CN104087283A - Fracturing thickening agent for fast dispersing and tackifying under acidic condition and preparation method thereof - Google Patents

Fracturing thickening agent for fast dispersing and tackifying under acidic condition and preparation method thereof Download PDF

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Publication number
CN104087283A
CN104087283A CN201410345598.8A CN201410345598A CN104087283A CN 104087283 A CN104087283 A CN 104087283A CN 201410345598 A CN201410345598 A CN 201410345598A CN 104087283 A CN104087283 A CN 104087283A
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thickening material
preparation
tackify
acidic conditions
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CN104087283B (en
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邓明宇
何建平
彭树华
崔俊杰
吴志明
尹恒
朱明山
巩沛鑫
陈卫平
籍淑贤
蒋杰
陆辉
肖青香
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Kunshan Jingkun Oilfield Chemical Technology Co ltd
China National Petroleum Corp
CNPC Great Wall Drilling Co
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KUNSHAN JINGKUN OIL FIELD CHEMISTRY SCIENCE AND TECHNOLOGY DEVELOPMENT Co
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    • 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • C08B37/0096Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
    • 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
    • C09K8/84Compositions based on water or polar solvents
    • C09K8/86Compositions based on water or polar solvents containing organic compounds
    • C09K8/88Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/90Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Life Sciences & Earth Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
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  • Polymers & Plastics (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention discloses a fracturing thickening agent for fast dispersing and tackifying under an acidic condition and a preparation method thereof. The fracturing thickening agent is characterized by being prepared through three-step etherification reaction under an alkaline condition; the three-step etherification reaction comprises etherified and modified reaction treatment on chlorine alkyl alcohol, epoxyalkane and negative ions respectively; then neutralizing by using acid, and washing by using alcohol water; carrying out solid-liquid separation; milling, crushing and drying. The guar gum fracturing thickening agent disclosed by the invention has the advantages of fast dispersion and tackifying, high thickening capacity, temperature resistance and anti-shearing capacity, can reach the final viscosity being more than 90% within 3 minutes under the acidic condition, and can be instantly used after being prepared, thereby meeting the requirement for continuous blending in the field, greatly saving the liquid cost and increasing the production efficiency.

Description

Pressure break thickening material of rapid dispersion tackify and preparation method thereof under a kind of acidic conditions
Technical field
The present invention relates to a kind of modified guar thickening material, relate to particularly a kind of can be in acid and neutral solution the modified guar thickening material of rapid dispersion and tackify, more specifically, the present invention relates to a kind of pressure break thickening material of the fracturing reform operation that can be used for the quick property of alkali stratum, can be under cold condition, in 3 minutes, reach the more than 90% of final viscosity, can meet the on-the-spot requirement of mixture continuously, and the preparation method of described thickening material.
Background technology
Waterfrac treatment is the Main Yield-increasing technique means of fine and close oil/gas output, and fracturing liquid, as making the medium that stitches and carry propping agent, is the important component part of fracturing technology, and fracturing liquid developing direction embodies three features: lower concentration, low cost and low injury.Application is mainly aqueous fracturing fluid at present, and thickening material is the host of aqueous fracturing fluid, in order to improve of the fracturing fluid viscosity, falls leak-off, suspends and carries propping agent.The thickening material using is at present mainly guar gum and derivative thereof.Although the hydroxyalkyl guar gum of the hydroxypropylguar gum occurring in recent years, hydroxyethyl melon that or oligomeric etherificate has good salt tolerance, but can not under acidic conditions, effectively be cross-linked to form frozen glue, and the conventional frozen glue heat-resisting ability forming is limited, use temperature is more than 120 DEG C time, need the concentration of guar gum very large, residue content is higher, after the fracturing liquid operation of making, flow conductivity to zone permeability, sand packed fracture etc. all has injury, hinder the unimpeded outflow of oil gas, affect production efficiency, carboxymethyl guar gum, hydroxyalkyl cationic guar gum and Carboxymethyl hydroxypropyl guar plasma guar gum have application in various degree at oil-gas field fracturing, particularly carboxymethyl guar gum and Carboxymethyl hydroxypropyl guar have the resistance to shear ability of good heatproof, can be resistance to 180 DEG C, even higher temperature, and can form good frozen glue at acidic conditions with metal crosslinking agents such as titanium zirconiums, but under acidic conditions, carboxylic acid methyl and sulfonic group do not resemble the very strong interionic repulsive interaction that carboxylate salt methyl and sulfonate produce on guar gum molecular chain, gap between molecular chain makes the permeating speed of water molecules between molecular chain fast not, thereby affect its hydration rate, rheological property can be subject to the impact of salt simultaneously.As everyone knows, mixture can improve pressing crack construction efficiency continuously, eliminates fracturing liquid waste, reduces environmental pollution, the current important dosing technology as large-scale horizontal well and factory operation.Carboxymethyl guar gum and Carboxymethyl hydroxypropyl guar because when preparation instantly-soluble can be undesirable, easily play flake and affect construction quality, be difficult to reach the requirement of continuous mixture construction.
In sum, for the quick property of alkali stratum, lacking under a kind of acidic conditions can the quick tackify of rapid dispersion and have stronger tackifying ability and the guar gum pressure break thickening material of high temperature resistant (more than 120 DEG C), anti-salt, shear resistant and low level of residue.Therefore, the mixture operation continuously fast under on-the-spot extensive dosing condition is realized in the urgent need to developing a kind of vegetable jelly pressure break thickening material instant and that have stronger tackifying ability and heatproof, anti-salt, shear resistant and a low level of residue in this area.
Summary of the invention
The first object of the present invention is to overcome the deficiencies in the prior art part, provide the one can be instant under cold condition, particularly instant under acidic conditions, and there is stronger tackifying ability and heatproof, anti-salt, the vegetable jelly pressure break thickening material of shear resistant and low level of residue, this thickening material is to obtain on the basis of oligomeric hydroxyalkyl etherificate guar gum, on the terminal hydroxyl of oligomeric hydroxyalkyl etherificate, connect again resistant to elevated temperatures anionic group, on guar gum molecular chain, form very long modification side chain, increase the gap between molecular chain, effectively improve hydration rate, and can meet the mixture operation continuously fast under the on-the-spot extensive dosing condition of the quick property of alkali oil and gas reservoir exploitation.The water-insoluble of this thickening material is lower than 2.5%, and residue content is lower than 80mg/L, and working temperature, from normal temperature to 200 DEG C, has the advantages such as high temperature resistant, anti-salt, low residue.
The second object of the present invention is to obtain a kind of method that obtains described pressure break thickening material.
The 3rd object of the present invention is to obtain the fracturing liquid that contains described thickening material.
The 4th object of the present invention is to obtain the purposes of described pressure break thickening material.
In a first aspect of the present invention, a kind of fracturing fluid thickener is provided, described fracturing fluid thickener is carried out three times etherification modified obtaining under alkaline condition by guar gum.
In a specific embodiment of the present invention, described three etherification modified comprising:
Single kind or multiple chlorine alkyl alcohol etherificate;
Single kind or multiple epoxy alkane etherificate;
Negatively charged ion etherificate.
In a specific embodiment of the present invention, described chlorine alkyl alcohol is preferably chloroethanol or propylene chlorohydrin.Epoxy alkane is oxyethane or propylene oxide, and negatively charged ion etherifying agent is carboxymethyl and sulfonic group.
In a specific embodiment of the present invention, in described negatively charged ion etherifying agent, sulfonic group can be sulfoethyl or 2-hydroxyl sulfopropyl.
In a specific embodiment of the present invention, the oligomeric hydroxyalkyl of structural formula that described fracturing fluid thickener has, oligomeric hydroxyalkyl anionic group and anionic group can be substituted in the C2 of semi-lactosi, C3, the hydroxyl of C4 and C6 and the C2 of seminose, on the hydroxyl of C3 and C6, its structural formula can be exemplified as (I), as shown in the table:
In described structural formula I, R is H and methyl, m, and n may be 0,1,2,3,4,5, oligomeric hydroxyalkyl hydroxyalkyl substitution value scope is at 0.15-0.5; Particularly 0.18-0.35; Nu is negatively charged ion etherificate base, and described negatively charged ion etherificate base comprises carboxylic acid group and sulfonic group, and wherein carboxylic acid group is preferably carboxymethyl, and sulfonic group is preferably sulfoethyl or 2-hydroxyl sulfopropyl, and the substitution value scope of carboxymethyl is at 0.05-0.40, particularly 0.18-0.30.Sulfonic substitution value scope is at 0.01-0.60, particularly 0.12-0.28.The mean chain length 1.0-2 of hydroxyalkyl, the per-cent that Nu is connected on hydroxyalkyl end is 0-80%.
In a specific embodiment of the present invention, the molecular weight of described fracturing fluid thickener is at 160-300 ten thousand.
A second aspect of the present invention provides a kind of preparation method of fracturing fluid thickener of the present invention, described thickening material can be guar gum, but being not limited only to guar gum, itself and solvent, alkali, ion etherifying agent and water carry out multiple chemical modification by required substitution value.
A third aspect of the present invention provides a kind of fracturing liquid of fracturing fluid thickener as described in the present invention that contains.
A fourth aspect of the present invention provides a kind of purposes of fracturing fluid thickener as described in the present invention.
Compared with prior art, beneficial effect of the present invention is:
The invention provides rapid dispersion and tackify, and there is the guar gum pressure break thickening material of stronger thickening capabilities, heatproof, anti-shear ability, this thickening material is under acidic conditions, within 3 minutes, reach the more than 90% of final viscosity, join and use, meet the requirement of on-the-spot continuous mixture, when greatly having saved liquid cost, improved production efficiency.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of oligomeric hydroxypropyl carboxy methyl guar gum;
Fig. 2 is the characteristic signal comparison diagram of methyl on common hydroxypropylguar gum and oligomeric hydroxypropyl carboxy methyl guar gum substituting group thereof;
Fig. 3 is oligomeric hydroxypropylguar gum and the characteristic signal comparison diagram that reacts methyl on the general substituting group of after product with negatively charged ion etherifying agent thereof;
Fig. 4 is the molecular weight analyse figure of the oligomeric hydroxypropylation guar gum of carboxymethyl;
Fig. 5 is the molecular weight analyse figure of the oligomeric hydroxyethylation guar gum of carboxymethyl;
Fig. 6 is the molecular weight analyse figure of the oligomeric hydroxypropylation guar gum of sulfoethyl;
Fig. 7 is the oligomeric hydroxypropylation guar gum of carboxymethyl, the tackify graphic representation under 5 DEG C of conditions;
Fig. 8 is the oligomeric hydroxypropylation guar gum of carboxymethyl, the tackify graphic representation under 25 DEG C of conditions;
Fig. 9 is the oligomeric hydroxyethylation guar gum of carboxymethyl, the tackify graphic representation under 25 DEG C of conditions;
Figure 10 is the flow curve figure of the oligomeric hydroxyalkylation guar gum of carboxymethyl.
Embodiment
With regard to concrete case study on implementation, viscosifying agent of the present invention and preparation method thereof is described below.
Embodiment 1:
100 kilograms of guar gums are risen in Virahol in 300-400, lead to N2 half an hour, under low temperature condition, 28 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, drip 12 kilograms of chloroethanols, be warming up to 70 DEG C, stirring reaction 3 hours, centrifugal, by gained solid cooled to room temperature, in logical nitrogen situation, 7 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, drip 3 kilograms, oxyethane, be warming up to 70 DEG C, stirring reaction 2 hours, centrifugal, by gained solid cooled to room temperature, in logical nitrogen situation, 55 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, drip 35 kilograms of Mono Chloro Acetic Acids, be warming up to 70 DEG C, stirring reaction 3 hours, cooling, with carbonic acid gas, citric acid or acetic acid neutralization, filter, alcohol water washing 2 times, dry, pulverize, finished product.
Embodiment 2:
100 kilograms of guar gums are risen in Virahol in 300-400, lead to N2 half an hour, under low temperature condition, 28 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, drip 12 kilograms of chloroethanols, be warming up to 70 DEG C, stirring reaction 3 hours, centrifugal, by gained solid cooled to room temperature, in logical nitrogen situation, 19 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, drip 8 kilograms, oxyethane, be warming up to 70 DEG C, stirring reaction 2 hours, centrifugal, by gained solid cooled to room temperature, in logical nitrogen situation, 75 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, add 50% chloroethyl sodium sulfonate suspension liquid 120 kg, be warming up to 80 DEG C, stirring reaction 4 hours, cooling, with carbonic acid gas, citric acid or acetic acid neutralization, filter, alcohol water washing 2 times, dry, pulverize, finished product.
Embodiment 3:
100 kilograms of guar gums are risen in Virahol in 300-400, lead to N2 half an hour, under low temperature condition, 28 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, drip 15 kilograms of chloro isopropanols, be warming up to 70 DEG C, stirring reaction 3 hours, centrifugal, by gained solid cooled to room temperature, in logical nitrogen situation, 12 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, drip 8 kilograms of propylene oxide, be warming up to 70 DEG C, stirring reaction 2 hours, centrifugal, by gained solid cooled to room temperature, in logical nitrogen situation, in logical nitrogen situation, be cooled to room temperature, 55 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, drip 30 kilograms of Mono Chloro Acetic Acids, be warming up to 70 DEG C, stirring reaction 3 hours, cooling, with carbonic acid gas, citric acid or acetic acid neutralization, filter, alcohol water washing 2 times, dry, pulverize, finished product.
Embodiment 4:
100 kilograms of guar gums are risen in Virahol in 300-400, lead to N2 half an hour, under low temperature condition, 28 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, drip 15 kilograms of chloro isopropanols, be warming up to 70 DEG C, stirring reaction 3 hours, centrifugal, by gained solid cooled to room temperature, in logical nitrogen situation, 10 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, drip 6 kilograms of propylene oxide, be warming up to 70 DEG C, stirring reaction 2 hours, centrifugal, by gained solid cooled to room temperature, in logical nitrogen situation, 70 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, add 110 kilograms of 50% chloroethyl sodium sulfonate suspension liquids, be warming up to 80 DEG C, stirring reaction 4 hours, cooling, with carbonic acid gas, citric acid or acetic acid neutralization, filter, alcohol water washing 2 times, dry, pulverize, finished product.
Embodiment 5:
By 100 kilograms of guar gums in 300 liters of acetone, lead to N2 half an hour, under low temperature condition, 28 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, drip 15 kilograms of chloro isopropanols, be warming up to 60 DEG C, stirring reaction 3 hours, centrifugal, be cooled to room temperature, 24 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, drip 13 kilograms of propylene oxide, be warming up to 60 DEG C, stirring reaction 2 hours, centrifugal, be cooled to room temperature, 75 kilograms of the sodium hydroxide solutions of dropping 40%, stir after half an hour, drip 40 kilograms of Mono Chloro Acetic Acids, be warming up to 70 DEG C, stirring reaction 3 hours, cooling, with carbonic acid gas, citric acid or acetic acid neutralization, filter, alcohol water washing 2 times, dry, pulverize, finished product.
While measuring quick thickening property curve, take 0.96g rubber powder, under use chandler engineering agitator stirs with 1500rpm, pour into and contain in the jar of distilled water that 400mLpH is 4-6, and start timing, stir after 2.5min, under 300rpm (511s-1) condition, measure viscosity data with the fast viscometer of Fan35 six.
Preparation sample fracturing liquid is evaluated; get fracturing fluid thickener certain mass of the present invention; put into the water of 500mL; stir swelling; take out 100mL glue, uses pH adjusting agent glue to be adjusted to 4-6, then adds organic zirconium solution crosslinking; stir into the frozen glue hanging with glass stick, then bring a certain amount of quartz sand in.
In working-yard, oil field, invention product continuous preparing fracturing fluid whenever and wherever possible, according to cultivation scale requirement, use glue and a certain amount of organic zirconium of fracturing fluid thickener of the present invention to be cross-linked into visco-elasticity frozen glue, stirring a certain amount of quartz sand brings in frozen glue again, high pressure is pressed into oil reservoir, cause the sand packed fracture of certain length, through breaking, glue is counter to be arranged fracturing liquid, the propping agent carrying is stayed on the oil duct of crack, and the not level of residue of broken glue staying goes seldom simultaneously, cause crude oil can pass through the unimpeded outflow in oil duct propping agent space, reach the effect that reduces formation damage raising output.
The foregoing is only preferred embodiments of the present invention; protection scope of the present invention is not limited with above-mentioned embodiment; in every case the equivalence that those of ordinary skill in the art do according to disclosed content is modified or is changed, and all should include in the protection domain of recording in claims.

Claims (8)

1. pressure break thickening material of rapid dispersion tackify and preparation method thereof under an acidic conditions, it is characterized in that: described thickening material is under alkaline condition, to be carried out three step etherification reactions to obtain by guar gum, it is respectively the etherification modified reaction treatment of chlorine alkyl alcohol, epoxy alkane and negatively charged ion, afterwards with acid neutralization, alcohol water washing, solid-liquid separation, rolls pulverizing, dry.
2. pressure break thickening material of rapid dispersion tackify and preparation method thereof under a kind of acidic conditions according to claim 1, is characterized in that: described guar gum and solvent, alkali, ion etherifying agent and water carry out chemical modification processing by required substitution value.
3. pressure break thickening material of rapid dispersion tackify and preparation method thereof under a kind of acidic conditions according to claim 1, is characterized in that: described three etherification modified comprising: single kind or multiple chlorine alkyl alcohol etherificate, single kind or multiple epoxy alkane etherificate, negatively charged ion etherificate.
4. pressure break thickening material of rapid dispersion tackify and preparation method thereof under a kind of acidic conditions according to claim 1, it is characterized in that: described chlorine alkyl alcohol is preferably chloroethanol or propylene chlorohydrin, described epoxy alkane is oxyethane or propylene oxide, and described negatively charged ion etherifying agent is carboxylic acid group and sulfonic group.
5. pressure break thickening material of rapid dispersion tackify and preparation method thereof under a kind of acidic conditions according to claim 4, is characterized in that: in described negatively charged ion etherifying agent, carboxylic acid group can be carboxymethyl, and sulfonic group can be sulfoethyl or 2-hydroxyl sulfopropyl.
6. pressure break thickening material of rapid dispersion tackify and preparation method thereof under a kind of acidic conditions according to claim 1, it is characterized in that: the oligomeric hydroxyalkyl of structural formula that described fracturing fluid thickener has, oligomeric hydroxyalkyl anionic group and anionic group can be substituted in the C2 of semi-lactosi, C3, the hydroxyl of C4 and C6 and the C2 of seminose, on the hydroxyl of C3 and C6.
7. pressure break thickening material of rapid dispersion tackify and preparation method thereof under a kind of acidic conditions according to claim 1, is characterized in that: the molecular weight of described fracturing fluid thickener is at 160-300 ten thousand.
8. pressure break thickening material of rapid dispersion tackify and preparation method thereof under a kind of acidic conditions according to claim 1, it is characterized in that: described thickening material can be guar gum, but being not limited only to guar gum, itself and solvent, alkali, ion etherifying agent and water carry out multiple chemical modification by required substitution value.
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Cited By (6)

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CN105542744A (en) * 2015-12-11 2016-05-04 中国石油天然气股份有限公司 Salt-resistant thickening agent and salt-resistant recoverable fracturing fluid containing same
CN106432526A (en) * 2016-10-19 2017-02-22 陕西科技大学 Fenugreek gum containing sulfo carboxymethyl and preparation method and application of fenugreek gum
CN106496342A (en) * 2016-10-19 2017-03-15 陕西科技大学 Trigonella bean gum of hydroxypropyl containing sulfonic group and its preparation method and application
CN106496341A (en) * 2016-10-19 2017-03-15 陕西科技大学 Trigonella bean gum containing sulfonic group and its preparation method and application
CN107522791A (en) * 2016-06-20 2017-12-29 中国石油化工股份有限公司 One kind is containing sulfonic natural plant gum and preparation method and application
CN118308084A (en) * 2024-06-11 2024-07-09 大庆恒辉石油钻采技术有限公司 Thickening agent for carbon dioxide fracturing and preparation method thereof

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CN102277141A (en) * 2011-04-26 2011-12-14 中国海洋石油总公司 Guar derivative-based betaine-type amphoteric thickening agent and preparation method thereof
CN102399298A (en) * 2010-09-15 2012-04-04 中国石油天然气股份有限公司 Preparation method of carboxymethyl guar gum
CN103525886A (en) * 2013-10-11 2014-01-22 北京国海能源技术研究院 Clean type liquid guanidine gum and preparation method thereof

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CN102399298A (en) * 2010-09-15 2012-04-04 中国石油天然气股份有限公司 Preparation method of carboxymethyl guar gum
CN102161709A (en) * 2011-04-01 2011-08-24 湖北菲特沃尔科技有限公司 Preparation method of low-polyether fast-hydrating guar gum
CN102277141A (en) * 2011-04-26 2011-12-14 中国海洋石油总公司 Guar derivative-based betaine-type amphoteric thickening agent and preparation method thereof
CN103525886A (en) * 2013-10-11 2014-01-22 北京国海能源技术研究院 Clean type liquid guanidine gum and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105542744A (en) * 2015-12-11 2016-05-04 中国石油天然气股份有限公司 Salt-resistant thickening agent and salt-resistant recoverable fracturing fluid containing same
CN105542744B (en) * 2015-12-11 2018-04-06 中国石油天然气股份有限公司 Salt-resistant thickening agent and salt-resistant recoverable fracturing fluid containing same
CN107522791A (en) * 2016-06-20 2017-12-29 中国石油化工股份有限公司 One kind is containing sulfonic natural plant gum and preparation method and application
CN107522791B (en) * 2016-06-20 2020-10-23 中国石油化工股份有限公司 Vegetable gum containing sulfonic group and preparation method and application thereof
CN106432526A (en) * 2016-10-19 2017-02-22 陕西科技大学 Fenugreek gum containing sulfo carboxymethyl and preparation method and application of fenugreek gum
CN106496342A (en) * 2016-10-19 2017-03-15 陕西科技大学 Trigonella bean gum of hydroxypropyl containing sulfonic group and its preparation method and application
CN106496341A (en) * 2016-10-19 2017-03-15 陕西科技大学 Trigonella bean gum containing sulfonic group and its preparation method and application
CN118308084A (en) * 2024-06-11 2024-07-09 大庆恒辉石油钻采技术有限公司 Thickening agent for carbon dioxide fracturing and preparation method thereof

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