CN113087817B - Guar gum derivative and preparation method and application thereof - Google Patents

Guar gum derivative and preparation method and application thereof Download PDF

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CN113087817B
CN113087817B CN202110562094.1A CN202110562094A CN113087817B CN 113087817 B CN113087817 B CN 113087817B CN 202110562094 A CN202110562094 A CN 202110562094A CN 113087817 B CN113087817 B CN 113087817B
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guar gum
etherifying agent
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CN113087817A (en
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李博
彭树华
邓明宇
陈家宝
陆伟
孙雪莲
谢文龙
王军民
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Kunshan Jingkun Oilfield Chemical Technology Co ltd
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    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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Abstract

The invention provides a guar gum derivative and a preparation method and application thereof, belonging to the technical field of petroleum fracturing. The invention provides a guar gum derivative, which contains hydroxyalkyl and dicarboxyl structural groups, wherein the hydroxyalkyl and the dicarboxyl structural groups can respectively appear at the 2, 3 and 6 positions in mannose and the 2, 3, 4 and 6 positions in galactose, and the dicarboxyl groups are introduced, so that the crosslinkable site density is higher, the crosslinking strength is higher, and the hydroxyalkyl and the dicarboxyl structural groups act together, so that the guar gum derivative not only has the excellent performances of quick tackifying and shearing resistance, but also can generate a higher-density crosslinking network with a zirconium and aluminum crosslinking agent under the condition of low concentration, so that jelly is more stable, and the crosslinking strength is higher.

Description

Guar gum derivative and preparation method and application thereof
Technical Field
The invention relates to the technical field of petroleum fracturing, in particular to a guar gum derivative and a preparation method and application thereof.
Background
Water-based fracturing fluids have been widely used in the oil and gas industry for their low cost, good performance and ease of handling. The main work in the research of water-based fracturing fluids is to develop and prefer thickeners and crosslinking agents, wherein the research of thickeners is a core project. The thickening agent is a main functional agent in the water-based fracturing fluid, the performance of the thickening agent directly influences the performance of the water-based fracturing fluid, the thickening agent of the water-based fracturing fluid which is widely applied at present is still guar gum and derivatives thereof, and the structural formula of the guar gum is shown as the following formula:
Figure BDA0003079369120000011
the existing water-based fracturing fluid thickening agent using guar gum and derivatives thereof has the problem of low crosslinking strength.
Disclosure of Invention
In view of the above, the present invention aims to provide a guar gum derivative, and a preparation method and an application thereof. The guar gum derivative prepared by the invention has high crosslinking strength.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a guar gum derivative, which has a structure shown in a formula I:
Figure BDA0003079369120000021
wherein R is H,
Figure BDA0003079369120000022
R1H or C1-C5 alkyl; r2，R3Independently C1-C5 alkyl, wherein R is a connecting site;
the weight average molecular weight of the guar gum derivative is 1-500 ten thousand.
Preferably, the substitution degree of hydroxyalkyl in the guar gum derivative is 0.1-0.3, and the substitution degree of dicarboxyl alkyl is 0.01-0.5.
The invention also provides a preparation method of the guar gum derivative, which comprises the following steps:
mixing guar gum, borax and a solvent, and then mixing the mixture with an alkaline reagent under a protective atmosphere for alkalization to obtain a guar gum suspension;
carrying out two-step etherification reaction on the guar gum suspension, a first etherifying agent and a second etherifying agent to obtain the guar gum derivative, wherein the first etherifying agent is C1-C5 alkylene oxide, and the second etherifying agent is halogenated dicarboxylic acid sodium salt or halogenated dicarboxylic acid ester; the order of the etherification reaction of the first etherifying agent and the second etherifying agent is not limited.
Preferably, the solvent is water, alcohol or an alcohol water system.
Preferably, the alkaline reagent is an organic base or an inorganic base, and the feeding mass of the alkaline reagent is 0.1-5 times of the mass of the guar gum.
Preferably, the organic base is triethanolamine and the inorganic base is sodium hydroxide, potassium hydroxide or potassium carbonate.
Preferably, the alkalization time is 0.1-2 h.
Preferably, the temperature of the etherification reaction of the first etherifying agent is 30-80 ℃ and the time is 0.1-5 h.
Preferably, the temperature of the second etherifying agent for etherification is 10-50 ℃ and the time is 0.1-3 h.
The invention also provides the application of the guar gum derivative in the technical scheme or the guar gum derivative prepared by the preparation method in the technical scheme as a crosslinking thickener for fracturing in the field of petroleum fracturing.
The invention provides a guar gum derivative, which contains hydroxyalkyl and dicarboxyl structural groups, wherein the hydroxyalkyl and the dicarboxyl structural groups can respectively appear at the 2, 3 and 6 positions in mannose and the 2, 3, 4 and 6 positions in galactose, and the dicarboxyl groups are introduced, so that the crosslinkable site density is higher, the crosslinking strength is higher, and the hydroxyalkyl and the dicarboxyl structural groups act together, so that the guar gum derivative not only has the excellent performances of quick tackifying and shearing resistance, but also can generate a higher-density crosslinking network with a zirconium and aluminum crosslinking agent under the condition of low concentration, so that jelly is more stable, and the crosslinking strength is higher.
The invention also provides a preparation method of the guar gum derivative in the technical scheme, the preparation method is simple to operate, and the guar gum derivative can be obtained by carrying out two-step etherification reaction.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the guar derivative prepared in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of the guar derivative prepared in example 2;
FIG. 3 is a rheological curve of guar gum derivatives prepared in comparative examples 1-2 and example 1;
fig. 4 is a rheological curve of the guar derivatives obtained in comparative example 2 and example 2;
FIG. 5 is a graph showing the change in viscosity of the aqueous solutions of the guar derivatives prepared in comparative examples 1 to 2 and example 1;
fig. 6 is a plot of the elastic modulus of guar derivatives prepared in comparative example 2 and example 2, as measured by frequency sweep.
Detailed Description
The invention provides a guar gum derivative, which has a structure shown in a formula I:
Figure BDA0003079369120000031
wherein R is H,
Figure BDA0003079369120000041
R1H or C1-C5 alkyl; r2，R3Independently C1-C5 alkyl, wherein R is a connecting site;
the weight average molecular weight of the guar gum derivative is 1-500 ten thousand.
In the present invention, the structural formula of the guar gum derivative is preferably represented by formula II:
Figure BDA0003079369120000042
in the formula II, R is H,
Figure BDA0003079369120000043
The weight average molecular weight of the guar gum derivative with the structure shown in the formula II is preferably 332 ten thousand or 315 ten thousand.
In the invention, the degree of substitution of hydroxyalkyl in the guar gum derivative is preferably 0.1-0.5, and the degree of substitution of dicarboxyl is preferably 0.05-0.5.
The invention also provides a preparation method of the guar gum derivative, which comprises the following steps:
mixing guar gum, borax and a solvent, and then mixing the mixture with an alkaline reagent under a protective atmosphere for alkalization to obtain a guar gum suspension;
carrying out two-step etherification reaction on the guar gum suspension, a first etherifying agent and a second etherifying agent to obtain the guar gum derivative, wherein the first etherifying agent is C1-C5 alkylene oxide, and the second etherifying agent is halogenated dicarboxylic acid sodium salt or halogenated dicarboxylic acid ester; the order of the etherification reaction of the first etherifying agent and the second etherifying agent is not limited.
According to the invention, guar gum, borax and a solvent are mixed and then mixed with an alkaline reagent under a protective atmosphere for alkalization, so as to obtain a guar gum suspension.
In the present invention, the solvent is preferably water, alcohol or an alcohol-water system, the alcohol is preferably ethanol, tert-butanol or isopropanol, and the volume ratio of the alcohol to the water in the alcohol-water system is not particularly limited in the present invention, and may be any volume ratio known to those skilled in the art.
In the invention, the borax is used for washing the reaction product with water.
In the invention, the mass ratio of the guar gum to the borax is preferably 100: 1.5.
In the invention, the alkaline reagent is preferably an organic base or an inorganic base, and the feeding mass of the alkaline reagent is preferably 0.1-5 times of the mass of guar gum.
In the present invention, the organic base is preferably triethanolamine, and the inorganic base is preferably sodium hydroxide, potassium hydroxide, or potassium carbonate. In the invention, the inorganic base is preferably added in the form of an inorganic base aqueous solution, the concentration and the dosage of the inorganic base aqueous solution are not particularly limited, and the feeding quality of the alkaline reagent can be ensured to be 0.1-5 times of the quality of the guar gum.
In the invention, the alkalization time is preferably 0.1-2 h, and more preferably 0.5-1.5 h.
In the present invention, the alkaline agent is preferably added dropwise to the resulting mixed system, and in a specific embodiment of the present invention, the time of the dropwise addition is preferably 30 min.
After obtaining the guar gum suspension, carrying out two-step etherification reaction on the guar gum suspension, a first etherifying agent and a second etherifying agent to obtain the guar gum derivative, wherein the first etherifying agent is C1-C5 alkylene oxide, and the second etherifying agent is halogenated dicarboxylic acid sodium salt or halogenated dicarboxylic acid ester; the order of the etherification reaction of the first etherifying agent and the second etherifying agent is not limited.
In the present invention, the structural formula of the second etherifying agent is preferably as shown in formula III:
Figure BDA0003079369120000051
x is halogen, R2，R3Independently is C1-C5 alkyl.
In the present invention, the sequence of the two etherification reactions is preferably that the etherification reaction is performed with the first etherifying agent first, and then the etherification reaction is performed with the second etherifying agent.
In the invention, the temperature of the first etherifying agent for the etherification reaction is preferably 30-80 ℃, more preferably 40-70 ℃, and the time is preferably 0.1-5 h.
In the invention, the molar ratio of the first etherifying agent to the guar gum is preferably 0.1-2: 1.
In the present invention, the first etherifying agent is preferably added dropwise to the reaction system.
After the first etherification reaction of the first etherifying agent is completed, the reaction intermediate is preferably obtained by sequentially carrying out suction filtration washing, suction filtration alcohol-water washing and drying on the obtained product. In the present invention, the number of times of the suction filtration water washing is preferably one, and the number of times of the suction filtration alcohol water washing is preferably two.
The present invention is not particularly limited to the specific manner of drying, and may be performed in a manner known to those skilled in the art.
After a reaction intermediate is obtained, the reaction intermediate, a second etherifying agent, borax and a solvent are mixed, and then mixed with an alkaline reagent under a protective atmosphere to perform a second etherification reaction, so that the guar gum derivative is obtained.
In the invention, the molar ratio of the second etherifying agent to the guar gum is preferably 0.1-1: 1.
In the invention, the temperature of the second etherifying agent for the etherification reaction is preferably 10-50 ℃, and the time is preferably 0.1-3 h.
In the present invention, the mass ratio of the first etherification product to borax is preferably 50: 0.8.
In the present invention, the kinds of the solvent and the alkaline agent are preferably the same as those in the above-mentioned embodiment, and are not described herein again.
In the present invention, the basic agent is preferably added dropwise at the time of the second etherification reaction, and the time of the dropwise addition is preferably 1 hour.
After the second etherification reaction is completed, the obtained second etherification product is preferably subjected to suction filtration water washing, suction filtration alcohol water washing and drying in sequence to obtain the guar gum derivative.
In the present invention, the number of times of the suction filtration water washing is preferably one, and the number of times of the suction filtration alcohol water washing is preferably two.
The present invention is not particularly limited to the specific manner of drying, and may be performed in a manner known to those skilled in the art.
The invention also provides the application of the guar gum derivative in the technical scheme or the guar gum derivative prepared by the preparation method in the technical scheme as a crosslinking thickener for fracturing in the field of petroleum fracturing.
In order to further illustrate the present invention, the guar derivatives provided by the present invention, as well as the preparation and use thereof, are described in detail below with reference to examples, which should not be construed as limiting the scope of the present invention.
Comparative example 1
Adding 100g of guar gum, 1.5g of borax and 200g of isopropanol into a three-neck flask, introducing nitrogen at room temperature, stirring for 30min, dropwise adding 35g of 50 wt% sodium hydroxide solution under the protection of nitrogen, dropwise adding for 30min, directly heating to 70 ℃ after dropwise addition, dropwise adding 10g of propylene oxide, stirring for reaction for 2h, discharging, performing suction filtration and washing once, washing alcohol water (mixed solution of ethanol and water in a volume ratio of 3: 7) twice, drying to obtain a reaction intermediate, adding 50g of the reaction intermediate, 23g of sodium chloroacetate and 0.8g of borax into the three-neck flask, pouring 100g of isopropanol, introducing nitrogen, stirring and dispersing for 30min to uniformly mix, heating to 50 ℃, dropwise adding 20g of 50 wt% sodium hydroxide solution under the protection of nitrogen, dropwise adding for 1h, after the dropwise addition, reacting for 1h, discharging, performing suction filtration and washing once, performing alcohol water washing twice, drying, the guar derivative is obtained and is marked as A for standby.
Comparative example 2
Adding 100g of guar gum, 1.5g of borax and 200g of isopropanol into a three-neck flask, introducing nitrogen at room temperature, stirring for 30min, dropwise adding 35g of 50 wt% sodium hydroxide solution under the protection of nitrogen, dropwise adding for 30min, directly heating to 70 ℃ after dropwise addition, dropwise adding 10g of propylene oxide, stirring for reaction for 2h, discharging, performing suction filtration and washing once, washing alcohol water (mixed solution of ethanol and water in a volume ratio of 3: 7) twice, drying to obtain a reaction intermediate, adding 50g of the reaction intermediate, 12g of sodium chloroacetate and 0.8g of borax into the three-neck flask, pouring 100g of isopropanol, introducing nitrogen, stirring and dispersing for 30min to uniformly mix, heating to 50 ℃, dropwise adding 20g of 50 wt% sodium hydroxide solution under the protection of nitrogen, dropwise adding for 1h, reacting for 1h, then discharging, performing suction filtration and washing once, performing alcohol water washing and drying twice, the guar derivative is obtained and is marked as B for standby.
Example 1
Adding 100g of guar gum, 1.5g of borax and 200g of isopropanol into a three-neck flask, introducing nitrogen gas at room temperature, stirring for 30min, dropwise adding 35g of 50 wt% sodium hydroxide solution under the protection of nitrogen gas, dropwise adding for 30min, directly heating to 70 ℃ after dropwise addition, dropwise adding 10g of propylene oxide, stirring for reaction for 2h, discharging, carrying out suction filtration and washing once, washing with alcohol water twice, drying to obtain a reaction intermediate, adding 50g of reaction intermediate, 45g of sodium chloromalonate and 0.8g of borax into the three-neck flask, pouring 100g of isopropanol, introducing nitrogen gas, stirring and dispersing for 30min, uniformly mixing, heating to 50 ℃, under the protection of nitrogen gas, dropwise adding 30g of 50 wt% sodium hydroxide solution slowly dropping for 1h, reacting for 1h after dropwise addition, discharging, carrying out suction filtration and washing once, washing with alcohol water twice, drying to obtain a guar gum derivative, and marking as C, and (5) standby.
The nuclear magnetic hydrogen spectrum obtained by performing nuclear magnetic characterization on the guar gum derivative obtained in this example is shown in fig. 1, and it can be known that the structural formula of the guar gum derivative obtained in this example is shown in the following formula:
Figure BDA0003079369120000081
wherein R is H,
Figure BDA0003079369120000082
The guar gum derivative obtained in example 1 was tested to have a weight average molecular weight of 332 ten thousand.
Example 2
Adding 100g of guar gum, 1.5g of borax and 200g of isopropanol into a three-neck flask, introducing nitrogen gas at room temperature, stirring for 30min, dropwise adding 35g of 50 wt% sodium hydroxide solution under the protection of nitrogen gas, dropwise adding for 30min, directly heating to 70 ℃ after dropwise addition, dropwise adding 10g of propylene oxide, stirring for reaction for 2h, discharging, carrying out suction filtration and washing once, washing with alcohol water twice, drying to obtain a reaction intermediate, adding 50g of reaction intermediate, 28g of sodium chloromalonate and 0.8g of borax into the three-neck flask, pouring 100g of isopropanol, introducing nitrogen gas, stirring and dispersing for 30min to uniformly mix, heating to 50 ℃, under the protection of nitrogen gas, dropwise adding 20g of 50 wt% sodium hydroxide solution, slowly dropping for 1h, reacting for 1h after dropwise addition, discharging, carrying out suction filtration and washing once, washing with alcohol water twice, drying to obtain a guar gum derivative, and recording as D, and (5) standby.
The nuclear magnetic hydrogen spectrum obtained by performing nuclear magnetic characterization on the guar gum derivative obtained in this example is shown in fig. 2, and it can be known that the structural formula of the guar gum derivative obtained in this example is shown in the following formula:
Figure BDA0003079369120000091
wherein R is H,
Figure BDA0003079369120000092
The guar gum derivative obtained in example 2 was tested to have a weight average molecular weight of 315 ten thousand.
A is hydroxypropyl carboxymethyl guar gum with a degree of substitution DS (hydroxypropyl) of 0.2 and DS (carboxymethyl) of 0.4; b is hydroxypropyl carboxymethyl guar gum with degree of substitution DS (hydroxypropyl) 0.2, DS (carboxymethyl) 0.2; c is hydroxypropyl dicarboxyl guar gum with degree of substitution DS (hydroxypropyl) 0.2, DS (dicarboxyl) 0.2; d is hydroxypropyl dicarboxyl guar with a degree of substitution DS (hydroxypropyl) 0.2 and DS (dicarboxyl) 0.1.
Preparing A into 0.4% aqueous solution (mass concentration), B into 0.4% aqueous solution (mass concentration), C into 0.4% aqueous solution (mass concentration), and D into 0.2% aqueous solution (mass concentration). And (3) respectively adjusting the pH value of the A, B, C, D aqueous solution to 4 by using dilute sulfuric acid to respectively obtain an A guar gum aqueous solution, a B guar gum aqueous solution, a C guar gum aqueous solution and a D guar gum aqueous solution.
And (3) taking 100g of the guar gum water solution, adding 1.0mL of organic zirconium crosslinking agent, quickly stirring, and testing viscosity change by using a rheometer.
FIG. 3 is a graph of the rheology curves of guar derivatives prepared in comparative examples 1-2 and example 1, illustrated at 170s-1At a shear rate of 90 ℃ for 1h, the guar derivatives prepared in example 1 have the highest final shear viscosity, and the guar derivatives prepared according to the invention are more resistant to shear than A and B under the same conditions.
FIG. 4 is a rheological curve of the guar derivatives obtained in comparative example 2 and in example 2, illustrated at 170s-1Guar derivative pairs prepared in example 2 at a shear rate of 90 ℃ for 1hThe final shear viscosity is highest, and the guar gum derivative prepared by the invention is more resistant to shear compared with B under the same conditions.
2.0g of solid A, B and C were mixed with 200g of water, respectively, and dispersed by magnetic stirring. The viscosity values of the aqueous solutions corresponding to different time points are tested by using a Brookfield viscometer, different curves are recorded, and as shown in figure 5, the viscosity of A and B still does not reach the peak value after stirring for 10min, and the viscosity of C4min already reaches the peak value, the guar gum derivative prepared by the invention has a faster viscosity release rate compared with A and B under the same conditions.
Fig. 6 is a plot of the elastic modulus of the guar derivatives prepared in comparative example 2 and example 2, and the rheometer tests the elastic modulus G 'in frequency sweep mode, comparing B and D, it can be seen that the G' of the high frequency zone sample D is higher than B, indicating that the guar derivatives provided by the present invention have high crosslinking strength.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (9)

1. A guar derivative having the structure of formula I:
Figure FDA0003510030920000011
wherein R is H,
Figure FDA0003510030920000012
R is a ligation site;
the weight average molecular weight of the guar gum derivative is 1-500 ten thousand; the substitution degree of hydroxyalkyl in the guar gum derivative is 0.1-0.3, and the substitution degree of dicarboxyl alkyl is 0.01-0.5.
2. The process for the preparation of guar derivatives according to claim 1, characterized in that it comprises the following steps:
mixing guar gum, borax and a solvent, and then mixing the mixture with an alkaline reagent under a protective atmosphere for alkalization to obtain a guar gum suspension;
carrying out two-step etherification reaction on the guar gum suspension, a first etherifying agent and a second etherifying agent to obtain the guar gum derivative, wherein the first etherifying agent is propylene oxide, and the second etherifying agent is sodium chloromalonate; the order of the etherification reaction of the first etherifying agent and the second etherifying agent is not limited.
3. The method of claim 2, wherein the solvent is water, alcohol, or an alcohol water system.
4. The preparation method according to claim 2, wherein the alkaline agent is an organic base or an inorganic base, and the mass of the alkaline agent is 0.1 to 5 times of the mass of the guar gum.
5. The method according to claim 4, wherein the organic base is triethanolamine and the inorganic base is sodium hydroxide, potassium hydroxide or potassium carbonate.
6. The preparation method according to claim 2 or 4, wherein the alkalization time is 0.1-2 h.
7. The preparation method according to claim 2, wherein the temperature of the first etherifying agent for the etherification reaction is 30 to 80 ℃ and the time is 0.1 to 5 hours.
8. The preparation method according to claim 2, wherein the second etherifying agent is used for etherification at a temperature of 10 to 50 ℃ for 0.1 to 3 hours.
9. Application of the guar gum derivative according to claim 1 or the guar gum derivative prepared by the preparation method according to any one of claims 2 to 8 as a crosslinking thickener for fracturing in the field of petroleum fracturing.
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