic acid cross-linking composition for use with high pH polymer solutions
CN106244123A (en) A kind of high temperature resistance organic borate cross-linker and preparation method thereof
CN105623640A (en) Preparation method of organoboron high-temperature crosslinking agent used for fracturing
CN111718704A (en) Multifunctional flow promoter and high-temperature-resistant polymer fracturing fluid system
CN106893573A (en) A kind of biological fracturing fluid system and its preparation and application
CN105778883A (en) Full-suspension cleaning polymer fracturing fluid and preparation method thereof
CN102504798B (en) Ground crosslinked acid liquid for acid fracturing and preparation method thereof
CN109957385A (en) Crosslinking enhancer and preparation method thereof and fracturing fluid

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20190129