CN113322057B - Adsorption inhibitor, preparation method and application thereof - Google Patents

Adsorption inhibitor, preparation method and application thereof Download PDF

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CN113322057B
CN113322057B CN202010126769.3A CN202010126769A CN113322057B CN 113322057 B CN113322057 B CN 113322057B CN 202010126769 A CN202010126769 A CN 202010126769A CN 113322057 B CN113322057 B CN 113322057B
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dimethoxybenzene
dimethylaminodydroxybenzene
dimethylamino
dimethylaminodimethoxybenzene
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CN113322057A (en
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林永茂
潘宝风
王世彬
兰林
谭佳
詹斌
杨东梅
刘徐慧
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China Petroleum and Chemical Corp
Sinopec Southwest Oil and Gas Co
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Abstract

The invention provides an adsorption inhibitor, a preparation method and application thereof. The structural formula of the adsorption inhibitor is shown as formula I:
Figure DDA0002394632140000011
wherein, the silicon dioxide is nano silicon dioxide particles, n is an integer which is greater than or equal to 0, and m is a natural number which is greater than or equal to 1.

Description

Adsorption inhibitor, preparation method and application thereof
Technical Field
The invention provides an adsorption inhibitor, in particular to a preparation method and application thereof.
Background
At present, most of fracturing fluids used in oil and gas field fracturing modification are fracturing fluids taking guar gum and derivatives thereof (such as hydroxypropyl guar gum) as thickening agents and boron organic matters or inorganic matters as cross-linking agents, and have good fracture-making and sand-carrying functions. However, the fracturing liquid system has some defects, and the fracturing modification effect is influenced to a certain extent. For example, the characteristics of guar gum and its modified products determine that a fracturing fluid system using guar gum as a thickening agent can only be crosslinked under alkaline conditions, the pH value is high (about 9), clay minerals in a reservoir are easy to swell during fracturing construction, and the fracturing fluid meets original ions in a stratum and has potential stratum damage. After the fracturing fluid is injected into the stratum, along the flow channel of the fracturing fluid, adsorption and retention effects exist between guar gum in the fracturing fluid and stratum rock, and part of guar gum is adsorbed on the surface of the rock, so that the concentration of guar gum in the fracturing fluid is reduced, and further, the concentration of guar gum in the return fluid is also obviously reduced. The adsorbed and retained guar gum cannot drain out of the formation along with the flowback fluid, so that the guar gum retained in the formation can cause damage to the reservoir. Moreover, due to the adsorption effect between the guar gum and the rock, the amount of the guar gum in the fracturing fluid is increased, and the economic cost is increased.
Disclosure of Invention
The invention provides an adsorption inhibitor, which has a structural formula shown in formula I:
Figure BDA0002394632120000011
wherein, the silicon dioxide is nano silicon dioxide particles, n is an integer which is greater than or equal to 0, and m is a natural number which is greater than or equal to 1.
In one embodiment, the nanosilica particles have a particle size of 2 to 10 nm.
The second aspect of the present invention provides a method for preparing the adsorption inhibitor as described in the first aspect of the present invention, which comprises the steps of: and reacting the hydroxylation modified nano silicon dioxide with dimethylamino dihydroxybenzene to obtain the adsorption inhibitor.
In one embodiment, the dimethylaminodydroxybenzene is 1, 4-dimethylamino-2, 5-dihydroxybenzene.
In one embodiment, the hydroxylated modified nanosilica is reacted with the dimethylaminodydroxybenzene in water at 40 to 80 ℃ for 4 to 6 hours to provide the adsorption inhibitor.
In one embodiment, the nanosilica particles have a particle size of 2 to 10nm before modification.
In one embodiment, the mass ratio of the hydroxylated modified nanosilica to the dimethylaminodydroxybenzene is 1: 0.6 to 1: 1.
In one embodiment, the hydroxylation-modified nanosilica is prepared by: the nano-silicon dioxide is reacted in concentrated sulfuric acid at 120 to 150 ℃ for 10 to 12 hours.
In a specific embodiment, the concentration of the concentrated sulfuric acid is 70% to 98%, and the mass ratio of the concentrated sulfuric acid to the nano-silica is 1: (0.01-0.1).
In one embodiment, dimethylaminodydroxybenzene is hydrolyzed with a base to provide the dimethylaminodydroxybenzene.
In one embodiment, the dimethylaminodydroxybenzene is 1, 4-dimethylamido-2, 5-dihydroxybenzene.
In one embodiment, the base is sodium hydroxide and/or potassium hydroxide.
In a specific embodiment, the mass ratio of the dimethylaminodydroxybenzene to the base is from 2:1 to 4: 1.
In one embodiment, the dimethylaminodydroxybenzene is hydrolyzed under the action of a base at 60 to 80 ℃ for 2 to 4 hours to obtain the dimethylaminodydroxybenzene.
In one embodiment, dimethylaminodimethoxybenzene is reacted with butyllithium to provide the dimethylaminodimethoxybenzene.
In one embodiment, the dimethylaminodimethoxybenzene is 1, 4-dimethylamido-2, 5-dimethoxybenzene and the dimethylaminodimethoxybenzene is 1, 4-dimethylamido-2, 5-dihydroxybenzene.
In a specific embodiment, the butyllithium is n-butyllithium.
In a specific embodiment, the molar ratio of dimethylaminodimethoxybenzene to butyllithium is 1: 1.5 to 1: 3.
in one embodiment, the dimethylaminodimethoxybenzene and the butyllithium are reacted in chloroform at 0 to 5 ℃ for 1 to 3 hours to provide the dimethylaminodimethoxybenzene.
In one embodiment, dimethylaminodimethoxybenzene is reacted with formic acid in ethanol at 50 to 70 ℃ for 2 to 3 hours to form dimethylaminodimethoxybenzene.
In one embodiment, the dimethylaminodimethoxybenzene is 1, 4-dimethylamino-2, 5-dimethoxybenzene and the dimethylaminodimethoxybenzene is 1, 4-dimethylaminod-2, 5-dimethoxybenzene.
In one embodiment, the molar ratio of the dimethylamino dimethoxybenzene to the formic acid is 1: 2 to 1: 4.
in one embodiment, the dimethylnitrile dimethoxybenzene and lithium aluminum hydride are reacted in diethyl ether at 20 to 40 ℃ for 2 to 5 hours to obtain dimethylamino dimethoxybenzene.
In one embodiment, the dicyanodimethoxybenzene is 1, 4-dicyanodi-2, 5-dimethoxybenzene and the dimethylaminododimethoxybenzene is 1, 4-dimethylamino-2, 5-dimethoxybenzene.
In one embodiment, the molar ratio of the dicyanobenzene to the lithium aluminum hydride is 1: 2.5 to 1: 3.5.
in one embodiment, dibromodimethoxybenzene is reacted with copper carbo-nitride in N-methylpyrrolidinone at 180 to 200 ℃ for 7 to 9 hours to give 1, 4-dicyano-2, 5-dimethoxybenzene.
In one embodiment, the dibromodimethoxybenzene is 1, 4-dibromo-2, 5-dimethoxybenzene and the dinitrile dimethoxybenzene is 1, 4-dinitrile-2, 5-dimethoxybenzene.
In one embodiment, the molar ratio of the dibromodimethoxybenzene to the copper carbonitride is 1: 0.9 to 1: 1.2.
the second invention provides the application of the adsorption inhibitor according to the first invention or the adsorption inhibitor prepared by the method according to the second invention in inhibiting guar gum from being adsorbed by formation rock.
In one embodiment, the adsorption inhibitor is present in the guar gum-containing fracturing fluid in an amount of 1 to 5g/L by mass.
The invention has the beneficial effects that:
the inhibitor is a nano material, has good solubility, can be attached to the surface of a rock along with the injection of fluid, and plays a role in inhibiting the guar gum from being retained and adsorbed on the rock, so that the adsorption retention of the guar gum on the surface of the rock is effectively reduced, and the permeability of the rock after modification is ensured; the adsorption inhibitor has high adsorption rate and efficiency in a rock porous medium, can completely cover the inner surface of a pore throat, and cannot cause additional reservoir damage.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of 1, 4-dimethylamino-2, 5-dihydroxybenzene.
FIG. 2 shows the mass spectrum of 1, 4-dimethylamino-2, 5-dihydroxybenzene.
Figure 3 shows a graph comparing the adsorption retention of a conventional guar fracturing fluid to a guar fracturing fluid supplemented with an adsorption inhibitor of the present invention on the surface of sandstone porous media.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary of the invention and are not to be construed as limiting the invention in any way.
Unless otherwise specified, the reagents used in the following examples are commercially available.
Example 1
Preparation of 1, 4-dicyan-2, 5-dimethoxybenzene
Into a flask was charged 25ml of N-methylpyrrolidone, and 2.96g of 1, 4-dibromo-2, 5-dimethoxybenzene and 0.99g of copper carbonate (molar ratio of 1, 4-dibromo-2, 5-dimethoxybenzene to copper carbonate: 1.1) were added under stirring, and heated to 190 ℃ to react for 8 hours, thereby obtaining 1, 4-dicyano-2, 5-dimethoxybenzene. The reaction equation is as follows:
Figure BDA0002394632120000041
the product was used in the next step without purification.
Example 2
Preparation of 1, 4-dicyan-2, 5-dimethoxybenzene
20ml of N-methylpyrrolidone was charged into a flask, and 2.96g of 1, 4-dibromo-2, 5-dimethoxybenzene and 1.08 carbon nitrogen copper (molar ratio of 1, 4-dibromo-2, 5-dimethoxybenzene to carbon nitrogen copper: 1: 1.2) were added under stirring, and heated to 180 ℃ to react for 7 hours, thereby obtaining 1, 4-dicyano-2, 5-dimethoxybenzene. The product was used in the next step without purification.
Example 3
Preparation of 1, 4-dicyan-2, 5-dimethoxybenzene
Into a flask was charged 18ml of N-methylpyrrolidone, and 2.96g of 1, 4-dibromo-2, 5-dimethoxybenzene and 0.81g of copper carbonate (molar ratio of 1, 4-dibromo-2, 5-dimethoxybenzene to copper carbonate: 1: 0.9) were added under stirring, and heated to 200 ℃ for reaction for 9 hours to obtain 1, 4-dicyano-2, 5-dimethoxybenzene. The product was used in the next step without purification.
Example 4
Preparation of 1, 4-dimethylamino-2, 5-dimethoxybenzene
50ml of diethyl ether was added to a beaker, and 1.88g of 1, 4-dicyano-2, 5-dimethoxybenzene and 0.95g of lithium aluminum hydride (molar ratio of 1, 4-dicyano-2, 5-dimethoxybenzene to lithium aluminum hydride is 1: 2.5) were added under stirring in a solvent of diethyl ether at 20 ℃ for 5 hours to obtain 1, 4-dimethylamino-2, 5-dimethoxybenzene. The reaction equation is as follows:
Figure BDA0002394632120000042
the product was used in the next step without purification.
Example 5
Preparation of 1, 4-dimethylamino-2, 5-dimethoxybenzene
50ml of diethyl ether was added to a beaker, and 1.88g of 1, 4-dicyanobenzene-2, 5-dimethoxybenzene and 1.14g of lithium aluminum hydride (molar ratio of 1, 4-dicyanobenzene-2, 5-dimethoxybenzene to lithium aluminum hydride was 1: 3) were added under stirring, and reacted at 30 ℃ for 4 hours to give 1, 4-dimethylamino-2, 5-dimethoxybenzene. The product was used in the next step without purification.
Example 6
Preparation of 1, 4-dimethylamino-2, 5-dimethoxybenzene
50ml of diethyl ether was added to a beaker, and 1.88g of 1, 4-dicyanobenzene-2, 5-dimethoxybenzene and 1.33g of lithium aluminum hydride (molar ratio of 1, 4-dicyanobenzene-2, 5-dimethoxybenzene to lithium aluminum hydride was 1: 3.5) were added under stirring, and reacted at 40 ℃ for 2 hours to give 1, 4-dimethylamino-2, 5-dimethoxybenzene. The product was used in the next step without purification.
Example 7
Preparation of 1, 4-dimethylamido-2, 5-dimethoxybenzene
50ml of diethyl ether is added into a beaker, 0.92g of formic acid is added under the stirring state, 1.96g of 1, 4-dimethylamino-2, 5-dimethoxybenzene (the molar ratio of the 1, 4-dimethylamino-2, 5-dimethoxybenzene to the formic acid is 1:2) is added after uniform stirring, the mixture is continuously stirred and reacts for 2 hours at 50 ℃, and 1, 4-dimethylamido-2, 5-dimethoxybenzene is generated. The reaction equation is as follows:
Figure BDA0002394632120000051
the product was used in the next step without purification.
Example 8
Preparation of 1, 4-dimethylamido-2, 5-dimethoxybenzene
50ml of diethyl ether is added into a beaker, 1.38g of formic acid is added under the stirring state, 1.96g of 1, 4-dimethylamino-2, 5-dimethoxybenzene (the molar ratio of the 1, 4-dimethylamino-2, 5-dimethoxybenzene to the formic acid is 1:3) is added after uniform stirring, the mixture is continuously stirred and reacts for 2.5 hours at the temperature of 60 ℃, and 1, 4-dimethylamido-2, 5-dimethoxybenzene is generated. The product was used in the next step without purification.
Example 9
Preparation of 1, 4-dimethylamido-2, 5-dimethoxybenzene
50ml of diethyl ether is added into a beaker, 1.52g of formic acid is added under the stirring state, 1.96g of 1, 4-dimethylamino-2, 5-dimethoxybenzene (the molar ratio of the 1, 4-dimethylamino-2, 5-dimethoxybenzene to the formic acid is 1:4) is added after uniform stirring, the mixture is continuously stirred and reacts for 3 hours at 70 ℃, and 1, 4-dimethylamido-2, 5-dimethoxybenzene is generated. The product was used in the next step without purification.
Example 10
Preparation of 1, 4-dimethylamido-2, 5-dihydroxybenzene
50ml of anhydrous chloroform is added into a beaker, the mixture is cooled to 0 ℃ by an ice water bath, 0.96g of n-butyllithium is slowly added, after the n-butyllithium is completely dispersed, 2.8g of 1, 4-dimethylamido-2, 5-dimethoxybenzene (the molar ratio of the 1, 4-dimethylamido-2, 5-dimethoxybenzene to the n-butyllithium is 1:1.5) is added, and the mixture is kept at 0 ℃ for reaction for 3 hours to generate 1, 4-dimethylamido-2, 5-dihydroxybenzene. The reaction equation is as follows:
Figure BDA0002394632120000061
the product was used in the next step without purification.
Example 11
Preparation of 1, 4-dimethylamido-2, 5-dihydroxybenzene
50ml of anhydrous chloroform was added to a beaker, and cooled to 2 ℃ in an ice-water bath, 1.28g of n-butyllithium was slowly added, and after the n-butyllithium was completely dispersed, 2.8g of 1, 4-dimethylamido-2, 5-dimethoxybenzene (molar ratio of 1, 4-dimethylamido-2, 5-dimethoxybenzene to n-butyllithium was 1:2) was added and reacted at 2 ℃ for 2 hours to produce 1, 4-dimethylamido-2, 5-dihydroxybenzene. The product was used in the next step without purification.
Example 12
Preparation of 1, 4-dimethylamido-2, 5-dihydroxybenzene
50ml of anhydrous chloroform was added to a beaker, and the mixture was cooled to 5 ℃ in an ice-water bath, and 1.92g of n-butyllithium was slowly added thereto, and after the n-butyllithium was completely dispersed, 2.8g of 1, 4-dimethylamido-2, 5-dimethoxybenzene (the molar ratio of 1, 4-dimethylamido-2, 5-dimethoxybenzene to n-butyllithium was 1:3) was added thereto, and the mixture was reacted at 5 ℃ for 1 hour to produce 1, 4-dimethylamido-2, 5-dihydroxybenzene. The product was used in the next step without purification.
Example 13
Preparation of 1, 4-dimethylamino-2, 5-dihydroxybenzene
2g of 1, 4-dimethylamido-2, 5-dihydroxybenzene and 0.5g of sodium hydroxide are hydrolyzed in 50ml of water at 60 ℃ for 2 hours to obtain 1, 4-dimethylamino-2, 5-dihydroxybenzene. The reaction equation is as follows:
Figure BDA0002394632120000071
the prepared product was recrystallized from ethanol, and the obtained pure product was subjected to nuclear magnetic resonance (see fig. 1) and mass spectrometry (see fig. 2).
As is clear from FIG. 1, the 4 absorption peaks delta are respectively 4.35ppm (b), 5.35ppm (d), 6.91ppm (a) and 8.68ppm (c) corresponding to the proton of benzene ring in 1, 4-dimethylamino-2, 5-dihydroxybenzene molecule, -CH2—，—NH2and-OH. As shown by comparison, 1, 4-dibromo-2, 5-dimethoxybenzene is used as an original raw material, and a target product 1, 4-dimethylamino-2, 5-dihydroxybenzene can be obtained through multi-step reaction.
As shown in FIG. 2, the molecular ion peaks of 1, 4-dimethylamino-2, 5-dihydroxybenzene were 168.1, [ M-CO ] 140.0]+(ii) a fragment ion peak of [ M-CHO ] 139.1]+The fragment ion peak of (2) is [ M- (CH) ]138.12＝NH2)+]Fragment ion peak of (1). From the analysis results of the molecular ion peak and the fragment ion peak, the target product 1, 4-dimethylamino-2, 5-dihydroxybenzene can be successfully synthesized by taking 1, 4-dibromo-2, 5-dimethoxybenzene as a raw material and carrying out multi-step reaction.
Both of the above fig. 1 and fig. 2 demonstrate that 1, 4-dibromo-2, 5-dimethoxybenzene is used as a raw material, and 1, 4-dimethylamino-2, 5-dihydroxybenzene can be synthesized by multi-step reaction.
Example 14
Preparation of 1, 4-dimethylamino-2, 5-dihydroxybenzene
2g of 1, 4-dimethylamido-2, 5-dihydroxybenzene and 0.8g of sodium hydroxide are hydrolyzed in 50ml of water at 70 ℃ for 3 hours to obtain 1, 4-dimethylamino-2, 5-dihydroxybenzene.
Example 15
Preparation of 1, 4-dimethylamino-2, 5-dihydroxybenzene
2g of 1, 4-dimethylamido-2, 5-dihydroxybenzene and 1g of potassium hydroxide are hydrolyzed in 50ml of water at 80 ℃ for 4 hours to obtain 1, 4-dimethylamino-2, 5-dihydroxybenzene.
Example 16
Preparation of hydroxylation modified nano-silica
1g of nano-silica with the particle size of 2-5nm is reacted in 100ml of 98 wt% concentrated sulfuric acid at 120 ℃ for 10 hours for hydroxylation modification to obtain hydroxylation-modified nano-silica No. 1. The reaction schematic equation is as follows:
Figure BDA0002394632120000081
however, since it is difficult to measure the number of hydroxyl groups on the surface of the nano-silica accurately, the number of hydroxyl groups on the surface of the nano-silica in the reaction formula is not an actual number, and thus it is merely a schematic illustration.
Example 17
Preparation of hydroxylation modified nano-silica
10g of nano-silica with the particle size of 5-10nm is reacted in 100ml of 70 wt% concentrated sulfuric acid at 130 ℃ for 12 hours for hydroxylation modification to obtain hydroxylation-modified nano-silica 2 #.
Example 18
Preparation of hydroxylation modified nano-silica
5g of nano-silica with the particle size of 2-7nm is reacted in 100ml of 85 wt% concentrated sulfuric acid at 150 ℃ for 10 hours for hydroxylation modification to obtain hydroxylation-modified nano-silica No. 3.
Example 19
Preparation of adsorption inhibitors
10g of hydroxylated modified silicon dioxide 1# and 6g of 1, 4-dimethylamino-2, 5-dihydroxybenzene react for 6 hours in 50ml of water at 40 ℃ to obtain the adsorption inhibitor 1 #. The reaction schematic equation is as follows:
Figure BDA0002394632120000082
among them, the number of hydroxyl groups on the surface of the nano-silica and the number of 1, 4-dimethylamino-2, 5-dihydroxybenzene reacted therewith in the reaction formula are not actual numbers, and thus are only schematically illustrated, since it is difficult to measure the exact number of hydroxyl groups on the surface of the nano-silica and the number of 1, 4-dimethylamino-2, 5-dihydroxybenzene reacted therewith.
Example 20
Preparation of adsorption inhibitors
10g of hydroxylated modified silicon dioxide 2# and 8g of 1, 4-dimethylamino-2, 5-dihydroxybenzene react in 50ml of water at 60 ℃ for 5 hours to obtain the adsorption inhibitor 2 #.
Example 21
Preparation of adsorption inhibitors
10g of hydroxylated modified silicon dioxide 3# and 10g of 1, 4-dimethylamino-2, 5-dihydroxybenzene react for 4 hours in 50ml of water at the temperature of 80 ℃ to obtain the adsorption inhibitor 3 #.
Example 22
Preparing a conventional carboxymethyl guar gum fracturing fluid, wherein the formula is as follows: 0.40 wt% of guar gum, 0.4 wt% of bactericide, 0.5 wt% of viscosity stabilizer, 0.5 wt% of cleanup additive and 0.15 wt% of Na2CO3The components of the fracturing fluid are commercially available. Taking a proper amount of carboxymethyl guar gum fracturing fluid, adding an adsorption inhibitor No. 1 into the carboxymethyl guar gum fracturing fluid under stirring, and enabling the content of the adsorption inhibitor No. 1 in the fracturing fluid to be 1 g/L.
Example 23
The fracturing fluid formulation was the same as in example 22.
Taking a proper amount of fracturing fluid, adding an adsorption inhibitor No. 2 into the fracturing fluid under stirring, and enabling the content of the adsorption inhibitor No. 2 in the fracturing fluid to be 1 g/L.
Example 24
The fracturing fluid formulation was the same as in example 22.
Taking a proper amount of fracturing fluid, adding an adsorption inhibitor No. 3 into the fracturing fluid under stirring, and enabling the content of the adsorption inhibitor No. 3 in the fracturing fluid to be 1 g/L.
Example 25
The fracturing fluid formulation was the same as in example 22.
Taking a proper amount of fracturing fluid, adding an adsorption inhibitor No. 1 into the fracturing fluid under stirring, and enabling the content of the adsorption inhibitor No. 1 in the fracturing fluid to be 5 g/L.
Comparative example 1
The same weight of carboxymethyl guar fracturing fluid without sorption inhibitor as the carboxymethyl guar fracturing fluid with sorption inhibitor in example 22.
Example 26
Performance test of adsorption inhibitor
The adsorption retention of the fracturing fluids of examples 22 to 25 and comparative example 1 on the surface of sandstone samples was tested according to standard SY/T5107-2016, and guar concentrations were sampled every 10min to determine the adsorption retention as a function of adsorption time, the results of which are shown in fig. 3.
As can be seen from fig. 3, the adsorption retention in the porous media on the surface of the sandstone sample after the addition of the adsorption inhibitor was reduced by 1.88 mg/g. The adsorption inhibitor has a good inhibition effect on the adsorption of the hydroxypropyl guar gum on the rock.
The porosity of sandstone rock samples and blank rock samples after impregnation with the fracturing fluids of examples 22-25 and comparative example 1 were measured according to standard SY/T5107-2016, respectively. The test results are shown in Table 1.
As can be seen from table 1, the porosity of the rock samples of sandstone rock sample # 1, sandstone rock sample # 2, rock sample/3 #, sandstone rock sample # 4 and sandstone rock sample # 5# is greater than that of the rock sample of comparative example 1, which fully indicates that the surface of the rock sample soaked with the fracturing fluid containing the adsorption inhibitor not only adsorbs less carboxymethyl guar, but also the porosity is increased, so that the flow ability of the fluid in the porous medium can be well improved. Thus, the adsorption inhibitor of the invention has an inhibiting effect on the adsorption of hydroxypropyl guar gum on rocks and improves the flow capacity of fluid.
TABLE 1 porosity of different rock samples
Figure BDA0002394632120000101
While the invention has been described with reference to specific embodiments, those skilled in the art will appreciate that various changes can be made without departing from the true spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation, material, composition of matter, and method to the essential scope and spirit of the present invention. All such modifications are intended to be included within the scope of the present invention as defined in the appended claims.

Claims (30)

1. A desorbent having a formula as shown in formula I:
Figure FDA0003575767450000011
wherein, the silicon dioxide is nano silicon dioxide particles, n is an integer which is greater than or equal to 0, and m is a natural number which is greater than or equal to 1.
2. Desorbent according to claim 1, characterized in that the particle size of the nanosilica particles is 2 to 10 nm.
3. A method of preparing a desorbent comprising the steps of: and reacting the hydroxylation modified nano silicon dioxide with dimethylamino dihydroxybenzene to obtain the desorbent.
4. The method of claim 3, wherein the dimethylaminodydroxybenzene is 1, 4-dimethylamino-2, 5-dihydroxybenzene.
5. The method according to claim 3, wherein the hydroxylated modified nanosilica is reacted with the dimethylaminodydroxybenzene in water at 40 to 80 ℃ for 4 to 6 hours to obtain the desorbent.
6. The method according to claim 3, wherein the nanosilica particles have a particle size of 2 to 10nm before modification.
7. The method of claim 3, wherein the mass ratio of the hydroxylated modified nanosilica to the dimethylaminodydroxybenzene is from 1: 0.6 to 1: 1.
8. the method according to claim 3, wherein the hydroxylated modified nanosilica is prepared by: the nano-silicon dioxide is reacted in concentrated sulfuric acid at 120 to 150 ℃ for 10 to 12 hours.
9. The method of claim 8, wherein the concentrated sulfuric acid has a concentration of 70% to 98%, and the volume/mass ratio of the concentrated sulfuric acid to the nano-silica is 1: (0.01-0.1).
10. The method of claim 3, wherein dimethylaminodydroxybenzene is hydrolyzed with a base to provide the dimethylaminodydroxybenzene.
11. The method of claim 10, wherein the dimethylaminodyidihydroxybenzene is 1, 4-dimethylamido-2, 5-dihydroxybenzene.
12. The method of claim 10, wherein the base is sodium hydroxide and/or potassium hydroxide.
13. The method of claim 10, wherein the mass ratio of dimethylaminodydroxybenzene to base is from 2:1 to 4: 1.
14. The method of claim 10, wherein the dimethylaminodydroxybenzene is hydrolyzed at 60 to 80 ℃ for 2 to 4 hours in the presence of a base to produce the dimethylaminodydroxybenzene.
15. The method of claim 10, wherein dimethylaminodimethoxybenzene is reacted with butyllithium to provide the dimethylaminodydroxybenzene.
16. The method of claim 15, wherein the dimethylaminodimethoxybenzene is 1, 4-dimethylaminod-2, 5-dimethoxybenzene and the dimethylaminodyidihydroxybenzene is 1, 4-dimethylaminod-2, 5-dihydroxybenzene.
17. The method of claim 15, wherein the butyl lithium is n-butyl lithium.
18. The method of claim 15, wherein the molar ratio of dimethylaminodimethoxybenzene to butyllithium is 1: 1.5 to 1: 3.
19. The method of claim 15, wherein the dimethylaminodimethoxybenzene and the butyllithium are reacted in chloroform at 0 to 5 ℃ for 1 to 3 hours to provide the dimethylaminodydroxybenzene.
20. The process of claim 15, wherein dimethylaminodimethoxybenzene is reacted with formic acid in ethanol at 50 to 70 ℃ for 2 to 3 hours to form the dimethylaminodimethoxybenzene.
21. The method of claim 20, wherein the dimethylaminodimethoxybenzene is 1, 4-dimethylamino-2, 5-dimethoxybenzene and the dimethylaminodimethoxybenzene is 1, 4-dimethylaminod-2, 5-dimethoxybenzene.
22. The process of claim 20, wherein the molar ratio of dimethylamino dimethoxybenzene to the formic acid is 1: 2 to 1: 4.
23. the process of claim 20, wherein the dimethylnitrilo dimethoxybenzene is reacted with lithium aluminum hydride in diethyl ether at 20 to 40 ℃ for 2 to 5 hours to obtain dimethylamino dimethoxybenzene.
24. The method of claim 23, wherein the dicyanodimethoxybenzene is 1, 4-dicyanodi-2, 5-dimethoxybenzene and the dimethylaminodimethoxybenzene is 1, 4-dimethylamino-2, 5-dimethoxybenzene.
25. The method of claim 23, wherein the molar ratio of the dicyano dimethoxybenzene to the lithium aluminum hydride is 1: 2.5 to 1: 3.5.
26. the process of claim 23, wherein dibromodimethoxybenzene is reacted with copper carbo-nitride in N-methylpyrrolidinone at 180 to 200 ℃ for 7 to 9 hours to obtain dinitrile dimethoxybenzene.
27. The method of claim 26, wherein the dibromodimethoxybenzene is 1, 4-dibromo-2, 5-dimethoxybenzene, and the dinitrile dimethoxybenzene is 1, 4-dinitrile-2, 5-dimethoxybenzene.
28. The method of claim 26, wherein the molar ratio of dibromodimethoxybenzene to the copper carbo-nitride is 1: 0.9 to 1: 1.2.
29. use of a desorbent according to claim 1 or 2 or prepared by a process according to any one of claims 3 to 28 for inhibiting adsorption of guar gum to formation rock.
30. The use according to claim 29, wherein the desorbent is present in the guar gum-containing fracturing fluid in an amount of from 1g/L to 5g/L by mass.
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