CN110776901A - Environment-friendly drag reducer for fracturing and preparation method thereof - Google Patents
Environment-friendly drag reducer for fracturing and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric surfactants
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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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
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Abstract
The invention relates to an environment-friendly drag reducer for fracturing and a preparation method thereof, wherein the environment-friendly drag reducer comprises the following components in parts by weight: 0.1-17 parts of gemini quaternary ammonium salt, 8-55 parts of fatty alcohol-polyoxyethylene ether, 0.4-0.7 part of polyoxyethylene resin, 1.4-50 parts of sulfonate, 1.4-5.0 parts of nonionic natural carboxylate surfactant, 0.2-2.5 parts of cloud point inhibitor, 0.5-2.4 parts of anion-cation phase transfer agent and 5-90 parts of water. The drag reducer is non-toxic and harmless to the environment and people, and conforms to the national environmental protection policy; the environment-friendly drag reducer has the advantages of ultralow surface interfacial tension, suitability for slickwater hydraulic fracturing, sterilization function, stability in storage, convenience in use and the like.
Description
Technical Field
The invention relates to the field of oilfield chemical application, in particular to a composition of an environment-friendly drag reducer for fracturing, which has good biodegradability and ultralow surface interfacial tension, is suitable for slickwater hydraulic fracturing and is supplemented with a sterilization function, and a preparation method thereof.
Background
The quality of oil and gas resources is gradually reduced, the exploration and development strength of low-permeability oil reservoirs, compact oil, shale gas and coal bed gas is continuously increased, and fracturing is an effective means for opening oil and gas channels and is a conventional measure for increasing the yield of the low-permeability oil reservoirs. The slickwater fracturing can improve the probability of forming the cutting seam, is beneficial to forming the reticular seam, greatly improves the volume of the seam and the effect after fracturing, has low cost, can save 40 to 60 percent of cost in the same-scale operation of slickwater fracturing and conventional gel fracturing, and the resistance reducing agent becomes an important component of the volume fracturing.
Slickwater fracturing fluids have become a research hotspot as in the invention patent with application number 201310712341.7, and the applicant: zhengzhou san shan oil technology ltd, inventor: wangyongzheng Zhao Jun Yongsun hong Wei Zhi Peng and the like, which discloses a resistance-reducing agent for fracturing shale gas slickwater and a preparation method thereof. Patent application No. 201010526794.7, applicant: beijing Hongyao Enze energy technology Limited company, inventor: tang Ru zhong, Zhangzhou, Mi Qiangbo, Gunn Yundi, Zhao wenna, it discloses a resistance-reducing agent for fracturing fluid and its preparation method. However, the main components of the above patents are mainly acrylamide, which is toxic and has a great risk at present, and the surface interfacial tension of the resistance reducing agent of the above patents is not ideal. Therefore, further improvements are necessary over the prior art.
Disclosure of Invention
The invention aims to provide an environment-friendly drag reducer for fracturing and a preparation method thereof, so as to solve the defects.
The purpose of the invention is realized by the following technical scheme.
The environment-friendly drag reducer for fracturing comprises the following components in parts by weight: 0.1-17 parts of gemini quaternary ammonium salt, 8-55 parts of fatty alcohol-polyoxyethylene ether, 0.4-0.7 part of polyoxyethylene resin, 1.4-50 parts of sulfonate, 1.4-5.0 parts of carboxylate surfactant, 0.2-2.5 parts of cloud point inhibitor, 0.5-2.4 parts of anion-cation phase transfer agent and 5-90 parts of water.
The cloud point inhibitor comprises one or more of erucamidopropyl betaine, cocamidopropyl hydroxysultaine and erucamidopropyl hydroxysultaine.
Further, the gemini quaternary ammonium salt is
Wherein R is dodecyl, R1 is methyl, R2 is hexadecyl, and X is halogen atom.
Further, the gemini quaternary ammonium salt is obtained by reacting two tertiary amines or derivatives thereof with a double halide, wherein the two tertiary amines or derivatives thereof are two same or different tertiary amine compounds or one compound containing two tertiary amine groups.
Further, the fatty alcohol-polyoxyethylene ether is represented by the general formula
Wherein n is a positive integer from 6 to 20.
Further, the water accounts for 35-65% of the total mass of the environment-friendly drag reducer.
Further, the fatty alcohol-polyoxyethylene ether: RO (CH)
2CH
2O)
nThe molecular weight of H is one or more of 80, 200 and 400 ten thousand.
Further, the sulfonate has the structural formula: RO (CH)
2CH
2O)
nSO
3Na, where R ═ C12-15 alkyl or C12-14 alkyl, and n ═ 2-3.
Further, the anion-cation phase transfer agent comprises dodecyl trimethyl benzyl ammonium chloride and/or bis 16 dimethyl ammonium chloride.
The carboxylate surfactant is a non-ionic carboxylate surfactant.
A preparation method of an environment-friendly drag reducer for fracturing comprises the following steps:
step 1: weighing each component in the environment-friendly drag reducer according to a proportion, adding water, gemini quaternary ammonium salt and fatty alcohol-polyoxyethylene ether into a reaction kettle, starting stirring at the rotating speed of 85-135 r/min, and starting heating;
step 2: when the temperature in the step 1 is raised to 50-75 ℃, adding polyoxyethylene resin, alkyl sulfonate and carboxylate surfactant into the reaction kettle, and then stirring for 1-6 hours at a constant temperature of 50-75 ℃;
and step 3: and continuously adding the cloud point inhibiting and anion-cation phase transfer agent, and continuously stirring for 2 hours to obtain the liquid of the emulsion, namely the final product, namely the environment-friendly drag reducer.
Further, in step 1, the gemini quaternary ammonium salt is any one of the following three types:
(1) designing a suitable linker and then bonding the two amphiphiles together at the head group, which process comprises the reaction of two tertiary amines or derivatives thereof with a double halide;
(2) selecting a molecular structure connected with two hydrophilic groups as a raw material, and introducing two hydrophobic chains, wherein the process comprises the reaction of long-chain halogenated alkane and tetramethyl ethylenediamine;
(3) the carboxylate surfactant is used as a raw material, and is subjected to activation reaction or reaction with a connecting agent after a chemical reaction active group is introduced.
The invention has the beneficial effects that:
(1) the environment-friendly drag reducer for fracturing does not contain polyacrylamide, is non-toxic, non-flammable and non-explosive, is harmless to the environment and people, and accords with the national environment protection policy;
(2) the environment-friendly drag reducer for fracturing has ultralow surface interfacial tension, is suitable for slickwater hydraulic fracturing, is assisted by a sterilization function, and has high drag reduction rate; stable storage, convenient use and the like.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The environment-friendly drag reducer for fracturing comprises the following components in percentage by mass:
gemini quaternary ammonium salt 10%
15 percent of fatty alcohol-polyoxyethylene ether
0.5 percent of polyoxyethylene resin
Alkyl sulfonate 15%
Nonionic carboxylate surfactant 3%
Cloud Point inhibitor 1%
1 percent of anion-cation phase transfer agent
The balance of water.
Wherein the gemini quaternary ammonium salt is
Wherein R is dodecyl, R1 is methyl, R2 is hexadecyl, and X is chlorine atom; fatty alcohol polyoxyethylene ether RO (CH)
2CH
2O)
nH molecular weight 200 ten thousand, alkylsulfonate RO (CH)
2CH
2O)
nSO
3Na (R is C12 alkyl, n is 2), the carboxylate surfactant is a nonionic natural carboxylate surfactant, the cloud point inhibitor is erucamidopropyl betaine, and the anion-cation phase transfer agent is dodecyl trimethyl benzyl ammonium chloride.
The preparation method of the environment-friendly drag reducer for fracturing comprises the following steps: adding 545Kg of water into a reaction kettle, adding 100Kg of water, a gemini quaternary ammonium salt surfactant and 150Kg of fatty alcohol-polyoxyethylene ether, starting stirring at the rotation speed of 85-135 r/min, heating to 50-75 ℃, adding 5Kg of polyoxyethylene resin, 150Kg of sulfonate and 30Kg of nonionic natural carboxylate, stirring at the constant temperature of 75 ℃ for 4 hours, and continuously adding 10Kg of cloud point inhibitor; 10Kg of anion-cation phase transfer agent; stirring is continued for 2 hours to obtain the product.
When the using concentration of the product is 2 per mill, the resistance reducing rate is 72.3 percent; the surface tension is 23.4 mN/m; interfacial tension 4.2X 10-3; the sterilization rate is 99 percent.
Example 2
The environment-friendly drag reducer for fracturing comprises the following components in percentage by mass:
gemini quaternary ammonium salt 10%
10 percent of fatty alcohol-polyoxyethylene ether
0.5 percent of polyoxyethylene resin
Alkyl sulfonate 10%
Nonionic carboxylate surfactant 3%
Cloud Point inhibitor 1%
1 percent of anion-cation phase transfer agent
The balance of water.
Wherein the gemini quaternary ammonium salt is
Wherein R is dodecyl, R1 is methyl, R2 is hexadecyl, and X is chlorine atom;
molecular weight of fatty alcohol polyoxyethylene ether 200 ten thousand, alkyl sulfonate RO (CH)
2CH
2O)
nSO
3In Na, R is C12 alkyl, n is 2, the cloud point inhibitor is cocamidopropyl hydroxysultaine, and the anion-cation phase transfer agent is dodecyl trimethyl benzyl ammonium chloride.
The preparation method of the environment-friendly drag reducer for fracturing comprises the following steps: adding 645Kg of water into a reaction kettle, then adding 100Kg of gemini quaternary ammonium salt surfactant and 100Kg of fatty alcohol-polyoxyethylene ether, starting stirring at the rotation speed of 85-135 r/min, heating to 50-75 ℃, adding 5Kg of polyoxyethylene resin, 100Kg of alkyl sulfonate and 30Kg of nonionic natural carboxylate surfactant, stirring at the constant temperature of 75 ℃ for 4 hours, and then continuously adding 10Kg of cloud point inhibitor; 10Kg of anion-cation phase transfer agent; stirring is continued for 2 hours to obtain the product.
When the using concentration of the product is 2 per mill, the resistance reducing rate is 73.5 percent; the surface tension is 22.7 mN/m; interfacial tension 3.3X 10-3; the sterilization rate is 99 percent.
Example 3
The environment-friendly drag reducer for fracturing comprises the following components in percentage by mass:
gemini quaternary ammonium salt 10%
15 percent of fatty alcohol-polyoxyethylene ether
0.5 percent of polyoxyethylene resin
Sulfonate 15%
Nonionic carboxylate surfactant 3%
Cloud Point inhibitor 1%
1 percent of anion-cation phase transfer agent
The balance of water.
Wherein the gemini quaternary ammonium salt is
Wherein R is dodecyl, R1 is methyl, R2 is hexadecyl, and X is chlorine atom;
the molecular weight of the fatty alcohol-polyoxyethylene ether is 400 ten thousand, and the sulfonate RO (CH)
2CH
2O)
nSO
3Na, wherein R is C12 alkyl, n is 2, the cloud point inhibitor is erucamide propyl hydroxy sulfobetaine, and the anion-cation phase transfer agent is dodecyl trimethyl benzyl ammonium chloride.
The preparation method of the environment-friendly drag reducer for fracturing comprises the following steps: adding 545Kg of water into a reaction kettle, adding 100Kg of water, a gemini quaternary ammonium salt surfactant and 150Kg of fatty alcohol-polyoxyethylene ether, starting stirring at the rotation speed of 85-135 r/min, heating to 50-75 ℃, adding 5Kg of polyoxyethylene resin, 150Kg of sulfonate and 30Kg of nonionic natural carboxylate, stirring at the constant temperature of 75 ℃ for 4 hours, and continuously adding 10Kg of cloud point inhibitor; 10Kg of anion-cation phase transfer agent; stirring for 2 hours to obtain clear and transparent liquid, namely the product.
When the using concentration of the product is 2 per mill, the resistance reducing rate is 73.5 percent; the surface tension is 22.7 mN/m; interfacial tension 3.3X 10
-3(ii) a The sterilization rate is 99 percent.
Example 4
The environment-friendly drag reducer for fracturing comprises the following components in percentage by mass:
gemini quaternary ammonium salt 10%
20 percent of fatty alcohol-polyoxyethylene ether
0.5 percent of polyoxyethylene resin
Sulfonate 20%
Nonionic natural carboxylate 3%
Cloud Point inhibitor 1%
1 percent of anion-cation phase transfer agent
The balance of water.
Wherein the molecular weight of the gemini quaternary ammonium salt is 8 ten thousand; the gemini quaternary ammonium salt is prepared by taking a surfactant as a raw material, and reacting with a connecting agent after an activation reaction or introduction of a chemical reaction active group.
Fatty alcohol polyoxyethylene ether has molecular weight of 400 ten thousand, and alkyl sulfonate RO (CH)
2CH
2O)nSO
3Na, wherein R is C12 alkyl, n is 2, the cloud point inhibitor is erucamide propyl hydroxy sulfobetaine, and the anion-cation phase transfer agent is dicetyl trimethyl ammonium chloride.
The preparation method of the environment-friendly drag reducer for fracturing comprises the following steps: firstly adding 445 Kg of water into a reaction kettle, firstly adding 100Kg of water, 100Kg of gemini quaternary ammonium salt surfactant and 200Kg of fatty alcohol-polyoxyethylene ether, starting stirring at the rotation speed of 85-135 r/min, heating to 50-75 ℃, adding 5Kg of polyoxyethylene resin, 200Kg of sulfonate and 30Kg of nonionic natural carboxylate, stirring at the constant temperature of 75 ℃ for 4 hours, and continuously adding 10Kg of cloud point inhibitor; 10Kg of anion-cation phase transfer agent; stirring for 2 hours to obtain clear and transparent liquid, namely the product.
When the using concentration of the product is 2 per mill, the resistance reducing rate is 74.7 percent; the surface tension is 22.1 mN/m; interfacial tension 2.7X 10
-3(ii) a The sterilization rate is 99 percent.
Comparative example 1
The gemini quaternary ammonium salt in the example 1 is changed into the common quaternary ammonium salt dioctadecyl dimethyl ammonium chloride, the general formula of which is shown as follows, and the rest is consistent with the example.
Comparative example 2
The fatty alcohol-polyoxyethylene ether in example 1 was removed, and the rest was completely the same as example 1.
Comparative example 3
The cloud point depressant in example 1 was changed to betaine (cas No. 107-43-7), and the rest was identical to example 1.
Comparative example 4
The nonionic natural carboxylate surfactant of example 1 was deleted and the remainder was identical to example 1.
Comparative example 5
The preparation method in example 1 was changed to: all the substances are added into a reaction kettle at the same time and stirred for 2 to 10 hours at the temperature of between 50 and 75 ℃.
Comparative example 6
The resistance reduction rate, surface tension, interfacial tension and sterilization rate in examples 1 to 4 and comparative examples 1 to 5 were measured, and the results are shown below.
Resistance reduction rate | Surface tension | Interfacial tension | Rate of sterilization | |
Example 1 | 72.3% | 22.1mN/m | 2.7×10 -3mN/m | 99% |
Example 2 | 73.5% | 22.7mN/m | 3.3×10 -3mN/m | 99% |
Example 3 | 73.5% | 22.7mN/m | 3.3×10 -3mN/m | 99% |
Example 4 | 74.7% | 22.1mN/m | 2.7×10 -3mN/m | 99% |
Comparative example 1 | 53.5% | 53.5mN/m | 9.5×10 -2mN/m | 68% |
Comparative example 2 | 59.4% | 58.7mN/m | 4.3×10 -1mN/m | 72% |
Comparative example 3 | 60.5% | 46.9mN/m | 1.8×10 -1mN/m | 81% |
Comparative example 4 | 58.8% | 38.5mN/m | 4.3×10 -1mN/m | 76% |
Comparative example 5 | 66.8% | 28.5mN/m | 3.3×10 -2mN/m | 86% |
The comparison shows that the effects of the comparative examples 1 to 4 are obviously lower than the data in the examples, and the inventor finds that the components in the formula of the invention have obvious interaction through years of research, and the final resistance reduction rate is high, the surface tension and the interfacial tension are ultralow, and the sterilization rate is high and stable through the interaction. And the main components in the formula are deleted or changed, so that the interaction relationship among the substances is broken, and the realization of the effect is greatly influenced. In addition, the sequence of addition and reaction conditions during the preparation process have obvious influence on the interaction between the substances.
The present invention is not limited to the above-mentioned preferred embodiments, and any other products in various forms can be obtained by anyone in the light of the present invention, but any changes in the shape or structure thereof, which have the same or similar technical solutions as those of the present application, fall within the protection scope of the present invention.
Claims (10)
1. The environment-friendly drag reducer for fracturing is characterized by comprising the following components in parts by weight: 0.1-17 parts of gemini quaternary ammonium salt, 8-55 parts of fatty alcohol-polyoxyethylene ether, 0.4-0.7 part of polyoxyethylene resin, 1.4-50 parts of sulfonate, 1.4-5.0 parts of carboxylate surfactant, 0.2-2.5 parts of cloud point inhibitor, 0.5-2.4 parts of anion-cation phase transfer agent and 5-90 parts of water.
The cloud point inhibitor comprises one or more of erucamidopropyl betaine, cocamidopropyl hydroxysultaine and erucamidopropyl hydroxysultaine.
2. The environmentally friendly drag reducer for fracturing of claim 1, wherein said gemini quaternary ammonium salt is
Wherein R is dodecyl, R1 is methyl, R2 is hexadecyl, and X is halogen atom.
3. The environmentally friendly drag reducer for fracturing of claim 2, wherein the gemini quaternary ammonium salt is obtained by reacting two tertiary amines or derivatives thereof with a dihalide, wherein the two tertiary amines or derivatives thereof are two same or different tertiary amine compounds or one compound containing two tertiary amine groups.
4. The environment-friendly drag reducer for fracturing as claimed in claim 3, wherein said fatty alcohol-polyoxyethylene ether is of the general formula
Wherein n is a positive integer from 6 to 20.
5. The environmentally friendly drag reducer for fracturing of claim 4, wherein the water comprises 35-65% of the total mass of the environmentally friendly drag reducer.
6. The environmentally friendly drag reducer for fracturing of claim 5, wherein the fatty alcohol-polyoxyethylene ether has a molecular weight of one or more of 80, 200 and 400 ten thousand.
7. The environmentally friendly drag reducer for fracturing of claim 6, wherein said drag reducer is a solid-liquid, or a liquid, and wherein said solid-liquid is a liquid, a solid, or a liquidThe structural formula of the sulfonate is: RO (CH)
2CH
2O)nSO
3Na, where R ═ C12-15 alkyl or C12-14 alkyl, and n ═ 2-3.
8. The environmentally friendly drag reducer for fracturing of claim 7, wherein the anion-cation phase transfer agent comprises dodecyl trimethyl benzyl ammonium chloride and/or bis 16 dimethyl ammonium chloride;
the carboxylate surfactant is a non-ionic carboxylate surfactant.
9. A preparation method of an environment-friendly drag reducer for fracturing is characterized by comprising the following steps: the preparation method comprises the following steps:
step 1: weighing each component in the environment-friendly drag reducer according to a proportion, adding water, gemini quaternary ammonium salt and fatty alcohol-polyoxyethylene ether into a reaction kettle, starting stirring at the rotating speed of 85-135 r/min, and starting heating;
step 2: when the temperature in the step 1 is raised to 50-75 ℃, adding polyoxyethylene resin, alkyl sulfonate and carboxylate surfactant into the reaction kettle, and then stirring for 1-6 hours at a constant temperature of 50-75 ℃;
and step 3: and continuously adding the cloud point inhibiting and anion-cation phase transfer agent, and continuously stirring for 2 hours to obtain the liquid of the emulsion, namely the final product, namely the environment-friendly drag reducer.
10. The method for preparing the environmentally friendly drag reducer for fracturing as recited in claim 1, wherein in step 1, the gemini quaternary ammonium salt is any one of the following three:
(1) designing a suitable linker and then bonding the two amphiphiles together at the head group, which process comprises the reaction of two tertiary amines or derivatives thereof with a double halide;
(2) selecting a molecular structure connected with two hydrophilic groups as a raw material, and introducing two hydrophobic chains, wherein the process comprises the reaction of long-chain halogenated alkane and tetramethyl ethylenediamine;
(3) the carboxylate surfactant is used as a raw material, and is subjected to activation reaction or reaction with a connecting agent after a chemical reaction active group is introduced.
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CN113088273A (en) * | 2021-04-07 | 2021-07-09 | 北京首科油源科技有限公司 | Preparation method of nano microcapsule fracturing fluid and fracturing fluid performance evaluation method |
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Application publication date: 20200211 |