CN107628955B - Amino inhibitor for water-based drilling fluid, water-based drilling fluid system and preparation method - Google Patents
Amino inhibitor for water-based drilling fluid, water-based drilling fluid system and preparation method Download PDFInfo
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Abstract
The embodiment of the application discloses an amino inhibitor for a water-based drilling fluid and a preparation method thereof, wherein the amino inhibitor comprises polyalkyl ammonium chloride, and the polyalkyl ammonium chloride at least comprises a compound 1 shown in a formula I, or at least comprises a compound 2 shown in a formula II and a compound 3 shown in a formula III. According to the amino inhibitor in the technical scheme, the hydrophilicity of the amino inhibitor is improved by introducing the alcoholic hydroxyl group or introducing the alcoholic hydroxyl group and the carboxyl group, so that the inhibiting performance of the amino inhibitor is improved, the influence of the amino inhibitor on the rheological property of a drilling fluid system is reduced, and the compatibility of the amino inhibitor is improved.
Description
Technical Field
The application relates to the field of inhibitors for water-based drilling fluids, in particular to an amino inhibitor for water-based drilling fluids. In addition, the application also relates to a preparation method of the amino inhibitor for the water-based drilling fluid and a water-based drilling fluid system.
Background
When the shale is drilled in the process of petroleum exploration and development, the shale well wall is easy to hydrate, expand and disperse, so that the well wall is unstable and even collapses. The drilling fluid is a circulating flushing medium used in oil drilling, has inhibition performance and can prevent well wall collapse. The oil-based drilling fluid has good inhibition performance on the shale, but has great environmental pollution. Water-based drilling fluids are increasingly being used for environmental reasons. However, water-based drilling fluids have poorer inhibitive performance than oil-based drilling fluids. Therefore, when using water-based drilling fluids, it is usually necessary to add shale inhibitors to the water-based drilling fluids to form a water-based drilling fluid system, so as to improve the stability of the shale structure.
The amino inhibitor is one of the existing shale inhibitors, can permeate into a shale matrix or react on the surface of a clay layer, and has a remarkable inhibiting effect. The amino inhibitors are classified according to the structure of the compound and mainly comprise monomeric amine inhibitors, oligomeric amine inhibitors and polymeric amine inhibitors. The polyamine inhibitor has better inhibition performance than a monomer amine inhibitor, but has larger influence on the rheological property of the water-based drilling fluid. The monomeric amine inhibitor has less influence on the rheological property of the water-based drilling fluid, but the inhibition performance is weaker than that of the polyamine inhibitor. When complex layers such as a shale layer which is easy to hydrate are drilled, the stability of the shale under the action of the monomeric amine inhibitor is still insufficient to meet the construction requirement.
Disclosure of Invention
In order to solve the technical problems, the application provides an amino inhibitor with better inhibition performance.
In a first aspect, an amine-based inhibitor for water-based drilling fluids is provided, the amine-based inhibitor comprising a polyallyl ammonium chloride, the polyallyl ammonium chloride comprising at least compound 1 of formula I:
the polyalkyi alcohol acid propyl ammonium chloride at least comprises a compound 2 shown in a formula II and a compound 3 shown in a formula III:
wherein R1 is-CH2CH2OH or H;
r2 is
R3 is
With reference to the first aspect, in a first possible implementation manner of the first aspect, when the polyallyl ammonium chloride includes a compound represented by formula I, the polyallyl ammonium chloride further includes a compound 4 represented by formula IV below:
with reference to the first aspect and the foregoing possible implementation manners, in a second possible implementation manner of the first aspect, the amine-based inhibitor further includes an alkenyl polyether polymer, where the alkenyl polyether polymer includes one or more of allyl dehydrated glycerol ether, polyethylene glycol monoallyl ether, and polypentaerythritol allyl ether.
In combination with the second possible implementation manner of the first aspect, in a third possible implementation manner of the first aspect, the weight fraction of the alkenyl polyether polymer is 10 wt% to 30 wt% based on the total weight of the amine-based inhibitor.
In a second aspect, a method for preparing an amine-based inhibitor for a water-based drilling fluid is provided, which comprises the following steps:
mixing polyalcohol amine with a chloropropane compound, and reacting to obtain polyallyl alcohol acid propyl ammonium chloride;
wherein the polyalcohol amine comprises triethanolamine and optional ethanolamine and/or diethanolamine, and the chloropropane compound is one or more selected from epichlorohydrin, methyl epichlorohydrin, trichloropropane, 2-methyl-2-chloropropane and 2-methyl-1-chloropropane.
With reference to the second aspect, in a first possible implementation manner of the second aspect, the preparation method of the amine-based inhibitor further includes the following steps:
uniformly mixing polyalkyi alcohol acid propyl ammonium chloride with alkenyl polyether polymer to obtain an amino inhibitor;
the alkenyl polyether polymer comprises one or more of allyl dehydrated glycerol ether, polyethylene glycol monoallyl ether and polypentaerythritol allyl ether.
With reference to the second aspect and the foregoing possible implementation manners, in a second possible implementation manner of the second aspect, the weight ratio of the polyalcohol amine to the chloropropane compounds is the weight of the polyalcohol amine, that is, the weight of the chloropropane compounds is (1-2): 1.
In a third aspect, a preparation method of an amine-based inhibitor for a water-based drilling fluid is provided, which comprises the following reaction steps:
adding polyalcohol amine into chloroacetic acid compounds to obtain a first intermediate;
adding chloropropane compounds into the first intermediate, and reacting to obtain polyaluminium propyl alcohol acid ammonium chloride;
wherein the polyalcohol amine is selected from one or more of triethanolamine, ethanolamine and diethanolamine, the chloroacetic acid compound is selected from one or more of chloroacetic acid, 2-chlorphenyl aminoacetic acid and p-chlorophenoxyacetic acid, and the chloropropane compound comprises one or more of epichlorohydrin, methyl epichlorohydrin, trichloropropane, 2-methyl-2-chloropropane and 2-methyl-1-chloropropane.
With reference to the third aspect, in a first possible implementation manner of the third aspect, the method for preparing the amine-based inhibitor further includes the following steps:
uniformly mixing polyalkyi alcohol acid propyl ammonium chloride with alkenyl polyether polymer to obtain an amino inhibitor;
the alkenyl polyether polymer comprises one or more of allyl dehydrated glycerol ether, polyethylene glycol monoallyl ether and polypentaerythritol allyl ether.
In a fourth aspect, there is provided a water-based drilling fluid system comprising any one of the amine-based inhibitors of the first aspect, the water-based drilling fluid system comprising the following components in weight percent:
in the technical scheme, the polyallyl ammonium chloride in the amine inhibitor at least comprises a compound 1, or at least comprises a mixture of compounds 2 and 3, and alcoholic hydroxyl is introduced, or the alcoholic hydroxyl and carboxyl are introduced to improve the hydrophilicity of the amine inhibitor. When the polyatomic alcohol acid propyl ammonium chloride is used, cation exchange is carried out between the polyatomic alcohol acid propyl ammonium chloride and the surface of the easily hydrated shale, the polyatomic alcohol acid propyl ammonium chloride is adsorbed on the surface of the shale, hydrophilic groups in the polyatomic alcohol acid propyl ammonium chloride form a hydration film on the surface of the shale, water molecules are prevented from entering the interior of the shale, and therefore the stability of the shale is improved. That is, the inhibiting performance of the amine-based inhibitor is improved.
In addition, the polyalkydrol acid propyl ammonium chloride in the amino inhibitor is introduced with the hydrophilic group, so that the hydrophilic group forms a hydration film around the polyalkydrol acid propyl ammonium chloride molecules, and the phenomenon of charge neutralization is reduced, thereby reducing the influence of the amino inhibitor on the colloid balance of a drilling fluid system, reducing the influence of the amino inhibitor on the rheological property of the drilling fluid system, and further improving the compatibility of the amino inhibitor.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the technical solution of the present invention will be further described with reference to the specific embodiments.
In a first embodiment of the present application, there is provided a method for preparing an amine-based inhibitor for a water-based drilling fluid, comprising the steps of:
mixing polyalcohol amine with a chloropropane compound, and reacting to obtain polyallyl alcohol acid propyl ammonium chloride;
wherein the polyalcohol amine comprises triethanolamine and optional ethanolamine and/or diethanolamine, and the chloropropane compound is one or more selected from epichlorohydrin, methyl epichlorohydrin, trichloropropane, 2-methyl-2-chloropropane and 2-methyl-1-chloropropane.
In the preparation method, when the polyalcohol amine comprises triethanolamine, the triethanolamine and the chloropropane compound undergo a nucleophilic substitution reaction to obtain a compound 1 shown in a formula I, as shown in a reaction formula I:
wherein, for example, the chloropropane compound comprises epichlorohydrin, and the group R2 is
Such as chloropropanes comprising methylepichlorohydrin, the radical R2 being
Such as chloropropanes including trichloropropane, the radical R2 being
And/or
For example, the chloropropane compound comprises 2-methyl-2-chloropropane, and the group R2 is
For example, the chloropropane compound comprises 2-methyl-1-chloropropane, and the group R2 is
The chloropropane compound may be one of the above 5 compounds, or a mixture of any several of them, which is not limited in this application. When the chloropropane compounds are mixtures, the compound 1 prepared in the first reaction formula is correspondingly a mixture of a plurality of products.
The polyalkyi alcohol acid propyl ammonium chloride prepared by the preparation method at least comprises a compound 1, and the hydrophilicity of the amino inhibitor is improved by introducing alcoholic hydroxyl. When the polyatomic alcohol acid propyl ammonium chloride is used, cation exchange is carried out between the polyatomic alcohol acid propyl ammonium chloride and the surface of the easily hydrated shale, the polyatomic alcohol acid propyl ammonium chloride is adsorbed on the surface of the shale, hydrophilic groups in the polyatomic alcohol acid propyl ammonium chloride form a hydration film on the surface of the shale, and water molecules are prevented from entering the interior of the shale, so that the stability of the shale is improved, and the inhibition performance of the amine-based inhibitor is improved.
In addition, the inventors have analyzed that conventional small molecule monomeric amine inhibitors have a positive charge and poor hydrophilicity at the chain ends, whereas aqueous drilling fluid colloids generally have a negative charge. When the water-based drilling fluid is used, the monomeric amine inhibitor is added into the water-based drilling fluid, and the negative charge in the water-based drilling fluid is neutralized by the positive charge in the monomeric amine inhibitor, so that the colloid balance of the water-based drilling fluid is damaged, the water-based drilling fluid added with the inhibitor is coagulated, and the rheological property of the water-based drilling fluid is influenced to a certain extent. In order to maintain the original performance of the water-based drilling fluid system, other additives with viscosity reduction effect are often required to be added. Different additives are required to be developed for matching with different monomeric amine inhibitors, so that the compatibility of the monomeric amine inhibitors is reduced.
The polyalkydrol propyl ammonium chloride prepared by the preparation method has the advantages that the hydrophilic groups are introduced, so that the hydrophilic groups form a hydration film around the polyalkyl propyl ammonium chloride molecules, and the phenomenon of charge neutralization is reduced, so that the influence of the amino inhibitor on the colloid balance of a drilling fluid system is reduced, the influence of the amino inhibitor on the rheological property of the drilling fluid system is reduced, and the compatibility of the amino inhibitor is improved.
Optionally, in the above preparation method, the polyalcohol amine may further include ethanolamine and/or diethanolamine, and the ethanolamine/diethanolamine and the chloropropane compound undergo a nucleophilic substitution reaction to obtain a compound 2, as shown in reaction formula two:
wherein the group R1 is-CH2CH2OH or H; the radical R2 is the same as described above and is
And will not be described in detail herein.
The chloropropane compound may be one of the above 5 compounds, or a mixture of any two of them, which is not limited in this application. When the chloropropane compounds are mixtures, the compound 2 prepared in the second reaction formula is correspondingly a mixture of a plurality of products.
When the polyalcohol amine comprises both triethanolamine and ethanolamine and/or diethanolamine, the polyallyl ammonium chloride comprises compound 2 in addition to compound 1 described above, i.e. a mixture of compound 1 and compound 2.
Optionally, the preparation method may further include the following steps:
and (3) uniformly mixing the polyalkynol propyl ammonium chloride and the alkenyl polyether polymer to obtain the amino inhibitor.
The alkenyl polyether polymer comprises one or more of allyl dehydrated glycerol ether, polyethylene glycol monoallyl ether and polypentaerythritol allyl ether. The weight fraction of the alkenyl polyether polymer is 10-30 wt% based on the total weight of the amine-based inhibitor.
The polyalkynoammonium chloride is compounded with alkenyl polyether polymers to obtain a compound serving as an amino inhibitor. The alkenyl polyether polymer can play a role in regulating the flow pattern and has a certain auxiliary inhibition effect. The alkenyl polyether polymer and the polyalkylamine alkyl chloride can synergistically improve the inhibition performance of the amino inhibitor, and simultaneously further reduce the influence of the amino inhibitor on the rheological property of the water-based drilling fluid.
In a second embodiment of the present application, there is provided a method for preparing an amine-based inhibitor for a water-based drilling fluid, comprising the following reaction steps:
adding polyalcohol amine into chloroacetic acid compounds to obtain a first intermediate;
adding chloropropane compounds into the first intermediate, and reacting to obtain polyaluminium propyl alcohol acid ammonium chloride;
wherein the polyalcohol amine is selected from one or more of triethanolamine, ethanolamine and diethanolamine, the chloroacetic acid compound is selected from one or more of chloroacetic acid, 2-chlorphenyl aminoacetic acid and p-chlorophenoxyacetic acid, and the chloropropane compound comprises one or more of epichlorohydrin, methyl epichlorohydrin, trichloropropane, 2-methyl-2-chloropropane and 2-methyl-1-chloropropane.
Alternatively, the weight ratio of the polyalcohol amine to the chloropropane compounds is (1-2): 1. Alternatively, the weight ratio of chloroacetic compounds to chloropropane compounds is (0.05-0.25): 1. Because the addition amount of the chloroacetic acid compounds is relatively small, part of the polyalcohol amine reacts with the chloroacetic acid compounds, and the other polyalcohol amine reacts with the chloropropane compounds.
In a first embodiment, the hydrophilicity of the amine-based inhibitor is improved by introducing alcoholic hydroxyl groups, so that the inhibiting performance of the amine-based inhibitor is improved, and the influence on the rheological property of the water-based drilling fluid is reduced. Compared with ethanolamine and diethanolamine, triethanolamine has more alcoholic hydroxyl groups, and is more beneficial to improving the hydrophilicity of the amine inhibitor. When the triethanolamine is not contained in the polyalcohol amine, a proper amount of chloroacetic acid compounds are added into the polyalcohol amine, so that part of the polyalcohol amine and chloroacetic acids are subjected to nucleophilic substitution reaction, and part of the polyalcohol amine is still reacted with chloropropanes, and thus, the carboxyl and alcoholic hydroxyl are introduced to jointly improve the hydrophilicity of the amino inhibitor, so that the finally prepared amino inhibitor has excellent inhibition performance, and the rheological effect on the water-based drilling fluid is small.
In the above preparation method, when the triethanolamine is not included in the polyalcohol amine, i.e. only ethanolamine, or only diethanolamine, or a mixture of ethanolamine and diethanolamine, a proper amount of chloroacetic acid compound reacts with part of ethanolamine/diethanolamine to obtain compound 3 shown in formula III, as shown in reaction formula III:
wherein the group R1 is-CH2CH2OH or H;
for example, chloroacetic compounds include chloroacetic acid, the group R3 is
For example, chloroacetic acids include 2-chlorophenylglycine, the radical R3 is
For example, the chloroacetic acid compound comprises p-chlorophenoxyacetic acid, and the group R3 is
When the triethanolamine is not included in the polyalcohol amine, nucleophilic substitution reaction is performed between another part of the ethanolamine/diethanolamine and the chloropropane compound to obtain a compound 2, and the reaction formula of the compound 2 is the same as the reaction formula II in the first embodiment, which is not described herein again.
In the embodiment of the present application, the chloroacetic acid-based compound may be any one of chloroacetic acid, 2-chlorophenylglycine and p-chlorophenoxyacetic acid, or a mixture of any several of them, which is not limited in the present application. When the chloroacetic acid-based compounds are a mixture, the compound 3 prepared in the above reaction formula III is correspondingly a mixture of a plurality of products.
When the polyalcohol amine comprises triethanolamine, part of the triethanolamine and chloroacetic acid compounds undergo nucleophilic substitution reaction, and the other part of the triethanolamine and chloropropane compounds undergo nucleophilic substitution reaction.
Specifically, triethanolamine reacts with chloroacetic acid compounds to obtain a compound 4 shown in a formula IV, as shown in a reaction formula IV:
wherein the radical R3 is the same as described above and is
And will not be described in detail herein.
In the embodiment of the present application, the chloroacetic acid-based compound may be any one of chloroacetic acid, 2-chlorophenylglycine and p-chlorophenoxyacetic acid, or a mixture of any several of them, which is not limited in the present application. When the chloroacetic compounds are a mixture, the compound 4 prepared in the above reaction formula IV is correspondingly a mixture of various products.
The reaction formula of the nucleophilic substitution reaction between the other part of triethanolamine and the chloropropane compound is the same as the reaction formula in the first embodiment, and is not described herein again.
In the above case, the polyalcohol amine comprises both ethanolamine and/or diethanolamine and triethanolamine, and the prepared polyallyl ammonium chloride is a mixture of compound 1, compound 2, compound 3 and compound 4.
In the actual reaction for preparing the polyaluminium propyl chloride, water may be added into the system during the reaction, and in this case, as an alternative scheme, the weight ratio of the water to the polyalcohol amine added into the reaction system is 1:1-1: 2.
Even if triethanolamine is included in the polyalcohol amine, a proper amount of chloroacetic acid compounds can be added into a reaction system of the polyalcohol amine and chloropropanes, and more hydrophilic groups are introduced, so that the hydrophilicity of the prepared polyaluminium propyl alcohol acid chloride is further improved, and the inhibition performance and the compatibility of an amine inhibitor are further improved. It can be seen from the results of the effect tests in examples 4 and 5 that the inhibition performance of the finally prepared amine-based inhibitor is better by replacing a part of ethanolamine in the polyalcohol amine with the same amount of triethanolamine and keeping other reaction conditions unchanged.
Optionally, the preparation method may further include the steps of:
and (3) uniformly mixing the polyalkynol propyl ammonium chloride and the alkenyl polyether polymer to obtain the amino inhibitor.
The alkenyl polyether polymer comprises one or more of allyl dehydrated glycerol ether, polyethylene glycol monoallyl ether and polypentaerythritol allyl ether. The weight fraction of the alkenyl polyether polymer is 10-30 wt% based on the total weight of the amine-based inhibitor. Here, the weight fraction of the alkenyl polyether polymer is always calculated based on the total weight of the amine-based inhibitor.
The effect test results of the embodiment 5 and the embodiment 8 show that the polyallyl ammonium chloride alkyd is compounded with the alkenyl polyether polymer, so that the polyallyl ammonium chloride alkyd and the alkenyl polyether polymer have the effect of synergistically improving the inhibition performance, and the influence of the amine-based inhibitor on the rheological property of the water-based drilling fluid is further reduced.
In a third embodiment of the present application, there is provided a water-based drilling fluid system, the amine-based inhibitor prepared in the previous embodiment, comprising the following components in weight percent:
the water-based drilling fluid has excellent inhibition performance and rheological property, and can meet construction requirements even when drilling complex layers such as shale layers which are easy to hydrate. The effect tests of example 12 and example 13 also show that the water-based drilling fluid system in the example of the present application can increase the shale expansion reduction rate by about 10% on the basis of the control group, which indicates that the amine-based inhibitor in the example of the present application can significantly improve the inhibition of the drilling fluid system and has better compatibility.
The humate filtrate reducer, the emulsion coating agent, the organic silicon viscosity reducer and other reagents are conventional corresponding reagents in the field, and the application is not limited in comparison.
The following examples further illustrate the above embodiments, but do not therefore limit the invention within the scope of the examples described. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions. Other reagents, materials and equipment not specifically described are commercially available directly.
Example 1
(1) Adding 100g of water into a 500mL three-neck flask;
(2) adding 100g of polyalcohol amine into a three-neck flask while stirring, wherein the polyalcohol amine is triethanolamine;
(3) dripping 100g of chloropropane compounds into a three-neck flask, wherein the chloropropane compounds are methyl epichlorohydrin;
(4) after the dripping is finished, the temperature is raised to 70 ℃, and the heat preservation reaction is carried out for 4 hours, thus obtaining the amido inhibitor 1.
Example 2
(1) Adding 100g of water into a 500mL three-neck flask;
(2) adding 127.5g of polyalcohol amine into a three-neck flask while stirring, wherein the polyalcohol amine is a mixture of triethanolamine and ethanolamine, and the weight ratio of the triethanolamine to the ethanolamine is 1: 10;
(3) dripping 90g of chloropropane compound into a three-neck flask, wherein the chloropropane compound is trichloropropane;
(4) after the dripping is finished, the temperature is raised to 70 ℃, and the heat preservation reaction is carried out for 4 hours, thus obtaining the amido inhibitor 2.
Example 3
(1) Adding 100g of water into a 500mL three-neck flask;
(2) adding 200g of polyalcohol amine into a three-neck flask while stirring, wherein the polyalcohol amine is a mixture of triethanolamine and diethanolamine, and the weight ratio of the triethanolamine to the diethanolamine is 1: 10;
(3) dropping 100g of chloropropane compound into a three-neck flask, wherein the chloropropane compound is 2-methyl-1-chloropropane;
(4) after the dripping is finished, the temperature is raised to 70 ℃, and the heat preservation reaction is carried out for 4 hours, thus obtaining the amido inhibitor 3.
Example 4
(1) Adding 100g of water into a 500mL three-neck flask;
(2) adding 4.5g of chloroacetic acid compound into a three-neck flask, wherein the chloroacetic acid compound is chloroacetic acid;
(3) 127.5g of polyalcohol amine is added into a three-neck flask while stirring, wherein the polyalcohol amine is ethanolamine;
(4) dripping 90g of chloropropane compound into a three-neck flask, wherein the chloropropane compound is trichloropropane;
(5) after the dripping is finished, the temperature is raised to 70 ℃, and the heat preservation reaction is carried out for 4 hours, thus obtaining the amido inhibitor 4.
Example 5
(1) Adding 100g of water into a 500mL three-neck flask;
(2) adding 4.5g of chloroacetic acid compound into a three-neck flask, wherein the chloroacetic acid compound is chloroacetic acid;
(3) adding 127.5g of polyalcohol amine into a three-neck flask while stirring, wherein the polyalcohol amine is a mixture of ethanolamine and triethanolamine, and the weight ratio of the triethanolamine to the ethanolamine is 1: 10;
(4) dripping 90g of chloropropane compound into a three-neck flask, wherein the chloropropane compound is trichloropropane;
(5) after the dripping is finished, the temperature is raised to 70 ℃, and the heat preservation reaction is carried out for 4 hours, thus obtaining the amido inhibitor 5.
Example 6
(1) Adding 100g of water into a 500mL three-neck flask;
(2) adding 25g of chloroacetic acid compounds into a three-neck flask, wherein the chloroacetic acid compounds are a mixture of 2-chlorophenylglycine and p-chlorophenoxyacetic acid, and the weight ratio of the 2-chlorophenylglycine to the chlorophenoxyacetic acid is 1: 1;
(3) adding 100g of polyalcohol amine into a three-neck flask while stirring, wherein the polyalcohol amine is ethanolamine;
(4) dropping 100g of chloropropane compounds into a three-neck flask, wherein the chloropropane compounds are a mixture of epoxy chloropropane and 2-methyl-2 chloropropane, and the weight ratio of the epoxy chloropropane to the 2-methyl-2 chloropropane is 1: 1;
(5) after the dripping is finished, the temperature is raised to 70 ℃, and the heat preservation reaction is carried out for 4 hours, thus obtaining the amido inhibitor 6.
Example 7
(1) Adding 100g of water into a 500mL three-neck flask;
(2) adding 5g of chloroacetic acid compound into a three-neck flask, wherein the chloroacetic acid compound is chloroacetic acid;
(3) adding 200g of polyalcohol amine into a three-neck flask while stirring, wherein the polyalcohol amine is diethanol amine;
(4) dropping 100g of chloropropane compound into the three-neck flask, wherein the chloropropane compound is trichloropropane;
(5) after the dripping is finished, the temperature is raised to 70 ℃, and the heat preservation reaction is carried out for 4 hours, thus obtaining the amido inhibitor 7.
Example 8
(1) Adding 100g of water into a 500mL three-neck flask;
(2) adding 4.5g of chloroacetic acid compound into a three-neck flask, wherein the chloroacetic acid compound is chloroacetic acid;
(3) adding 127.5g of polyalcohol amine into a three-neck flask while stirring, wherein the polyalcohol amine is a mixture of ethanolamine and triethanolamine, and the weight ratio of the triethanolamine to the ethanolamine is 1: 10;
(4) dripping 90g of chloropropane compound into a three-neck flask, wherein the chloropropane compound is trichloropropane;
(5) after the dripping is finished, heating to 70 ℃, and carrying out heat preservation reaction for 4 hours to obtain polyalkyi alcohol acid propyl ammonium chloride;
(6) and mixing and stirring the polyalkylamine with the alkenyl polyether polymer for 0.5h according to the weight ratio of 90:10, wherein the alkenyl polyether polymer is allyl dehydrated glycerol ether, and thus obtaining the amino inhibitor 8.
Example 9
Steps (1) to (4) were the same as Steps (1) to (4) of example 8;
(5) after the dripping is finished, heating to 90 ℃, and carrying out heat preservation reaction for 2 hours to obtain polyaluminium propyl alcohol acid ammonium chloride;
(6) and (2) mixing and stirring polyallyl ammonium chloride and an alkenyl polyether polymer for 0.5h according to the weight ratio of 70:30, wherein the alkenyl polyether polymer is a mixture of polyethylene glycol monoallyl ether and polypentaerythritol allyl ether, and the weight ratio of the polyethylene glycol monoallyl ether to the polypentaerythritol allyl ether is 1:1, so as to obtain the amino inhibitor 9.
Example 10
Steps (1) to (5) were the same as Steps (1) to (5) of example 8;
(6) and mixing and stirring the polyalkylamine and the alkenyl polyether polymer for 0.5h according to the weight ratio of 95:5, wherein the alkenyl polyether polymer is allyl dehydrated glycerol ether, and thus obtaining the amino inhibitor 10.
Example 11
Steps (1) to (5) were the same as Steps (1) to (5) of example 8;
(6) and mixing and stirring the polyallyl ammonium chloride and the alkenyl polyether polymer for 0.5h according to the weight ratio of 65:35, wherein the alkenyl polyether polymer is allyl dehydrated glycerol ether, and thus obtaining the amino inhibitor 11.
Example 12
Adding the amino inhibitor 8 prepared in the example 8 into water-based drilling fluid, and uniformly mixing to obtain a water-based drilling fluid system 1, which comprises the following components in percentage by weight:
example 13
Adding the amino inhibitor 8 prepared in the example 8 into water-based drilling fluid, and uniformly mixing to obtain a water-based drilling fluid system 2, which comprises the following components in percentage by weight:
effect example 1Rheological Effect
The viscosity, Plastic Viscosity (PV) and yield value (YP) of the blank sample, the test sample and the control sample were measured, respectively, using the base slurry as a blank sample, the mixture of the base slurry and the amine-based inhibitor prepared in the examples of the present application as a test sample, and the mixture of the base slurry and trimethylammonium chloride as a control sample.
Blank sample: the components of the base slurry are 400mL of water, 20g of calcareous soil and 1g of soda ash.
Test sample 1: the content of the amine inhibitor 2 in the base slurry + the amine inhibitor 2 prepared in example 2 was 1% of that in the test sample 1.
Test sample 2: the amount of the amine inhibitor 4 in the base slurry + the amine inhibitor 4 prepared in example 4 was 1% of that in test sample 2.
Test sample 3: the slurry + the amine-based inhibitor 5 obtained in example 5 contained 1% of the amine-based inhibitor 5 in the test sample 3.
Test sample 4: the slurry + the amine-based inhibitor 8 obtained in example 8 contained 1% of the amine-based inhibitor 8 in the test sample 4.
Test sample 5: the slurry + the amine-based inhibitor 10 obtained in example 10 contained 2% of the amine-based inhibitor 10 in the test sample 5.
Control sample: the content of the base slurry and the trimethyl ammonium chloride is 2 percent of that of the control sample.
The results of the test are shown in Table 1.
TABLE 1 Effect of amine-based inhibitors on the rheology of a calcareous soil-based slurry
As can be seen from table 1, trimethylammonium chloride, as a conventional monomeric amine inhibitor, rapidly increases in viscosity when added to the basestock as compared to the blank basestock. The amino inhibitor prepared by the embodiment of the application has small influence on the rheological property of the base slurry after being added, and does not need to develop a corresponding viscosity reduction additive, so that the amino inhibitor has good compatibility.
As can be seen from the rheological results of the test sample 1 and the test sample 2, when triethanolamine is not included in the polyalcohol amine, the chloroacetic acid compound is added into the reaction system, the carboxyl group is introduced, and the chloroacetic acid compound and the alcoholic hydroxyl group in the polyalcohol amine are jointly used as a hydrophilic group, so that the influence of the two groups on the rheological property of the base slurry is not obviously different.
As can be seen from the rheological results of the test sample 2 and the test sample 3, part of ethanolamine in the polyalcohol amine is replaced by equal amount of triethanolamine, and other reaction conditions are unchanged, so that the amino inhibitor 4 and the amino inhibitor 5 are respectively prepared, wherein the influence of the former on the rheological property of the water-based drilling fluid is greater than that of the latter.
According to rheological results of the test sample 3, the test sample 4 and the test sample 5, the alkenyl polyether polymer is added into the polyallyl ammonium chloride for compounding to prepare the amino inhibitor, so that the influence of the amino inhibitor on the rheological property of the water-based drilling fluid can be further reduced. As can be seen from the rheological results of the test sample 4 and the test sample 5, when the alkenyl polyether polymer accounts for 10-30% of the weight of the amino inhibitor, the prepared amino inhibitor has smaller influence on the rheological property of the water-based drilling fluid, and the amino inhibitor has better compatibility.
Effect example 2Relative inhibition rate
In the petroleum industry, the relative inhibition rate is the simplest detection method for measuring the inhibition of the shale inhibitor.
1. Preparation of base slurry
Adding 1.05g of sodium carbonate into 350mL of water, stirring at 10000r/min for 5min, slowly adding 35.00g of bentonite for drilling fluid, stirring at 10000r/min for 20min, hot rolling at 120 ℃ for 16h, cooling, stirring at 10000r/min for 5min, and measuring phi 'of base slurry at 24 +/-3 ℃ according to the specification of SY/T5621'100Values (all to the nearest 0.01 g).
2. Preparation of slurry
Dissolving 10.5mL of sample in 350mL of distilled water, stirring uniformly, adding 1.05g of sodium carbonate, stirring for 5min at 10000r/min, slowly adding 35.00g of bentonite for drilling fluid, stirring for 20min at 10000r/min, hot rolling for 16h at 120 ℃, cooling, stirring for 5min at 10000r/min, and measuring the phi of the slurry at 24 +/-3 ℃ according to the specification of SY/T5624100The value is obtained. (all to 0.01g)
3. Calculation of results
The relative inhibition rate is calculated according to the formula (1):
in the formula:
x-relative inhibition,%;
φ100-reading of mud at 100 r/min;
φ'100reading the base slurry at 100 r/min.
The results of the relative inhibition ratios finally measured using the amine-based inhibitors prepared in the foregoing examples are shown in table 2.
TABLE 2 comparison of relative inhibition ratios for amine-based inhibitor samples
As can be seen from the data in Table 2, the amine-based inhibitors prepared in the examples of the present application have superior inhibitory properties to conventional monomeric amine-based inhibitors. And the relative inhibition rate detection results of the amino inhibitor 2 and the amino inhibitor 4 show that when triethanolamine is not included in the polyalcohol amine, chloroacetic acid compounds are added into a reaction system, carboxyl groups are introduced, and the chloroacetic acid compounds and the alcoholic hydroxyl groups in the polyalcohol amine are jointly used as hydrophilic groups, so that the inhibition performances of the chloroacetic acid compounds and the hydrophilic groups are not obviously different.
And replacing part of ethanolamine in the polyalcohol amine with triethanolamine with the same amount, and keeping other reaction conditions unchanged to respectively prepare the amino inhibitor 4 and the amino inhibitor 5. As can be seen from the results of the relative inhibition rate detection of the amine-based inhibitor 4 and the amine-based inhibitor 5, the relative inhibition rate of the amine-based inhibitor 5 is superior to that of the amine-based inhibitor 4.
The result of the detection of the relative inhibition rate of the amino inhibitor 5 and the amino inhibitor 8 shows that the alkenyl polyether polymer is added into the polyallyl ammonium chloride for compounding to prepare the amino inhibitor, and the polyallyl ammonium chloride and the allyl dehydrated glycerol ether have the effect of synergistically improving the inhibition performance of the amino inhibitor.
As can be seen from the results of the relative inhibition rates of the amino inhibitor 8, the amino inhibitor 10 and the amino inhibitor 11, when the alkenyl polyether polymer accounts for 10-30% of the weight of the amino inhibitor, the prepared amino inhibitor has better inhibition performance.
Effect example 3Shale expansion reduction rate
The method comprises the steps of extruding calcium bentonite under certain pressure for certain time to form a mud block for simulating an easily hydrated shale core in a stratum, putting the core into clear water and a shale inhibitor solution with certain concentration, detecting the expansion length of the core within a specified time by using a professional instrument, and calculating to obtain the shale expansion reduction rate. The shale expansion reduction rate may also be used to characterize the inhibition performance of shale inhibitors.
Measurement method
Weighing 10g (accurate to 0.01g) of calcium bentonite which is sieved by a 0.125mm standard sieve, dried for 4h at 105 +/-3 ℃, cooled to room temperature, filling into a measuring cylinder, inserting a plug rod into the measuring cylinder, and keeping for 5min under the pressure of 4MPa to prepare the test core. And (3) mounting the measuring cylinder with the core on an NP-02A type shale expansion tester, injecting a sample solution into the measuring cylinder, soaking the core for 8 hours, recording the linear expansion amount of the core, and simultaneously using distilled water for a blank test.
Formula for calculation
In the formula:
b-core relative expansion reduction,%;
delta H is the linear expansion amount of the core after the sample solution is soaked for 8 hours, and is mm.
TABLE 3 shale swell reduction ratio comparison of amine-based inhibitor samples
| Sample (I) | Shale expansion reduction rate |
| Amino inhibitors 1 | 62.3 |
| Amino inhibitors 2 | 66.7 |
| Amino inhibitors 3 | 62.8 |
| Amino inhibitors 4 | 66.4 |
| Amine-based inhibitors 5 | 69.7 |
| Amine-based inhibitors 8 | 79.1 |
| Amino group inhibitionAgent 10 | 74.5 |
| Amine-based inhibitors 11 | 75.6 |
| Trimethyl ammonium chloride | 54.5 |
| Choline chloride | 58.7 |
| Allyl anhydroglycerol ether | 55.7 |
Note: generally, the shale expansion reduction rate is more than or equal to 50, and the shale is qualified product.
Trimethyl ammonium chloride and choline chloride are conventional monomer amine inhibitors, the shale expansion reduction rate of which is more than 50 percent, and the common requirements can be met.
As can be seen from the data in Table 3, the amine-based inhibitors prepared in the examples of the present application have superior inhibitory properties to conventional monomeric amine-based inhibitors. Moreover, as can be seen from the results of the shale expansion reduction rate of the amine inhibitor 2 and the amine inhibitor 4, when triethanolamine is not included in the polyalcohol amine, the chloroacetic acid compound is added into the reaction system, the carboxyl group is introduced, and the chloroacetic acid compound and the alcoholic hydroxyl group in the polyalcohol amine are jointly used as hydrophilic groups, so that the inhibition performances of the two groups are not obviously different.
As can be seen from the results of shale expansion reduction rate of the amine-based inhibitor 4 and the amine-based inhibitor 5, the inhibition performance of the amine-based inhibitor 5 is better than that of the amine-based inhibitor 4.
As can be seen from the results of shale expansion reduction rate of the amino inhibitor 5 and the amino inhibitor 8, the alkenyl polyether polymer is added into the polyallyl ammonium chloride for compounding, and the prepared amino inhibitor has the effect of synergistically improving the inhibition performance of the amino inhibitor between the polyallyl ammonium chloride and allyl dehydrated glycerol ether.
As can be seen from the results of shale expansion reduction rates of the amino inhibitor 8, the amino inhibitor 10 and the amino inhibitor 11, when the alkenyl polyether polymer accounts for 10-30% of the weight of the amino inhibitor, the prepared amino inhibitor has better inhibition performance.
Effect example 4Performance of water-based drilling fluid systems
Control system: a control was prepared using a water-based drilling fluid without the addition of an amine-based inhibitor.
System 1: the water-based drilling fluid system of example 12.
System 2: the water-based drilling fluid system of example 12.
The viscosity, Plastic Viscosity (PV), yield value (YP), and shale expansion reduction rate were measured for the control system, system 1, and system 2, respectively.
From the rheological properties, the three-group system remained essentially stable before and after hot rolling. Compared with a control group, the shale expansion reduction rate of the water-based drilling fluid system prepared by the embodiment of the application is respectively increased by 9.2% and 10.6%. The water-based drilling fluid system of the control group is a common system, can be used in drilling construction and has certain inhibition performance. The system 1 and the system 2 in the embodiment of the application can improve the shale expansion reduction rate by about 10% on the basis of the control group, which shows that the amine inhibitor in the embodiment of the application can obviously improve the inhibition of the system and has better compatibility.
The same and similar parts in the various embodiments in this specification may be referred to each other. The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention.
Claims (10)
1. An amino inhibitor for a water-based drilling fluid, which is characterized by comprising polyalkyl ammonium chloride, wherein the polyalkyl ammonium chloride at least comprises a compound 1 shown in a formula I:
the polyalkyi alcohol acid propyl ammonium chloride at least comprises a compound 2 shown in a formula II and a compound 3 shown in a formula III:
wherein R1 is-CH2CH2OH or H;
in compound 1, R2 is
In compound 2, R2 is
R3 is
2. The amine-based inhibitor for water-based drilling fluids of claim 1 wherein when the polyallyl ammonium chloride comprises a compound of formula I, the polyallyl ammonium chloride further comprises a compound 4 of formula IV:
wherein R3 is
3. The amine-based inhibitor for the water-based drilling fluid as claimed in claim 1 or 2, further comprising an alkenyl polyether polymer, wherein the alkenyl polyether polymer comprises one or more of allyl dehydrated glycerol ether, polyethylene glycol monoallyl ether and polypentaerythritol allyl ether.
4. The amine-based inhibitor for the water-based drilling fluid according to claim 3, wherein the weight fraction of the alkenyl polyether polymer is 10 wt% to 30 wt% based on the total weight of the amine-based inhibitor.
5. The preparation method of the amino inhibitor for the water-based drilling fluid is characterized by comprising the following steps of:
mixing polyalcohol amine with a chloropropane compound, and reacting to obtain polyallyl alcohol acid propyl ammonium chloride;
wherein the polyalcohol amine comprises triethanolamine and optional ethanolamine and/or diethanolamine, and the chloropropane compounds are selected from one or more of methyl epichlorohydrin, trichloropropane, 2-methyl-2-chloropropane and 2-methyl-1-chloropropane;
the polyalkyi alcohol acid propyl ammonium chloride at least comprises a compound 1 shown in the following formula I:
the polyalkyi alcohol acid propyl ammonium chloride at least comprises a compound 2 shown in a formula II and a compound 3 shown in a formula III:
wherein R1 is-CH2CH2OH or H;
in compound 1, R2 is
In compound 2, R2 is
R3 is
6. The method for preparing the amine-based inhibitor for the water-based drilling fluid according to claim 5, further comprising the following steps:
uniformly mixing polyalkyi alcohol acid propyl ammonium chloride with alkenyl polyether polymer to obtain an amino inhibitor;
the alkenyl polyether polymer comprises one or more of allyl dehydrated glycerol ether, polyethylene glycol monoallyl ether and polypentaerythritol allyl ether.
7. The preparation method of the amine-based inhibitor for the water-based drilling fluid, according to claim 5, is characterized in that the weight ratio of the polyalcohol amine to the chloropropane compounds is (1-2) to 1.
8. The preparation method of the amino inhibitor for the water-based drilling fluid is characterized by comprising the following reaction steps of:
adding polyalcohol amine into chloroacetic acid compounds to obtain a first intermediate;
adding chloropropane compounds into the first intermediate, and reacting to obtain polyaluminium propyl alcohol acid ammonium chloride;
wherein the polyalcohol amine is selected from one or more of triethanolamine, ethanolamine and diethanolamine, the chloroacetic acid compound is selected from one or more of chloroacetic acid, 2-chlorphenyl aminoacetic acid and p-chlorophenoxyacetic acid, and the chloropropane compound comprises one or more of epichlorohydrin, methyl epichlorohydrin, trichloropropane, 2-methyl-2-chloropropane and 2-methyl-1-chloropropane;
the polyalkyi alcohol acid propyl ammonium chloride at least comprises a compound 1 shown in the following formula I:
the polyalkyi alcohol acid propyl ammonium chloride at least comprises a compound 2 shown in a formula II and a compound 3 shown in a formula III:
wherein R1 is-CH2CH2OH or H;
in compound 1, R2 is
In compound 2, R2 is
R3 is
9. The method for preparing the amine-based inhibitor for the water-based drilling fluid according to claim 8, further comprising the following steps:
uniformly mixing polyalkyi alcohol acid propyl ammonium chloride with alkenyl polyether polymer to obtain an amino inhibitor;
the alkenyl polyether polymer comprises one or more of allyl dehydrated glycerol ether, polyethylene glycol monoallyl ether and polypentaerythritol allyl ether.
10. An aqueous drilling fluid system comprising the amine-based inhibitor of any of claims 1-4, the aqueous drilling fluid system comprising the following components in weight percent:
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