CN106398664B - Clay stabilizer and preparation method thereof - Google Patents
Clay stabilizer and preparation method thereof Download PDFInfo
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- CN106398664B CN106398664B CN201610807359.9A CN201610807359A CN106398664B CN 106398664 B CN106398664 B CN 106398664B CN 201610807359 A CN201610807359 A CN 201610807359A CN 106398664 B CN106398664 B CN 106398664B
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
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- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
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- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
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Abstract
The invention discloses a clay stabilizer, which is tetrachloro pentaerythritol tetra (triethylammonium) acetate obtained by the reaction of pentaerythritol chloroacetate and triethylamine. The invention also correspondingly discloses a preparation method of the clay stabilizer, which has the advantages of simple synthesis method, high synthesis yield, good anti-swelling effect and strong scouring resistance.
Description
Technical Field
The invention relates to a clay stabilizer for water injection in oil exploitation.
Background
At present, most of oil exploitation in China is water injection exploitation, and clay minerals in a stratum can expand and disperse when meeting water-based substances in the oil field exploitation process, so that the permeability of the reservoir is reduced, and the oil and gas reservoir is damaged. In order to protect the permeability of an oil-gas layer, a clay stabilizer is added into various water-based working fluids, so that the damage of clay to the oil-gas layer can be effectively inhibited. Cations electrolyzed by the clay stabilizer in a water-based substance can be adsorbed on the surfaces of clay particles through electrostatic action to reduce the electronegativity of the clay particles, and can also be coated on the surfaces of the clay particles to inhibit the clay swelling.
The clay stabilizer commonly used in the oil field at present mainly comprises inorganic salt clay stabilizer and organic cation clay stabilizer. The inorganic salt clay stabilizer has higher initial anti-swelling rate but poorer scouring resistance, and the anti-swelling effect is only temporary; the organic cation clay stabilizer has long-acting property and can stabilize clay for a long time. However, for low permeability reservoirs, cationic polymers of relatively large molecular mass can exacerbate damage to field permeability. In the face of complicated and variable stratum conditions, more and more scientific researchers put forward the use of organic cation clay stabilizers with medium and small molecular mass.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a clay stabilizer which has a dendritic structure, high charge density, strong adsorption bridging effect, good anti-expansion performance and small molecular weight, and is not easy to cause secondary damage to a low-permeability oil layer.
The invention also correspondingly provides a preparation method of the clay stabilizer.
The technical scheme adopted by the invention for solving the technical problems is as follows:
pentaerythritol tetra (triethylammonium) acetate (hereinafter referred to as PE-3) having a structural formula:
the reaction formula is as follows:
。
a preparation method of a clay stabilizer comprises the steps of mixing pentaerythritol chloroacetate and acetonitrile, adding triethylamine, refluxing and stirring, and protecting with nitrogen in the reaction process to obtain a reaction product.
Preferably, the solvent is subjected to a water removal operation.
Preferably, after the reaction is finished, the product is centrifuged to obtain the final product. By centrifugal separation, the product can be separated quickly to prevent oxidation of the product due to long-term contact with air.
Preferably, the product is washed by the solvent for multiple times, and is subjected to vacuum filtration under the protection of nitrogen, and the obtained product is dried in vacuum.
More preferably, the reaction conditions are: the reaction temperature is as follows: the reaction time is as follows at 78-90 deg.C: 3.8-6 h, n (triethylamine): n (pentaerythritol tetrachloroacetate) is 4.6-6.0, and the usage amount of acetonitrile solvent is 45-85%.
More preferably, the reaction conditions are: the reaction temperature is 82 ℃, the reaction time is 4 hours, n (triethylamine) = n (pentaerythritol tetrachloroacetate) =5.2:1, and the solvent acetonitrile accounts for 65 percent of the total mass of the reaction system.
The advantages of the present invention are illustrated in detail by examples.
Drawings
FIG. 1 is a graph showing the effect of reaction temperature on yield in examples of the present invention.
FIG. 2 is a graph showing the effect of reaction time on yield in examples of the present invention.
FIG. 3 is a graph showing the effect of the ratio of the amount of the starting material on the yield in the example of the present invention.
FIG. 4 is a graph showing the effect of the amount of solvent added on the yield in examples of the present invention.
FIG. 5 is a graph of an infrared spectrum of a product in an example of the invention.
FIG. 6 is a drawing of a product in an embodiment of the invention1HNMR spectrogram.
FIG. 7 is a graph of the anti-swelling rate of the product according to the example of the invention as a function of concentration.
FIG. 8 is a graph of the percent swell as a function of concentration for the formulated product of this example of the invention.
Detailed Description
The invention is further described with reference to the following embodiments.
Preparation of a clay stabilizer: putting pentaerythritol tetrachloracetate and a certain amount of dried polar solvent into a three-neck flask, adding triethylamine, refluxing and stirring for a certain time, and protecting with nitrogen gas in the reaction process. After completion of the reaction, the resultant was centrifuged for 20min, and the upper yellow liquid was decanted. And (5) repeatedly using the anhydrous solvent to flush the product, and performing reduced pressure suction filtration under the protection of nitrogen. Finally, the obtained product is put into a vacuum drying oven and dried at 50 ℃ for standby.
The preparation conditions were investigated by the following examples:
1 Effect of solvent type on product yield
Selecting solvents with different polarities and different boiling points, and inspecting the influence of the types of the solvents on the product yield. The fixed reaction conditions were reaction temperature T =80 ℃, reaction time T =6h, n (triethylamine): n (pentaerythritol chloroacetate) is 5.2:1, and the addition amount of the solvent accounts for w% of the reaction raw materials by weight percent (= 65%). The kind of the reaction solvent was changed to examine the influence on the product yield. The measurement results are shown in table 1.
TABLE 1 influence of reaction solvent type on product yield
| Solvent(s) | Isopropanol (I-propanol) | Ethanol | N-propanol | Acetonitrile | Petroleum ether | Acetone (II) |
| Yield/% | 49.18 | 21.21 | 35.21 | 83.8 | - | - |
As can be seen from table 1, the product yield was higher when acetonitrile was used as the solvent. When alcohols are used as solvents, the post-treatment is complicated and the product loss is high due to the high water content and the high solubility of the product in alcohols and water. When solvents such as petroleum ether, acetone and the like are used, the viscosity is high in the reaction process due to the solubility problem, the whole system presents a mass of viscous paste after reduced pressure distillation, great difficulty is brought to product purification, and a pure product is difficult to obtain.
The most suitable solvent is acetonitrile, and it is dried before use.
2 Effect of reaction temperature on product yield
The fixed reaction conditions were reaction time t =4h, n (triethylamine): n (pentaerythritol chloroacetate) =5.2:1, and the solvent addition accounts for w% =65% of the reaction raw materials, and the influence of the reaction temperature on the product yield is examined by changing the reaction temperature. The results are shown in FIG. 1.
As can be seen from FIG. 1, the reaction yield increased with the increase of the reaction temperature, and reached a maximum value at a reaction temperature of 82 ℃. This indicates that the activation energy of the reaction is large, and increasing the temperature is favorable for the reaction to proceed to the right, increasing the product yield. When the quaternization temperature is lower, the molecular activity degree is obviously reduced compared with that under the high temperature condition, and the quaternization reaction is incomplete. When the reaction temperature is further increased, the triethylamine is oxidized more rapidly, the solution color is deepened, and byproducts are increased continuously, so that the yield of the quaternary ammonium salt is reduced.
In summary, suitable reaction temperatures are: 78-90 ℃, and the optimum reaction temperature is as follows: and (2) 82 ℃.
3 Effect of reaction time on product yield
The fixed reaction conditions were reaction temperature T =82 ℃, n (triethylamine): n (pentaerythritol chloroacetate) =5.2:1, and the solvent addition accounts for w% of the reaction raw materials by weight% = 65%. The reaction time was varied and the effect on the product yield was examined, and the results are shown in FIG. 2.
As can be seen from FIG. 2, the yield of the product continuously increased with the increase of the reaction time, and when the reaction time reached 4h, the product yield reached the maximum value, indicating that the reaction was completed within 4h under reflux. As the reaction time is further extended, part of the quaternary ammonium salt may be oxidized or decomposed, resulting in a decrease in product yield.
In summary, suitable reaction times are: 3.8-6 h, the optimum reaction temperature is as follows: and 4 h.
4 influence of molar ratio of starting Material on product yield
The reaction conditions were set to a reaction temperature T =82 ℃, a reaction time T =4h, and the solvent addition amount was w% =65% of the reaction raw material percentage. The molar ratio of the raw materials is changed, and the influence of the raw materials on the product yield is inspected. The results are shown in FIG. 3.
As can be seen from fig. 3, when n (triethylamine): when n (pentaerythritol chloroacetate) is less than 4.6:1, the reaction solution is weak in alkaline environment, so that the product yield is low; the product yield is continuously improved along with the increase of the molar ratio of the raw materials; when n (triethylamine): when n (pentaerythritol chloroacetate) is increased to 5.2:1, the product yield reaches the maximum value; further increases the content of triethylamine, and reduces the yield of the product.
Thus, a suitable n (triethylamine): n (pentaerythritol tetrachloroacetate) is 4.6-6.0:1, preferably 5.2: 1.
Influence of the amount of solvent on the product yield
The fixed reaction conditions were reaction temperature T =82 ℃, reaction time T =4h, n (triethylamine): n (pentaerythritol chloroacetate) = 5.2. The influence of the amount of the solvent on the product yield was examined, and the results are shown in FIG. 4.
As can be seen from fig. 4, the product yield increased with the increase in the amount of solvent used. When the solvent dosage is higher than 65%, the concentration of triethylamine and pentaerythritol chloroacetate is reduced, the reaction rate is reduced, and the product yield is reduced.
Therefore, the appropriate solvent dosage is 45-85%, and the optimal solvent addition amount is w% = 65%.
By combining the experimental results, the optimal synthesis process conditions obtained by taking the reaction yield as an index are as follows: the reaction temperature is 82 ℃, the reaction time is 4 hours, n (triethylamine) = n (pentaerythritol tetrachloroacetate) =5.2:1, the solvent acetonitrile accounts for 65% of the total mass of the reaction system, and the product yield is 96.5% under the condition.
II, determination of reaction products
1. The respective reaction products obtained under the above-mentioned suitable reaction conditions were analyzed by the following methods to determine the structures of the products:
(1) the product was ground in an agate mortar and subjected to infrared spectroscopic analysis by KBr pellet method using a Spectrum one infrared spectrometer from Perkin Elmer corporation for pentaerythritol tetra (triethylammonium) acetate (PE-3).
(2) Selecting CDCl3As a solvent, the PE-3 product was subjected to NMR spectroscopy using a Bruker AMX-400 NMR spectrometer, model Bruker, Switzerland, and the structure of the product was finally determined.
2. The products meeting the requirements obtained in the above reactions were analyzed by infrared spectroscopy (FT-IR), and the IR spectra are shown in fig. 5.
2900 cm can be found by analysis of spectrogram 5-1、2850 cm-1Nearby is respectively-CH3，-CH2Absorption peak of stretching vibration of C-H in-1460 cm-1、1408 cm-1Are respectively-CH3，-CH2Flexural vibration absorption Peak of-Medium C-H, 1746 cm-1The absorption peak of ester carbonyl group stretching vibration is 1114 cm-1And 1230 cm-1The vicinity is a C-O-C stretching vibration absorption peak in COO-. According to the result of map analysis, each group in the map is identical with the structure of the target product.
3. The satisfactory products obtained in the above reactions were analyzed by nuclear magnetic resonance, and the results are shown in FIG. 6.
As can be seen from fig. 6, δ =5.24 ppm (8H) is-CH attached to an oxygen atom2-middle hydrogen proton peak, δ =4.47ppm (8H) is-CH attached to carbonyl2-middle hydrogen proton peak, δ =3.75 ppm (24H) is-CH attached to N atom2-medium hydrogen proton peak, δ =1.46 ppm (36H) is-CH3Hydrogen proton peak of (1). The number ratio of four hydrogen atoms is 1:1:3:4.5, which is consistent with the target product.
Performance of three products
1. Evaluation of anti-swelling Properties
Under the laboratory conditions, the anti-swelling rate of the product is determined by referring to the centrifugal method of SY/T5971-94 'evaluation method of performance of clay stabilizer for water injection', and the anti-swelling performance of the product obtained under the reaction conditions is tested.
At room temperature (20 ℃), PE-3, KCl, NH4Cl, CHPTAC (small cationic species) produced by Toyobo Fine chemical Co., Ltd, and HuabinI (cationic polymer species) produced by Huabin chemical Co., Ltd in Shengli oil field were tested at different concentrations by centrifugation, and the results are shown in FIG. 7.
As can be seen from FIG. 7, the anti-swelling ratio is continuously increased with the increase of the used concentration of the stabilizer: when the concentration is lower than 1%, the anti-swelling rate is increased at a higher rate; at concentrations above 1%, the rate of increase in the anti-swelling rate tends to be moderate. When the mass concentration of PE-3 is increased to 1%, the anti-swelling rate reaches 90.7%, and the field requirement is met. At the concentration, the PE-3 anti-swelling performance is slightly poorer than that of the inorganic salt anti-swelling agent, but is higher than that of other organic anti-swelling agents; at a mass concentration of 2%, the anti-swelling ratio is 95.4%, and NH4Cl has equivalent anti-swelling effect. The result shows that the quaternary ammonium salt obtained by the reaction has better anti-swelling effect, the anti-swelling effect and the economic cost are comprehensively considered, and the optimal addition amount of the clay stabilizer PE-3 is 1%.
2. Evaluation of scouring resistance
Taking 6 graduated centrifuge tubes, putting 0.5g of bentonite into the centrifuge tubes, adding products with different mass fractions, standing for 2h at room temperature (20 ℃), and measuring and recording the anti-swelling rate by using a centrifugal method. And then pouring out the upper clear liquid, adding a certain amount of deionized water, testing once every 2h, calculating the anti-swelling rate of each test, and simultaneously comparing the anti-swelling rate with the anti-scouring performance of other common inorganic and organic clay stabilizers, wherein the experimental results are respectively shown in tables 2 and 3.
As can be seen from Table 2, the anti-swelling rate of the experimental product is always maintained at a high level through multiple washing and scouring under different concentrations, and the change of the anti-swelling rate is small compared with the initial anti-swelling rate, which shows that the synthetic product has good inhibition on scouring of injected water, namely the clay stabilizer has good long-term effect and can be used in actual water injection operation.
As shown in Table 3, when the concentration is 1%, the product PE-3 has the scouring resistance and inorganic salt (NH)4Cl, KCl), small cations (commercially available CHPTAC), cationic polymers (commercially available capene I) were significantly improved. For analysis reasons, on one hand, the product contains four ammonium ions in the molecular structure, the higher charge density can effectively neutralize the electronegativity of the clay,so that the ion exchange membrane has better ion exchange capacity; on the other hand, the dendritic structure of the quaternary ammonium salt can be adsorbed on the surface of the clay particles through the adsorption bridging effect, so that the contact between water molecules and the clay particles is effectively prevented. Therefore, the composite material has higher expansion prevention rate and long-term effect and can meet the requirement of oil field production.
TABLE 2 flushing resistance of different concentrations of PE-3
TABLE 3 scouring resistance of different clay stabilizers
In conclusion, the product obtained by the reaction is a cationic clay stabilizer with a dendritic structure, and has the advantages of simple synthesis method, high synthesis yield, good anti-swelling effect and strong scouring resistance.
Fourthly, compound composition and effect
Because the inorganic salt has good anti-swelling effect and low price, the inorganic salt clay stabilizer is mainly used in the initial stage of oil field production. But it has a short period of inhibiting clay swelling and also causes a certain harm to the environment. The research of the invention obtains that PE-3 is respectively reacted with KCl and NH4Cl and investigating the anti-swelling rate and the flushing resistance of a compounded product.
1 measurement of anti-swelling Rate
Reacting PE-3 with NH4Cl or KCl is compounded according to the mass ratio of 1:1, the anti-swelling rates of the Cl or KCl under different concentrations are respectively tested, and the results are compared with the effects before compounding, and are shown in figure 8.
As can be seen from FIG. 8, the anti-swelling rate of each product was positively correlated with the concentration of each product used. In addition, the anti-swelling rate of the compound clay stabilizer is improved compared with that of PE-3 before compounding under various use concentrations, which shows that the PE-3 and inorganic salts have a compounding effect. Wherein, PE-3 and NH4The Cl has better compounding effect, and the anti-swelling rate reaches 93.6 percent when the dosage of the compound is 1 percent.
2 evaluation of washing resistance and washing resistance
At the mass concentration of 1%, the PE-3 and NH are mixed4Cl and KCl are compounded according to different mass ratios, then the washing resistance and scouring resistance of the mixture are tested, the comprehensive anti-swelling effect of the mixture is inspected, and the result is shown in tables 4 and 5.
TABLE 4 PE-3 and NH4Washing resistance of clay stabilizer after Cl compounding
As can be seen from tables 4 and 5, the ratio by mass of the components in the range of 3:1 to 1:3, the initial anti-swelling rate of the compound clay stabilizer is higher than that of PE-3. Although the scouring resistance of the composite clay stabilizer is a little lower than that of PE-3, NH is compared with that of the inorganic salt4The scouring resistance of Cl or KCl is greatly enhanced, the comprehensive anti-swelling effect is better, and the purpose of compounding and enhancing the effect is achieved.
TABLE 5 Wash resistance of Clay stabilizers after PE-3 compounding with KCl
Claims (7)
1. A clay stabilizer suitable for a hypotonic oil layer is characterized in that: which is tetrachloro pentaerythritol tetra (triethylammonium) acetate obtained by the reaction of pentaerythritol chloroacetate and triethylamine.
2. A preparation method of a clay stabilizer suitable for a hypotonic oil layer comprises the steps of mixing pentaerythritol chloroacetate and acetonitrile, adding triethylamine, refluxing and stirring, and protecting with nitrogen in the reaction process to obtain a reaction product; the reaction conditions are as follows: the reaction temperature is as follows: the reaction time is as follows at 78-90 deg.C: 3.8-6 h, n (triethylamine): n (pentaerythritol chloroacetate) is 4.6-6.0, and the dosage of acetonitrile serving as a solvent is as follows: 45-85 percent; the solvent is first subjected to a water removal operation.
3. The method for preparing a clay stabilizer for hypotonic oil layer according to claim 2, wherein: the reaction temperature is 82 ℃, the reaction time is 4 hours, n (triethylamine) = n (pentaerythritol tetrachloroacetate) =5.2:1, and the solvent accounts for 65% of the total mass of the reaction system.
4. A method of preparing a clay stabilizer for hypotonic oil layer according to claim 3, wherein: after the reaction, the product was centrifuged.
5. A method of preparing a clay stabilizer for hypotonic oil layer according to claim 3, wherein: and washing the product by using a solvent for multiple times, carrying out reduced pressure suction filtration under the protection of nitrogen, and finally carrying out vacuum drying.
6. A clay stabilizer suitable for hypotonic oil layer contains pentaerythritoltetrakis (triethylammonium) acetate tetrachloride and NH4Cl in a weight ratio of 3:1 to 1: 3.
7. a clay stabilizer suitable for use in hypotonic oil layers comprising pentaerythritol tetra (triethylammonium) acetate tetrachloride and KCl in a ratio of 3:1 to 1: 3.
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| CN103820097A (en) * | 2014-02-13 | 2014-05-28 | 东方宝麟科技发展(北京)有限公司 | Reagent for fracture of shale oil and gas well and product thereof |
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| CN102952023A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Star-shaped hydrate anti-agglomerant and its preparation method |
| CN103820097A (en) * | 2014-02-13 | 2014-05-28 | 东方宝麟科技发展(北京)有限公司 | Reagent for fracture of shale oil and gas well and product thereof |
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