CN109111906B - Thick oil emulsifying viscosity reducer - Google Patents
Thick oil emulsifying viscosity reducer Download PDFInfo
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Abstract
The invention discloses a thick oil emulsifying viscosity reducer which consists of a nonionic surfactant, a cationic oligomeric surfactant, a high molecular polymer and water, wherein the cationic oligomeric surfactant is selected from compounds shown in a structural formula in a formula (I), wherein R is C4～C18Alkyl groups of (a); x is selected from F‑、Cl‑、Br‑、I‑One or more than two of them. The emulsifying viscosity reducer has strong capability of reducing the tension of an oil-water interface, has better viscosity reduction and emulsification effects on thick oil, is particularly suitable for thick oil with high wax content, has strong salt resistance, low use concentration and lower cost, does not need to add alkali when in use, and is suitable for alkali-sensitive strata.
Description
Technical Field
The invention relates to a thick oil emulsifying viscosity reducer, in particular to a thick oil emulsifying viscosity reducer containing a specific cationic type oligomeric surfactant.
Background
The emulsification viscosity reduction technology is a commonly used technology for exploiting thick oil at present due to the characteristics of strong field implementation operability, flexible and various technologies, strong environmental adaptability and the like. The technology mainly reduces the tension of an oil-water interface by the adsorption of the emulsification viscosity reducer on the oil-water interface, so that the thick oil is converted into an oil-in-water emulsion from a water-in-oil emulsification state, the viscosity is greatly reduced, and normal exploitation is realized.
In recent years, the proportion of heavy oil recovery in the whole oil recovery is gradually increased, the geological conditions are increasingly complicated, the use effect of the emulsifying viscosity reducer is influenced by the physical properties of the heavy oil and the formation conditions, the addition of the emulsifying agent is increased due to the complicated formation conditions, the viscosity reducing effect is correspondingly poor and even fails, and the cost is greatly increased. In general, alkali is added into the emulsifying viscosity reducer to reduce the dosage of the external surfactant, but the emulsifying viscosity reducer is not suitable for alkali-sensitive formations. On the other hand, the existing thick oil emulsifying viscosity reducer mainly comprises an anionic surfactant, a nonionic surfactant, a cosurfactant and the like, is suitable for common thick oil and super thick oil systems, has a good viscosity reducing effect, but has poor adaptability to special thick oil with high wax content, and is not suitable for thick oil emulsifying viscosity reduction of high calcium magnesium ion-containing formation water. Therefore, at present, a thick oil emulsifying viscosity reducer which has the advantages of pertinently reducing the viscosity of thick oil with high wax content, having high salt resistance (including calcium and magnesium ions), having low use concentration, being free from alkali addition, being suitable for alkali-sensitive stratum and the like is needed.
CN102618245A discloses a novel emulsification viscosity reducer, which is prepared by mixing the following raw materials in parts by weight: 63-65 parts of petroleum sulfonate, 9-15 parts of anionic surfactant and 20-30 parts of pH value regulator, wherein the pH value regulator is prepared from caustic soda and water in a weight ratio of 50: 50 by mixing. The method has the advantages of wide application range of the thick oil, high mineral salt resistance, capability of converting the thick oil from a water-in-oil emulsified state into an oil-in-water emulsion, low viscosity of the emulsified thick oil, low emulsification cost and the like, and is suitable for the thick oil with the viscosity lower than 2400mPa.s and the thick oil with the viscosity higher than 2400 mPa.s. The viscosity reducer comprises sodium dodecyl sulfate, sulfonate anionic surfactant, alkylbenzene sulfonate anionic surfactant and carboxylate anionic surfactant. The viscosity reducer can realize the emulsification and viscosity reduction of common thick oil and ultra-thick oil under the condition that the mineralization degree is 20000 mg/L.
CN106032466A discloses a thick oil emulsifying viscosity reducer, which comprises a nonionic surfactant, an anionic oligomeric surfactant, alcohol and water, has a good viscosity reducing effect on super-extra thick oil and thick oil with high asphalt content, and is suitable for mineralized water with a mineralization degree of 50000mg/L and a calcium and magnesium ion concentration of not more than 2000 mg/L. On the other hand, the viscosity reducer has low use concentration and low cost, and does not need to add alkali when in use.
CN 106398675a discloses an emulsifying viscosity reducer, which contains a cationic surfactant, a nonionic surfactant, an alcohol and a high molecular polymer. Also discloses a preparation method of the emulsifying viscosity reducer and application of the emulsifying viscosity reducer in thick oil emulsifying viscosity reduction. Also discloses a method for emulsifying and reducing the viscosity of the thick oil by adopting the emulsifying viscosity reducer. The emulsifying viscosity reducer can effectively reduce the viscosity of the thick oil, is particularly suitable for the thick oil with high wax content, can also be applied to common thick oil and super thick oil with low wax content, and has excellent adaptability to the thick oil of formation water containing high calcium and magnesium ions. The used cationic surfactant is selected from dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride, but the compound system needs to be added with alcohol, and the viscosity reduction effect is reduced when the alcohol content is low.
Disclosure of Invention
Aiming at the prior art, the invention provides a thick oil emulsifying viscosity reducer which has a good viscosity reducing effect on high-wax-content thick oil. And the viscosity reduction effect similar to that of a single-chain surfactant can be achieved under the condition of lower concentration, the cost is low, alkali does not need to be added when the viscosity reduction agent is used, and the viscosity reduction agent is suitable for alkali-sensitive strata.
The invention is realized by the following technical scheme:
the thick oil emulsifying viscosity reducer consists of non-ionic surfactant 0.01-1 wt%, cationic oligomer surfactant 0.02-3 wt%, polymer 0.01-1 wt% and water for the rest.
The nonionic surfactant is selected from alkylphenol polyoxyethylene ether and/or alkyl alcohol polyoxyethylene ether.
The cationic oligomeric surfactant is selected from one or more than two of a compound A, a compound B and a compound C; the structural formulas of the compound A, the compound B and the compound C are respectively shown as (a), (B) and (C) in the formula (I); in the formula (I), R is C4～C18Is preferably C8～C16Alkyl groups of (a); x is selected from F-、Cl-、Br-、I-One or more than two of them.
The three compounds of the structure shown in formula (I) are all self-made in the laboratory, and the Preparation method is the synthesis method in the following literature (Preparation, Characterization and Properties of Novel Cationic GeminiSurfactants with structured amino Spacers group.J. surfactants Deerg.2016, (1): 91-99). Specifically, the compound is synthesized with high yield by using DL-dimethyl malate, trimethyl citrate or ethylene diamine tetraacetic acid as main raw materials through two-step reaction.
The high molecular polymer is selected from one or more of polyacrylamide, xanthan gum, hydroxypropyl guar gum, carboxymethyl cellulose and polyvinyl alcohol.
Further, the polymerization degree of the alkylphenol polyoxyethylene ether and/or the alkyl alcohol polyoxyethylene ether is 3-30, and the alkyl chain length is 6-20. For example, the series products such as nonylphenol polyoxyethylene ether series NP-7, NP-10 and NP-15 produced by Jiangsu Heian petrochemical plant or fatty alcohol polyoxyethylene ether AEO-7, AEO-9 and AEO-13 can be selected.
Preferably, the viscosity average molecular weight of the polyacrylamide is 400 × 104～3000×104。
Preferably, the nonionic surfactant accounts for 0.04-0.3%, the cationic oligomeric surfactant accounts for 0.05-1.5%, the high molecular polymer accounts for 0.04-0.3%, and the balance is water.
The preparation method of the thick oil emulsifying viscosity reducer comprises the following steps: completely dissolving the nonionic surfactant, the cationic oligomeric surfactant and the high molecular polymer in water (the specific dissolving mode has no special requirement, and various modes can be adopted by those skilled in the art) to obtain the cationic oligomeric surfactant.
Further, the preparation method comprises the following steps: under the condition of mechanical stirring, adding high molecular polymer into partial water, stirring until the high molecular polymer is fully dissolved, then adding a nonionic surfactant and a cationic oligomeric surfactant, adding the balance of water, and stirring until the high molecular polymer is fully dissolved.
The thick oil emulsifying viscosity reducer can effectively reduce the viscosity of thick oil with high wax content, has good salt resistance, and has good adaptability to thick oil of formation water with high calcium and magnesium ions; the viscosity reducer has the advantages of low dosage (the dosage of the viscosity reducer is more than 20 percent of the viscous oil when the viscosity reducer is used for reducing the viscosity of the viscous oil, preferably 20 to 70 percent), low use concentration, low cost, no need of adding alkali, and suitability for alkali-sensitive stratum.
In the present invention, the stirring is generally performed at a rotation speed of 200 to 400 rpm. The part of water is 1/3-2/3 of the total amount of water. The conditions for fully dissolving the high molecular polymer are as follows: stirring for 3-5 hours at normal temperature, for example, 15-30 ℃; the conditions of stirring to complete dissolution after adding other components are as follows: generally, the mixture is stirred for 20-30 min at normal temperature, for example, 15-30 ℃.
All documents cited herein are incorporated by reference in their entirety and to the extent such documents do not conform to the meaning of the present invention, the present invention shall control. Further, the various terms and phrases used herein have the ordinary meaning as is well known to those skilled in the art.
Detailed Description
The present invention will be further described with reference to the following examples. However, the scope of the present invention is not limited to the following examples. It will be understood by those skilled in the art that various changes and modifications may be made to the invention without departing from the spirit and scope of the invention.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
EXAMPLES preparation of an emulsifying viscosity reducer
Under the mechanical stirring conditions of normal temperature (15-30 ℃) and rotation speed of 200-400 rpm, adding the high molecular polymer into water with total water amount of 1/3-2/3, and stirring for 3-5 hours until the polymer is fully dissolved; and then adding a nonionic surfactant and a cationic oligomeric surfactant, adding the balance of water, stirring for 20-30 min until the surfactant is completely dissolved, and preparing the emulsifying viscosity reducer.
The composition of the emulsification viscosity reducer in each example and comparative example (cationic single-chain surfactant replaces cationic oligomeric surfactant, no cationic oligomeric surfactant or high molecular polymer is added, or neither cationic single-chain surfactant or high molecular polymer is added) is shown in table 1, wherein R is straight-chain alkyl.
TABLE 1 compositions of emulsifying viscosity reducer in examples and comparative examples
Test example thick oil emulsification viscosity reduction test
Two kinds of high wax content thick oil are selected as the oil for the test. The thick oil A is the wax-containing thick oil of the original oilfield (the viscosity is 98000mPa.s at 50 ℃, the wax content is 13 percent, and the wax content in the crude oil is determined according to SY/T0537-2008); the thick oil B is the wax-containing thick oil (viscosity 9630mPa.s at 50 ℃ and wax content 25%) of the Jiangsu oilfield. The viscosity reduction process comprises: in a beaker, a certain mass of the emulsification viscosity reducer in the above examples or comparative examples is added into a certain mass of test oil, the beaker is placed in a water bath at 50 ℃ for constant temperature for 2h, stirred for 10min, the thick oil emulsification shape is observed, and then the viscosity is measured at 50 ℃.
In order to test the salt resistance of the emulsifying viscosity reducer, when a thick oil B emulsifying viscosity reduction performance test is carried out, water in the viscosity reducer preparation method is mineralized water with the mineralization degree of 160000mg/L, wherein Ca2+The concentration is as follows: 10000Mg/L, Mg2+The concentration is as follows: 10000 mg/L; when thick oil A emulsification viscosity reduction performance test is carried out, deionized water is selected as water in the viscosity reducer preparation method, the mineralization degree is 0mg/L, wherein Ca2+The concentration is as follows: 0Mg/L, Mg2+The concentration is as follows: 0 mg/L.
In the test example, for convenience of comparison, the dosage of the emulsifying viscosity reducer selected in the viscosity reduction test is 30% of that of the thick oil uniformly, and the dosage is calculated by weight.
Measurement of viscosity in the present invention: using a Brookfield DV-II viscometer at 50 ℃ at a shear rate of 7.34s-1Under the conditions of (1). The measurement results are shown in Table 2.
TABLE 2 viscosity reduction test results of examples and comparative examples
Comparing examples 1 to 4 with examples 5 and 6, it can be seen that the effect of reducing the viscosity of the thick oil is better when the content of the nonionic surfactant is 0.04% to 0.3%, the content of the cationic oligomeric surfactant is 0.05% to 1.5%, and the content of the high molecular polymer is 0.04% to 0.3%, based on the weight of the emulsifying viscosity reducer.
As can be seen by comparing examples 1-6 with example 7, R in the cationic oligomeric surfactant is C8-C16And when the alkyl chain is long, the effect of reducing the viscosity of the thickened oil is better.
Comparing example 1 with comparative example 1, it can be seen that the cationic oligomeric surfactant can significantly reduce the viscosity of the heavy oil at higher concentrations (0.1%) than the cationic single chain surfactant. However, under the condition of lower concentration (less than 0.05%), the viscosity reducing effect of the example 6 and the comparative example 2 is achieved, and the concentration of the used viscosity reducing system of the oligomeric surfactant is lower.
Comparing example 1 with comparative examples 3 to 5, it can be seen that the cationic oligomeric surfactant and the high molecular polymer are indispensable in the emulsifying viscosity reducer of the invention, otherwise the thick oil is not emulsified. Namely: aiming at the conditions of high wax-containing heavy oil and high calcium-magnesium-containing formation water, the components of the nonionic surfactant, the cationic oligomeric surfactant and the high molecular polymer are all absent.
The above examples are provided to those of ordinary skill in the art to fully disclose and describe how to make and use the claimed embodiments, and are not intended to limit the scope of the disclosure herein. Modifications apparent to those skilled in the art are intended to be within the scope of the appended claims.
Claims (10)
1. A thick oil emulsifying viscosity reducer is characterized in that: the water-soluble cationic oligomeric surfactant is composed of 0.01-1 wt% of nonionic surfactant, 0.02-3 wt% of cationic oligomeric surfactant, 0.01-1 wt% of high molecular polymer and the balance of water;
the nonionic surfactant is selected from alkylphenol polyoxyethylene ether and/or alkyl alcohol polyoxyethylene ether;
the cationic oligomeric surfactant is selected from one or more than two of a compound A, a compound B and a compound C;
the structural formulas of the compound A, the compound B and the compound C are respectively shown as (a), (B) and (C) in the formula (I); in the formula (I), R is C4～C18Alkyl groups of (a); x is selected from F-、Cl-、Br-、I-One or more than two of the above;
(a)
(b)
(c)
the high molecular polymer is selected from polyacrylamide or hydroxypropyl guar gum.
2. The thick oil emulsifying viscosity reducer of claim 1, characterized in that: the polymerization degree of the alkylphenol polyoxyethylene ether and/or the alkyl alcohol polyoxyethylene ether is 3-30, and the alkyl chain length is 6-20.
3. The thick oil emulsifying viscosity reducer of claim 2, characterized in that: the alkylphenol polyoxyethylene ether is selected from nonylphenol polyoxyethylene ether series NP-7, NP-10 and NP-15; the alkyl alcohol polyoxyethylene ether is selected from fatty alcohol polyoxyethylene ether series AEO-7, AEO-9 and AEO-13.
4. The thick oil emulsifying viscosity reducer of claim 1, wherein the viscosity average molecular weight of the polyacrylamide is 400 × 104～3000×104。
5. The thick oil emulsifying viscosity reducer of claim 1, characterized in that: the thick oil emulsifying viscosity reducer consists of the following components: 0.04-0.3 percent of nonionic surfactant, 0.05-1.5 percent of cationic oligomeric surfactant, 0.04-0.3 percent of high molecular polymer and the balance of water.
6. The thick oil emulsifying viscosity reducer according to any one of claims 1 to 5, wherein: the thick oil emulsifying viscosity reducer is selected from one of the following components:
① comprises nonylphenol polyoxyethylene ether NP-10 0.05%, cationic oligomeric surfactant 0.1%, polyacrylamide with viscosity average molecular weight of 1000 ten thousand 0.1%, and water in balance, wherein the cationic oligomeric surfactant has a structural formula shown as (a) in formula (I), and R is C12Alkyl, X is Br-；
② comprises nonylphenol polyoxyethylene ether NP-7 0.3%, cationic oligomeric surfactant 0.8%, polyacrylamide with viscosity average molecular weight of 400 ten thousand 0.3%, and water in balance, wherein the cationic oligomeric surfactant has a structural formula shown as (b) in formula (I), and R is C14Alkyl, X is Br-；
③ comprises 0.1% fatty alcohol polyoxyethylene ether AEO-9, 0.05% cationic oligomeric surfactant, 0.04% polyacrylamide with viscosity average molecular weight of 3000 ten thousand, and water in balance, wherein the cationic oligomeric surfactant has a structural formula shown as (C) in formula (I), and R is C10Alkyl, X is Br-；
④ comprises 0.04% fatty alcohol polyoxyethylene ether AEO-13, 1.5% cationic oligomeric surfactant, 0.2% hydroxypropyl guar gum, and water in balance, wherein the cationic oligomeric surfactant has a structural formula shown as (a) in formula (I), and R is C8Alkyl, X is Cl-。
7. The thick oil emulsifying viscosity reducer according to any one of claims 1 to 5, wherein: the thick oil emulsifying viscosity reducer is selected from one of the following components:
⑤ comprises nonylphenol polyoxyethylene ether NP-10 0.01%, cationic oligomeric surfactant 0.1%, polyacrylamide with viscosity average molecular weight of 1000 ten thousand 0.1%, and water in balance, wherein the cationic oligomeric surfactant has a structural formula shown as (a) in formula (I), and R is C10Alkyl, X is Br-；
⑥ comprises nonylphenol polyoxyethylene ether NP-10 0.05%, cationic oligomeric surfactant 0.02%, polyacrylamide 0.01% with viscosity average molecular weight of 1000 ten thousand, and water in balance, wherein the cationic oligomeric surfactant has a structural formula shown as (C) in formula (I), and R is C10Alkyl, X is Br-；
⑦ comprises nonylphenol polyoxyethylene ether NP-10 0.05%, cationic oligomeric surfactant 0.1%, polyacrylamide with viscosity average molecular weight of 1000 ten thousand 0.1%, and water in balance, wherein the cationic oligomeric surfactant has a structural formula shown as (a) in formula (I), and R is C18Alkyl, X is F-。
8. The method for preparing the thick oil emulsifying viscosity reducer according to any one of claims 1 to 7, which is characterized in that: and (3) completely dissolving the nonionic surfactant, the cationic oligomeric surfactant and the high molecular polymer in water to obtain the water-soluble cationic oligomeric surfactant.
9. The method for preparing the thick oil emulsifying viscosity reducer according to claim 8, wherein: under the condition of mechanical stirring, adding high molecular polymer into partial water, stirring until the high molecular polymer is fully dissolved, then adding a nonionic surfactant and a cationic oligomeric surfactant, adding the balance of water, and stirring until the high molecular polymer is fully dissolved.
10. Use of the thick oil emulsification viscosity reducer of any one of claims 1 to 7 in reducing the viscosity of wax-containing thick oil.
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| CN109852361B (en) * | 2019-03-20 | 2021-10-01 | 天津开发区天盈企业有限公司 | Temperature-resistant and salt-resistant composite viscosity reducer and preparation method and application thereof |
| CN112680293B (en) * | 2019-10-18 | 2022-07-08 | 中国石油化工股份有限公司 | Emulsifier, preparation method and application thereof, and method for emulsifying butter in alkaline washing tower |
| CN113930230A (en) * | 2021-12-16 | 2022-01-14 | 中海油田服务股份有限公司 | Thick oil viscosity reducer and preparation method thereof |
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