CN103113486B - Sulfonic acid modified Carboxymethyl hydroxypropyl guar and its preparation method and application - Google Patents
Sulfonic acid modified Carboxymethyl hydroxypropyl guar and its preparation method and application Download PDFInfo
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- CN103113486B CN103113486B CN201310052242.0A CN201310052242A CN103113486B CN 103113486 B CN103113486 B CN 103113486B CN 201310052242 A CN201310052242 A CN 201310052242A CN 103113486 B CN103113486 B CN 103113486B
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Abstract
The present invention relates to a kind of sulfonic acid modified Carboxymethyl hydroxypropyl guar and its preparation method and application, described sulfonic acid modified Carboxymethyl hydroxypropyl guar structural formula is as follows:
Description
Technical field
The invention relates to a kind of sulfonic acid modified Carboxymethyl hydroxypropyl guar and its preparation method and application, described application specifically refers to that it is for the preparation of fracturing liquid.
Background technology
Plant gum fracturing fluid polymerization-filling thing thickening material mainly comprises guar gum, fenugreek gum, Mierocrystalline cellulose and chemical modification product (as hydroxypropylguar gum, Carboxymethyl hydroxypropyl guar etc.) thereof, because melon adhesive capacity is high, low price, execute-in-place are simple, frictional resistance is low and large-area applications, but because former powder residue content is high, reach 19% ~ 28%, this kind of of the fracturing fluid broken glue residue and remaining polymer can block the flow-guiding channel that propping agent is formed to some extent, reduce the effect of Oil/gas Well transformation.
Sandstone reservoir is generally anion systems, and the negatively charged ion vegetable jelly of exploitation and reservoir have good compatibleness, preferably water soluble characteristic, and thickening capabilities is strong, and can use at low concentrations, water-insoluble is low, Heat stability is good, and antibiont degraded.In order to reach the multiplex object of potion, to the essential substance producing insolubles and broken glue residue in guar gum----protein and Mierocrystalline cellulose realize chemical hydrolysis and grafting, it is made to be converted into more easily chemistry and biological degradation, novel substance containing wetting ability sulfonate, long-chain organic sulfonate is introduced in carboxymethyl melon plastic structure, cleanup additive effect can be played, simultaneously in conjunction with the cost factor of vegetable jelly, Carboxymethyl hydroxypropyl guar being carried out sulfonation, to prepare vegetable jelly be have polyfunctional effective way, the fracturing liquid formed through modified thickening material after broken glue, produce less residue and polymer remains, the more oxidizable degraded of the cross-linked network structure formed with linking agent, prisoner this it is lower to the injury of reservoir and fracture flow capacity.Meanwhile, contain wetting ability degradable biological tensio-active agent by modified product, there is the characteristic of breakdown of emulsion, low surface and interface tension force, prisoner and the fracturing liquid that formed does not need to add emulsion splitter and cleanup additive, the consumption of chemical agent can be saved.
Summary of the invention
One object of the present invention is to provide a kind of sulfonic acid modified Carboxymethyl hydroxypropyl guar, and described guar gum multiviscosisty efficiency is high, surface and interface tension force is low, broken glue is easy, be beneficial to the row of returning.
Another object of the present invention is to the preparation method that described sulfonic acid modified Carboxymethyl hydroxypropyl guar is provided.
The third object of the present invention is to provide described sulfonic acid modified Carboxymethyl hydroxypropyl guar preparing answering in fracturing liquid
The fourth object of the present invention is the fracturing liquid providing described sulfonic acid modified Carboxymethyl hydroxypropyl guar to prepare.
For reaching above-mentioned purpose, on the one hand, the invention provides a kind of sulfonic acid modified Carboxymethyl hydroxypropyl guar, its structural formula is as follows:
Wherein, R=H, n=0,1,2 or 3; Or, the integer of R=OH, n=0 ~ 6.
The present invention is in order to provide the impact of performance better sulfonic acid modified Carboxymethyl hydroxypropyl guar, and preferred n is 0 or 1.
Carboxymethyl hydroxypropyl guar fracturing fluid system is a kind of lower concentration, Low Damage, resistant to elevated temperatures fracturing fluid system.The shortcoming of this system is that salt resistant character (as KCl) and crosslinked pH scope are narrower.The present invention is by carrying out Carboxymethyl hydroxypropyl guar suitable sulfonic group modifiedly improving its salt tolerance and surfactivity.
According to specific embodiment of the invention scheme, the sulfonic group substitution value of sulfonic acid modified Carboxymethyl hydroxypropyl guar of the present invention is 0.01 ~ 0.2;
Wherein sulfonic group substitution value is more preferably 0.027 ~ 0.18.
Substitution value of the present invention is molar substitution.
According to specific embodiment of the invention scheme, the present invention preferably wherein degree of substitution by carboxymethyl be 0.12 ~ 0.25, hydroxypropyl substitution value 0.15 ~ 0.4.
According to specific embodiment of the invention scheme, the further preferred described sulfonic acid modified Carboxymethyl hydroxypropyl guar molecular weight of the present invention is 160 ~ 2,000,000.
Wherein sulfonic acid modified Carboxymethyl hydroxypropyl guar molecular weight is weight-average molecular weight.
On the other hand, present invention also offers the preparation method of described guar gum, comprise the steps:
(1) Carboxymethyl hydroxypropyl guar is added reaction vessel, add the aqueous solution of alcohol;
(2) under nitrogen atmosphere, drip aqueous sodium hydroxide solution, stir and be warmed up to 65 ~ 80 DEG C, drip sulphonating agent, react 3 ~ 10 hours;
(3) then adjust pH value of solution=7 with acid, filter, collect solid drying, obtain pale yellow powder, be organic sulfonic acid modified carboxy methyl hydroxypropylguar gum.
Described alcohol solution can with reference to the alcohol solution of reaction similar in prior art, and according to specific embodiment of the invention scheme, the aqueous solution of preferred described alcohol is aqueous ethanolic solution or isopropanol water solution.
Described alcohol solution concentration can with reference to the alcohol solution concentration of reaction similar in prior art, and according to specific embodiment of the invention scheme, the concentration of the aqueous solution of preferred described alcohol is mass percent 50% ~ 80%.
The present invention can the concentration of preferred described aqueous sodium hydroxide solution further be also 10 ~ 30%, is more preferably 15%.
The present invention also can preferred steps (2) stirring heat up for being warmed up to 70 DEG C;
In order to optimize reaction of the present invention further, the present invention, preferably after step (2) drips aqueous sodium hydroxide solution, stirs 0.5h, then stirring is warmed up to 65 ~ 80 DEG C.
Even can also be further preferred after stirring is warmed up to 65 ~ 80 DEG C, stir 0.5h, then drip sulphonating agent.
The reaction times of the further preferred steps of the present invention (2) is 3 hours.
The further preferred steps of the present invention (2) sodium hydroxide time for adding is 0.5h.
Described sulphonating agent time for adding is preferably 0.5 ~ 2h.
The kind of described sulphonating agent according to target compound, adopt the corresponding sulphonating agent that art technology is conventional, and according to specific embodiment of the invention scheme, preferred described sulphonating agent can be vinyl sulfonic acid or 3-chlorine-2-hydroxyl propanesulfonate.
The consumption of described sulphonating agent can be determined according to the similar sulfonation reaction consumption in this area, and according to specific embodiment of the invention scheme, when preferred described sulphonating agent is vinyl sulfonic acid, the mass ratio of vinyl sulfonic acid: Carboxymethyl hydroxypropyl guar: NaOH is (2-45): 200: (1.5-35);
When described sulphonating agent is 3-chlorine-2-hydroxyl propanesulfonate, 3-chlorine-2-hydroxyl propanesulfonate: the mass ratio of Carboxymethyl hydroxypropyl guar: NaOH is (4-80): 200: (1.5-35).
Sulfonic group is a kind of anionic group, and carboxymethyl is also a kind of anionic group, and when a kind of anionic group is connected on molecular chain time, another anionic group prisoner causes more difficult connecting for the effect that like charges repels each other, and transformation efficiency is lower.And the present invention is by controlling the substitution value of reactant, and the addition of sulfonic acid etherifying agent, thus perfectly solve the problems referred to above.
The acid of the adjust ph that the acid of step of the present invention (3) can be commonly used with this area, such as organic acid or mineral acid, the reaction that those skilled in the art record according to specification sheets of the present invention, can select suitable acid to carry out adjust ph.Wherein employing preferred for this invention is hydrochloric acid, acetic acid or citric acid.
The third aspect, present invention also offers described sulfonic acid modified Carboxymethyl hydroxypropyl guar and is preparing the application in fracturing liquid.
Fourth aspect, present invention also offers fracturing liquid prepared by described sulfonic acid modified Carboxymethyl hydroxypropyl guar.
The concentration of guar gum described in fracturing liquid can with reference to concentration of the prior art, and according to specific embodiment of the invention scheme, the concentration of preferred described sulfonic acid modified Carboxymethyl hydroxypropyl guar is mass percent 0.1% ~ 0.3%.
Wherein said of the fracturing fluid composition can be prepared with reference to other fracturing liquids of prior art, and those skilled in the art, according to record of the present invention and in conjunction with prior art fracturing liquid, can be easy to obtain fracturing liquid of the present invention.
The present invention can further preferably, and described fracturing liquid is also containing, for example lower mass percent composition: linking agent 0.2 ~ 1%, crosslinking accelerator 0.15 ~ 0.4%, expansion-resisting agent 0.25 ~ 0.4%.
Wherein said linking agent can adopt the linking agent that this area preparing fracturing fluid is conventional, and the present invention is organic boron, organic zirconium or organic titanium preferably.
Wherein crosslinking accelerator and expansion-resisting agent are also the conventional crosslinking accelerator of this area preparing fracturing fluid and expansion-resisting agent, those skilled in the art when selecting crosslinking accelerator and expansion-resisting agent without the need to paying more creative work.
For example conventional crosslinking accelerator can be sodium hydroxide, sodium carbonate and sodium bicarbonate etc.
Conventional expansion-resisting agent can be Repone K, ammonium chloride and polyquaternium etc.
In sum, the invention provides the fracturing liquid of a kind of sulfonic acid modified Carboxymethyl hydroxypropyl guar, its purposes, preparation method and preparation thereof.Guar gum tool provided by the present invention has the following advantages:
1, the organic sulfonic acid modified carboxy methyl hydroxypropylguar gum that prepared by the present invention has certain surfactivity, sufficiently high viscosity and lower surfactivity is had when job execution, (Fig. 1 has investigated the sulfonic group hydroxypropylguar gum (0.6%) of embodiment 1 respectively in the viscosity situation of 0 ~ 0.5%NaCl and KCl to salt tolerant simultaneously, as can be seen from Figure, viscosity is very little by the impact of 0 ~ 0.5% salinity), high temperature resistant, readily biodegradable, crosslinked easily, after broken glue viscosity is low, breaking glue solution surface tension is low, residue is few, the easy row of returning, and can be applicable in oil field.
2, the organic sulfonic acid modified carboxy methyl hydroxypropylguar gum that prepared by the present invention have good water-soluble, leakoff coefficent is less, filtration property good, self have multifunctionality, low viscosity fluid can be become in post-fracturing certain hour, can the row of returning completely, reduce additive types, greatly reduce fracturing liquid to the injury of reservoir.
3, the organic sulfonic acid modified carboxy methyl hydroxypropylguar gum that prepared by the present invention introduces long-chain organic sulfonate in the structure, cleanup additive effect can be played, simultaneously in conjunction with the cost factor of vegetable jelly, Carboxymethyl hydroxypropyl guar is carried out sulfonation to prepare the fracturing liquid that vegetable jelly formed and do not need to add emulsion splitter and cleanup additive, the consumption of chemical agent can be saved.
Accompanying drawing explanation
Fig. 1 is the sulfoethyl substituted carboxymethyl hydroxypropylguar gum viscosity profile of embodiment 1.
Fig. 2 is the molecular weight distribution collection of illustrative plates of the sulfoethyl substituted carboxymethyl hydroxypropylguar gum of embodiment 1, molecular weight Mn=158.5 ten thousand.
Fig. 3 is the molecular weight distribution collection of illustrative plates of the hydroxyl sulfopropyl substituted carboxymethyl hydroxypropylguar gum of embodiment 2, molecular weight Mn=188.8 ten thousand.
Wherein Fig. 2,3 forms for using BI-DNDC differential refractometer to detect drafting.
Fig. 4 is the NMR collection of illustrative plates of the sulfoethyl substituted carboxymethyl hydroxypropylguar gum of embodiment 1: degree of substitution by carboxymethyl is 0.12 ~ 0.25, hydroxypropyl substitution value 0.15 ~ 0.4, sulfonic group substitution value substitution value: 0.01 ~ 0.1.
Fig. 5 is the NMR collection of illustrative plates of the hydroxyl sulfopropyl substituted carboxymethyl hydroxypropylguar gum of embodiment 2: degree of substitution by carboxymethyl is 0.12 ~ 0.25, hydroxypropyl substitution value 0.15 ~ 0.4, sulfonic group substitution value 0.05 ~ 0.15.
Embodiment
Describe the beneficial effect of implementation process of the present invention and generation below by way of specific embodiment in detail, be intended to help reader to understand essence of the present invention and feature better, not as can the restriction of practical range to this case.
Embodiment 1:
A preparation method for organic sulfonic acid modified carboxy methyl hydroxypropylguar gum, step is as follows:
(1) in the reactor that 3L65% ethanolic soln is housed, 1000.0g Carboxymethyl hydroxypropyl guar (degree of substitution by carboxymethyl is 0.19, hydroxypropyl substitution value 0.28) is added;
(2) under nitrogen atmosphere, drip 15% aqueous sodium hydroxide solution 150g, stir and be warmed up to 65 ~ 70 DEG C after 0.5 hour, stir 0.5 hour, drip vinyl sulfonic acid 68g, constant temperature 70 DEG C, dropwises for 2 hours, continues stirring 4 hours;
(3) use hydrochloric acid neutralization reaction liquid to pH=7, filter, solid product is dry at 70 DEG C, obtains pale yellow powder product SCMHPG;
R=H, n=0 in this structure.
The mensuration of product property index:
(1) molecular weight determination:
Adopt the system combined multi-angle laser light scattering apparatus of gel chromatography, moving phase: 0.1N NaNO
3the aqueous solution, PLaquagelOH series gel column is separator column, and sample concentration is 0.70 ‰, measures molecular weight of product;
(2) surface and interface tension detection:
K100C full-automatic surface tension instrument chart interfacial tension;
(3) dynamically performance measurement is injured:
Coal dust is broken, and cross 100 mesh sieves, take 30g coal dust and load in core holding unit, at 6MPa pressure 10min, for subsequent use, survey rate of permeation with 2%KCl, breaking glue solution injures;
(4) viscosity affects change detection by salinity: investigate the present embodiment sulfoethyl substituted carboxymethyl hydroxypropylguar gum (0.6%) respectively in the viscosity situation of 0 ~ 0.5%NaCl and KCl, as can be seen from Figure, viscosity is very little by the impact of 0 ~ 0.5% salinity, other embodiments have also been made same experiment, and obtain the consistent curve of variation tendency, illustrate that sulfonic acid modified Carboxymethyl hydroxypropyl guar viscosity of the present invention all affects by salinity very little.
Product performance measurement result:
(1) product number-average molecular weight: 158.5 ten thousand (Fig. 2 is the molecular weight distribution collection of illustrative plates of sulfoethyl substituted carboxymethyl hydroxypropylguar gum, molecular weight Mn=158.5;
(2) sulfonic group substitution value: 0.027 (Fig. 4 is the NMR collection of illustrative plates of sulfoethyl substituted carboxymethyl hydroxypropylguar gum: degree of substitution by carboxymethyl is 0.12 ~ 0.25, hydroxypropyl substitution value 0.15 ~ 0.4, sulfonic group substitution value: 0.01 ~ 0.1);
(3) apparent viscosity (0.6%): 109.5mPas;
(4) product configuration is become massfraction be 0.12% the aqueous solution, viscosity: 12mPa.s;
(4.1) crosslinked rear viscosity: 360mPa.s;
(4.2) static filtration performance: static filtration performance leakoff coefficent
static spurt loss volume Qsp=1.27 × 10
-3m
3/ m
2, fluid loss rate V=2.25 × 10
-4m/min;
(4.3) the injury rate in coal seam: 12.6%;
(4.4) surface tension: 31.54mN/m, interfacial tension: 2.20mN/m;
(4.5) broken glue under ammonium persulphate (0.5 ‰) S-WAT (0.5 ‰) exists, level of residue: 54.0mg/L after broken glue, breaking glue solution viscosity: 1.60mPa.s.
Embodiment 2:
A preparation method for organic sulfonic acid modified carboxy methyl hydroxypropylguar gum, comprises the following steps successively:
(1) in the reactor that 3L65% aqueous isopropanol is housed, 1000.0g Carboxymethyl hydroxypropyl guar (degree of substitution by carboxymethyl is 0.16, hydroxypropyl substitution value 0.23) is added;
(2) under nitrogen atmosphere, drip 30% aqueous sodium hydroxide solution 110g, stir and be warmed up to 80 DEG C after 0.5 hour, stir 0.5 hour, drip the 3-chlorine-2-hydroxyl propanesulfonate aqueous solution 250g of 40%, maintain the temperature at 80 DEG C, within 1.5 hours, dropwise, continue stirring 5 hours;
(3) with 5% hydrochloric acid neutralization reaction liquid to pH=7, filter, solid product is dry at 70 DEG C, obtains pale yellow powder;
R=OH, n=1 in this structure.
The mensuration of product property index:
(1) molecular weight determination:
Adopt the system combined multi-angle laser light scattering apparatus of gel chromatography, moving phase: 0.1N NaNO
3the aqueous solution, PLaquagelOH series gel column is separator column, and sample concentration is 0.70 ‰, measures molecular weight of product;
(2) surface and interface tension detection:
K100C full-automatic surface tension instrument chart interfacial tension;
(3) dynamically performance measurement is injured:
Coal dust is broken, and cross 100 mesh sieves, take 30g coal dust and load in core holding unit, at 6MPa pressure 10min, for subsequent use, survey rate of permeation with 2%KCl, breaking glue solution side is injured;
(4) viscosity affects change detection by salinity: investigate the present embodiment hydroxyl sulfopropyl substituted carboxymethyl hydroxypropylguar gum (0.6%) respectively in the viscosity situation of 0 ~ 0.5%NaCl and KCl, obtain the curve consistent with Fig. 1 variation tendency, illustrate that the hydroxyl sulfopropyl substituted carboxymethyl hydroxypropyl guar adhesive capacity of the present embodiment all affects by salinity very little.
Product performance measurement result:
(1) product number-average molecular weight: 188.8 ten thousand (Fig. 3 is the molecular weight distribution collection of illustrative plates of hydroxyl sulfopropyl substituted carboxymethyl hydroxypropylguar gum, molecular weight Mn=188.8 ten thousand);
(2) sulfonic group substitution value: 0.11 (Fig. 5 is the NMR collection of illustrative plates of hydroxyl sulfopropyl substituted carboxymethyl hydroxypropylguar gum: degree of substitution by carboxymethyl is 0.12 ~ 0.25, hydroxypropyl substitution value 0.15 ~ 0.4, sulfonic group substitution value 0.05 ~ 0.15);
(3) apparent viscosity (0.6%): 105.2mPas;
(4) product configuration is become massfraction be 0.12% the aqueous solution, viscosity: 15mPa.s;
(4.1) crosslinked rear viscosity: 300mPa.s;
(4.2) static filtration performance: leakoff coefficent
static spurt loss volume Qsp=5.79 × 10
-3m
3/ m
2, fluid loss rate V=7.51 × 10
-4m/min;
(4.3) the injury rate in coal seam: 18.5%;
(4.4) surface tension: 32.78mN/m; Interfacial tension: 3.10mN/m;
(4.5) broken glue under ammonium persulphate (0.5 ‰)-S-WAT (0.5 ‰) exists, level of residue: 58.0mg/L after broken glue, viscosity is 1.80mPa.s.
During the application of this organic sulfonic acid modified carboxy methyl hydroxypropylguar gum as pressure break viscosifying agent, working concentration is 0.1%-0.3% (m/m).
Embodiment 3:
A preparation method for organic sulfonic acid modified carboxy methyl hydroxypropylguar gum, step is as follows:
(1) in the reactor that 3L65% ethanolic soln is housed, 1000.0g Carboxymethyl hydroxypropyl guar (degree of substitution by carboxymethyl is 0.12, hydroxypropyl substitution value 0.35) is added;
(2) under nitrogen atmosphere, drip 30% aqueous sodium hydroxide solution 360g, stir and be warmed up to 80 DEG C after 0.5 hour, stir 0.5 hour, drip the 3-chlorine-2-hydroxyl propanesulfonate aqueous solution 650g of 40%, maintain the temperature at 80 DEG C, within 1.5 hours, dropwise, continue stirring 5 hours;
(3) with 5% citric acid neutralization reaction liquid to pH=7, filter, solid product is dry at 70 DEG C, obtains pale yellow powder product SCMHPG;
R=OH, n=1 in this structure.
The mensuration of product property index:
(1) molecular weight determination:
Adopt the system combined multi-angle laser light scattering apparatus of gel chromatography, moving phase: 0.1N NaNO
3the aqueous solution, PLaquagelOH series gel column is separator column, and sample concentration is 0.70 ‰, measures molecular weight of product;
(2) surface and interface tension detection:
K100C full-automatic surface tension instrument chart interfacial tension;
(3) dynamically performance is injured:
Coal dust is broken, and cross 100 mesh sieves, take 30g coal dust and load in core holding unit, at 6MPa pressure 10min, for subsequent use, survey rate of permeation with 2%KCl, breaking glue solution injures;
(4) viscosity affects change detection by salinity: investigate the present embodiment hydroxyl sulfopropyl substituted carboxymethyl hydroxypropylguar gum (0.6%) respectively in the viscosity situation of 0 ~ 0.5%NaCl and KCl, obtain the curve consistent with Fig. 1 variation tendency, illustrate that the hydroxyl sulfopropyl substituted carboxymethyl hydroxypropyl guar adhesive capacity of the present embodiment all affects by salinity very little.
Product performance measurement result:
(1) product number-average molecular weight: 1,650,000;
(2) sulfonic group substitution value: 0.18;
(3) apparent viscosity (0.6%): 97.9mPas;
(4) product configuration is become massfraction be 0.12% the aqueous solution, viscosity: 12mPa.s;
(4.1) crosslinked rear viscosity: 134mPa.s;
(4.2) static filtration performance static filtration performance:
Leakoff coefficent
static spurt loss volume Qsp=2.67 × 10
-3m
3/ m
2, fluid loss rate V=2.16 × 10
-4m/min;
(4.3) the injury rate in coal seam: 21.0%;
(4.4) surface tension: 27.54mN/m, interfacial tension: 2.05mN/m;
(4.5) broken glue under ammonium persulphate (0.5 ‰)-S-WAT (0.5 ‰) exists, level of residue: 53.0mg/L after broken glue, viscosity: 1.70mPa.s.
Embodiment 4:
A preparation method for organic sulfonic acid modified carboxy methyl hydroxypropylguar gum, step is as follows:
(1) in the reactor that 3L65% ethanolic soln is housed, 1000.0g Carboxymethyl hydroxypropyl guar (degree of substitution by carboxymethyl is 0.15, hydroxypropyl substitution value 0.32) is added;
(2) under nitrogen atmosphere, drip 40% aqueous sodium hydroxide solution 325g, stir and be warmed up to 65 ~ 70 DEG C after 0.5 hour, stir 0.5 hour, drip vinyl sulfonic acid 360g, constant temperature 70 DEG C, dropwises for 2 hours, continues stirring 4 hours;
(3) use hydrochloric acid neutralization reaction liquid to pH=7, filter, solid product is dry at 70 DEG C, obtains pale yellow powder product SCMHPG;
R=H, n=0 in this structure.
The mensuration of product property index:
(1) molecular weight determination:
Adopt the system combined multi-angle laser light scattering apparatus of gel chromatography, moving phase: 0.1N NaNO
3the aqueous solution, PLaquagelOH series gel column is separator column, and sample concentration is 0.70 ‰, measures molecular weight of product;
(2) surface and interface tension detection:
K100C full-automatic surface tension instrument chart interfacial tension;
(3) dynamically performance measurement is injured:
Coal dust is broken, and cross 100 mesh sieves, take 30g coal dust and load in core holding unit, at 6MPa pressure 10min, for subsequent use, survey rate of permeation with 2%KCl, breaking glue solution injures;
(4) viscosity affects change detection by salinity: investigate the present embodiment sulfoethyl substituted carboxymethyl hydroxypropylguar gum (0.6%) respectively in the viscosity situation of 0 ~ 0.5%NaCl and KCl, obtain the curve consistent with Fig. 1 variation tendency, illustrate that the sulfoethyl substituted carboxymethyl hydroxypropyl guar adhesive capacity of the present embodiment all affects by salinity very little.
Product performance measurement result:
(1) product number-average molecular weight: 1,640,000;
(2) sulfonic group substitution value: 0.25;
(3) apparent viscosity (0.6%): 105.3mPas;
(4) product configuration is become massfraction be 0.12% the aqueous solution, viscosity: 10.5mPas;
(4.1) crosslinked rear viscosity: 36mPa.s;
The product of this example, because sulfonic group substitution value is higher, its cross-linking properties is deteriorated, and crosslinked gel performance can not meet actual pressing crack construction requirement.
Claims (14)
1. a sulfonic acid modified Carboxymethyl hydroxypropyl guar, is characterized in that, its structural formula is as follows:
Wherein, R=H, n=0,1,2 or 3; Or, R=OH, n=0 ~ 6; The molecular weight of this sulfonic acid modified Carboxymethyl hydroxypropyl guar is 160 ~ 2,000,000; Wherein sulfonic group substitution value is 0.01 ~ 0.18, and degree of substitution by carboxymethyl is 0.12 ~ 0.25, hydroxypropyl substitution value 0.15 ~ 0.4.
2. the preparation method of sulfonic acid modified Carboxymethyl hydroxypropyl guar according to claim 1, it is characterized in that, the method comprises the steps:
(1) Carboxymethyl hydroxypropyl guar is added reaction vessel, add the aqueous solution of alcohol, stirring and dissolving;
(2) under nitrogen atmosphere, drip aqueous sodium hydroxide solution, stir and be warmed up to 65 ~ 80 DEG C, drip sulphonating agent, react 3 ~ 10 hours;
(3) be then cooled to 30 ~ 40 DEG C, be adjusted to pH value of solution=7 with acid, filter, collect solid drying, obtain pale yellow powder, be described sulfonic acid modified Carboxymethyl hydroxypropyl guar.
3. method according to claim 2, is characterized in that: described alcohol is ethanol or Virahol.
4. method according to claim 2, is characterized in that: the concentration of the aqueous solution of described alcohol is mass percent 50% ~ 80%, and weight consumption is 5 ~ 8 times of Carboxymethyl hydroxypropyl guar weight; Described aqueous sodium hydroxide solution concentration is 10% ~ 30%.
5. method according to claim 4, is characterized in that: described aqueous sodium hydroxide solution concentration is 15%.
6. method according to claim 2, is characterized in that: described sulphonating agent is vinyl sulfonic acid or 3-chlorine-2-hydroxyl propanesulfonate.
7. method according to claim 2, is characterized in that: drip aqueous sodium hydroxide solution for dripping 0.5h.
8. method according to claim 2, is characterized in that: wherein stir and be warmed up to 70 DEG C.
9. method according to claim 2, is characterized in that: dripping sulphonating agent is dropping 0.5 ~ 2h.
10. method according to claim 2, is characterized in that: wherein react 3 hours.
11. methods according to claim 2, is characterized in that: when described sulphonating agent is vinyl sulfonic acid, and the mass ratio of vinyl sulfonic acid: Carboxymethyl hydroxypropyl guar: NaOH is (2-45): 200:(1.5-35);
When described sulphonating agent is 3-chlorine-2-hydroxyl propanesulfonate, 3-chlorine-2-hydroxyl propanesulfonate: the mass ratio of Carboxymethyl hydroxypropyl guar: NaOH is (4-80): 200:(1.5-35).
12. sulfonic acid modified Carboxymethyl hydroxypropyl guar according to claim 1 are preparing the application in fracturing liquid.
13. 1 kinds of fracturing liquids, is characterized in that, comprise sulfonic acid modified Carboxymethyl hydroxypropyl guar according to claim 1 in this fracturing liquid.
14. fracturing liquids according to claim 13, is characterized in that, the concentration of described sulfonic acid modified Carboxymethyl hydroxypropyl guar in fracturing liquid is mass percent 0.1% ~ 0.3%.
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| CN105061624B (en) * | 2015-08-11 | 2018-03-20 | 陕西延长石油(集团)有限责任公司研究院 | A kind of modified guar gum and preparation method thereof |
| 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 |
| CN112341035B (en) * | 2020-09-24 | 2022-02-11 | 鹤壁宝来化工科技有限公司 | Concrete rheology regulator and preparation method thereof |
| CN115838443B (en) * | 2022-11-22 | 2024-03-22 | 南通昕源生物科技有限公司 | Sulfonated guar gum ether and preparation method and application thereof |
| CN116655828A (en) * | 2023-04-04 | 2023-08-29 | 胜利油田凯渡石油技术开发有限公司 | Modified guar gum for fracturing and preparation method thereof |
| CN117264088B (en) * | 2023-11-17 | 2024-02-06 | 东营市宝泽能源科技有限公司 | Instant guar gum and synthetic method and application thereof |
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| CN101475668A (en) * | 2008-12-25 | 2009-07-08 | 刘东辉 | Guar gum derivative containing sulfonic group, and preparation and use 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 |
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| WO2011055038A1 (en) * | 2009-11-05 | 2011-05-12 | IFP Energies Nouvelles | Injection fluid and assisted petroleum recovery method |
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| DE2652395A1 (en) * | 1975-11-17 | 1977-05-18 | Celanese Corp | POLYGALACTOMANNANAETHER AND PROCESS FOR THEIR PRODUCTION |
| CN101475668A (en) * | 2008-12-25 | 2009-07-08 | 刘东辉 | Guar gum derivative containing sulfonic group, and preparation and use 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 |
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