CN111454388B - Enol/alpha-olefin copolymer pipeline drag reducer and preparation method and application thereof - Google Patents
Enol/alpha-olefin copolymer pipeline drag reducer and preparation method and application thereof Download PDFInfo
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- CN111454388B CN111454388B CN202010308307.3A CN202010308307A CN111454388B CN 111454388 B CN111454388 B CN 111454388B CN 202010308307 A CN202010308307 A CN 202010308307A CN 111454388 B CN111454388 B CN 111454388B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
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Abstract
The invention discloses an enol/alpha-olefin copolymer pipeline drag reducer as well as a preparation method and application thereof, belonging to the technical field of synthesis and preparation of macromolecular compounds and pipeline transportation. The preparation method adopts a bulk polymerization method, enol and C6-C18 alpha-olefin are used as raw materials, a Ziegler-Natta catalyst system is adopted, a plasticizer, a molecular weight regulator and the like are added, nitrogen is introduced, heating and ultraviolet radiation modes are adopted to initiate reaction, the enol/alpha-olefin copolymer is synthesized, and the enol/alpha-olefin copolymer can be used as an oil product drag reducer to be applied to oil product pipeline transportation. The enol/alpha-olefin copolymer drag reducer prepared by the invention has the advantages of higher conversion rate, low gel rate, low cost, difficult implosion, low molecular weight dispersion degree and easy dispersion in various crude oils, can improve the pipeline conveying efficiency, particularly improves the drag reduction effect of the hydrous crude oil and the complex crude oil of a gathering pipeline by 30-50 percent compared with the common alpha-olefin polymer product, and has good application prospect.
Description
Technical Field
The invention discloses an enol/alpha-olefin copolymer pipeline drag reducer and a preparation method thereof, belonging to the technical field of synthesis and preparation of macromolecular compounds and pipeline conveying systems.
Background
When the fluid contains certain specific substances, the friction resistance of the fluid in a turbulent flow state is greatly reduced, the phenomenon is called drag reduction, and the additive capable of realizing the drag reduction and transportation enhancement effects in the transportation process of pipeline crude oil and finished oil is called an oil product drag reducer. Oil drag reducers are divided into two categories according to the action principle: one is high flexible linear polymer with ultrahigh molecular weight, mainly including olefin homopolymer or copolymer, polymethacrylate, etc.; another class is surface-active compounds. A great deal of research and practice proves that the copolymer oil drag reducer has better drag reduction effect than the current commonly used poly alpha-olefin drag reducer, because the molecular weight control is easier in the synthesis process of the copolymer drag reducer, and because the copolymerized alpha-olefin with different functional groups is introduced, the dissolution and dispersion properties of the polymerization product are better.
Polyolefin polymer drag reducers are generally synthesized by the bulk polymerization of Ziegler-Natta catalysts. The Ziegler-Natta system catalyst consists of a main catalyst and a cocatalyst, and how to prepare the high-efficiency Ziegler-Natta system catalyst directly influences the resistance reduction performance of a polymer product. The history of the polyolefin industry is ultimately the history of Ziegler-Natta catalysts. How to adjust the amount and distribution of TiC14 on the final catalyst, the selection and combination of non-toxic high-efficiency cocatalyst, and the improvement of the orientation capability of the catalyst and the isotacticity of the polymer is a key technical point and difficulty in the current synthesis of oil product drag reducers.
The addition of additives such as molecular weight regulator can obviously improve the physical properties of the high molecular copolymer and improve the molecular weight dispersity and isotacticity of the polymer.
Aiming at the complex crude oil of the water-containing crude oil and the gathering pipeline, the common alpha-olefin polymer product is used, the use effect is greatly reduced, and the enol/alpha-olefin copolymer pipeline drag reducer can effectively solve the problem.
Disclosure of Invention
The invention aims to solve the technical problem of providing an enol/alpha-olefin copolymer pipeline drag reducer and a preparation method thereof. The preparation method has the advantages of simple operation, low cost, short reaction time, difficult implosion in the reaction process, accurate control of the molecular weight of the copolymer and reduction of the molecular weight dispersion degree of the generated copolymer; the pipeline drag reducer prepared by the enol/alpha-olefin copolymer has low gel rate, is easy to disperse in the crude oil containing water and the crude oil of the gathering and transporting pipeline, and improves the pipeline transportation efficiency.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: an enol/alpha-olefin copolymer drag reducer for pipelines, which is prepared by the following steps:
1) adding alpha-olefin of C6-C18 into a closed container, uniformly mixing, introducing nitrogen, adding enol, adding a Ziegler-Natta main catalyst, heating for a period of time, and adding a Ziegler-Natta cocatalyst;
2) placing the closed container in a cold bath, and simultaneously carrying out ultraviolet radiation; adding molecular weight regulator, and stopping ultraviolet radiation after a while to obtain stable enol/alpha-olefin copolymer.
Preferably, the enol/α -olefin copolymer pipeline drag reducer in step 1) is prepared by compounding one or more of C6-C18 α -olefin, C6 α -olefin, C8 α -olefin, C10 α -olefin, C12 α -olefin, C14 α -olefin, C16 α -olefin and C18 α -olefin.
Preferably, in the enol/α -olefin copolymer pipeline drag reducer, in the step 1), the weight ratio of α -olefin of C6-C18: the enol is 1: 6-2: 5.
preferably, in the above-mentioned enol/α -olefin copolymer pipeline drag reducer, in step 1), the enol is one or a mixture of two or more of 2-butenol, 3-buten-2-ol, 2-methyl-3-buten-2-ol, 1, 5-hexadiene-3, 4-diol, 2-hexenol, 3-hexenol, 1-hexen-3-ol and 5-hexen-1-ol.
Preferably, in the above enol/α -olefin copolymer pipeline drag reducer, in step 1), the mass of the Ziegler-Natta main catalyst is 0.05% to 5% of the total mass of the mixed enol/α -olefin; the Ziegler-Natta main catalyst is MgCl 2 、ZnCl 2 Or SiO 2 One or more of titanium tetrachloride, titanium trichloride, titanium tribromide, vanadium tetrachloride and zirconium tetrachloride are loaded.
Preferably, in the enol/alpha-olefin copolymer drag reducer for pipelines, in the step 1), the heating temperature is 40-60 ℃, and the heating time is 5-15 min;
preferably, the above-mentioned enol/alpha-olefin copolymer pipeline drag reducer, the mass of the Ziegler-Natta cocatalyst is 0.1% -5% of the total mass of the mixed enol/alpha-olefin; the Ziegler-Natta cocatalyst is one or a compound of more than two of triethyl aluminum, trimethyl aluminum, diethyl aluminum monochloride and diisobutyl aluminum monochloride.
Preferably, in the step 2), the cold bath temperature is-50 to-20 ℃, and the irradiance under the ultraviolet radiation intensity of 340nm wavelength is 0.9 to 1.2W/(m) of the enol/alpha-olefin copolymer drag reducer for pipelines 2 Nm) and the radiation time is 15-45 min.
Preferably, in the above enol/α -olefin copolymer pipeline drag reducer, in the step 2), the mass of the molecular weight regulator is 0.02% to 0.3% of the total mass of the mixed enol/α -olefin; the molecular weight regulator is one or more than two of dodecyl mercaptan, 1, 3-propanedithiol, 2, 3-dimercaptopropanol, phenol, acetic acid, isopropanol, 1, 3-dimethyl butyl sodium xanthate and diisopropyl disulfide xanthate.
The application of any enol/alpha-olefin copolymer pipeline drag reducer in the transportation of water-containing crude oil and complex crude oil of gathering pipelines.
The invention has the beneficial effects that: the invention effectively solves the problem that the conventional drag reducer fails under the complex condition of high-water-content crude oil and oil products in gathering and transporting pipelines by a method for copolymerizing the enol and the alpha-olefin.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments. It should not be construed as limiting the present invention, and modifications or substitutions of methods, steps or conditions, etc., without departing from the spirit and substance of the present invention, should be made within the scope of the claims of the present invention.
Example 1
100g of alpha-olefin having a cut of C6 and 200g of alpha-olefin having a cut of C18 were weighed, respectively, and the weighed materials were put into a three-necked flask, stirred, and introduced with nitrogen gas at a rate of 50ml/min for 10 min. Then 100g of 3-hexenol were added. 0.4g of ZnCl was added 2 Supported TiCl 4 Wherein TiCl is 4 Was heated at 50 ℃ for 20min with a loading of 0.2g, and then 2g of triethylaluminum was added. Placing in a cold bath at-20 deg.C, and irradiance at 340nm is 0.9W/(m) 2 Nm), the irradiation time was 45 min. 0.1g of dodecyl mercaptan and 0.1g of 1, 3-propanedithiol were added, and the ultraviolet radiation was stopped after 25 minutes to obtain an enol/α -olefin copolymer having a conversion of 99.1% and a molecular weight of about 670 ten thousand.
Example 2
150g and 150g of alpha-olefin having a C8 and C12 cut-off were weighed out separately and charged into a three-necked flask, and nitrogen gas was introduced at a rate of 100ml/min for 10 min. Then 80g of 3-butenol were added. 0.5g of ZnCl was added 2 Supported TiCl 4 Wherein TiCl is 4 Was heated at 45 ℃ for 20min with a loading of 0.3g, and then 2.5g of triethylaluminum was added. Placing in a cold bath at-30 deg.C, and irradiating with irradiance of 0.9W/(m2 nm) at 340nm wavelength for 30 min. Adding 0.1g dodecyl mercaptan, stopping ultraviolet radiation after 15minTo obtain the enol/alpha-olefin copolymer, wherein the conversion rate is 99.6 percent, and the molecular weight is about 780 ten thousand.
Example 3
100g and 200g of alpha-olefin with the fractions of C10 and C12 were weighed out and charged into a three-necked flask, and nitrogen gas was introduced thereinto at a rate of 100ml/min for 20 min. Then 120g of 2-hexenol were added. 0.6g of ZnCl was added 2 Supported TiCl 4 Wherein TiCl is 4 Was heated at 45 ℃ for 5min with a loading of 0.4g, and then 2.5g of triethylaluminum was added. Placing in a cold bath at-30 deg.C, and irradiating with irradiance of 0.9W/(m2 nm) at 340nm wavelength for 35 min. 0.1g of 1, 3-propanedithiol was added, and after 20 minutes, the ultraviolet radiation was stopped to obtain an enol/α -olefin copolymer having a conversion of 99.8% and a molecular weight of about 810 ten thousand.
Example 4
100g and 200g of alpha-olefin having a C6 and C16 cut-off were weighed out, respectively, and charged into a three-necked flask, and nitrogen gas was introduced thereinto at a rate of 50ml/min for 10 min. Then 80g of 2-hexenol were added. 0.5g of ZnCl was added 2 Supported TiCl 4 Wherein TiCl is 4 Was heated at 45 ℃ for 15min with a loading of 0.3g, and then 3g of triethylaluminum was added. Placing in a cold bath at-20 deg.C, and irradiating with irradiance of 0.9W/(m2 nm) at 340nm wavelength for 45 min. 0.1g of dodecyl mercaptan and 0.1g of 1, 3-propanedithiol were added, and the ultraviolet radiation was stopped after 25 minutes to obtain an enol/α -olefin copolymer having a conversion of 99.3% and a molecular weight of about 690 ten thousand.
Example 5
150g and 150g of alpha-olefin having a C6 fraction and a C12 fraction were weighed out and charged into a three-necked flask, and nitrogen gas was introduced thereinto at a rate of 100ml/min for 20 min. 100g of 3-butenol are then added. 0.6g of ZnCl was added 2 Supported TiCl 4 Wherein TiCl is 4 Was heated at 40 ℃ for 5min with a loading of 0.4g, and then 3g of triethylaluminum were added. Placing in a cold bath at-50 deg.C, and irradiating with irradiance of 0.9W/(m2 nm) at 340nm wavelength for 30 min. 0.1g of dodecyl mercaptan is added, and the ultraviolet radiation is stopped after 15min to obtain the enol/alpha-olefin copolymer, wherein the conversion rate is 99.6 percent, and the molecular weight is about 760 ten thousand.
Example 6
The ratio of drag reduction ratios is shown in Table 1 when commercial EP oil drag reducers, OD-L drag reducers and the drag reducers described in examples 1 to 5 are added in the common crude oil in an amount of 20 ppm.
TABLE 1
The drag reduction ratios are shown in Table 2 when commercially available EP oil drag reducers, OD-L drag reducers, and the drag reducers described in examples 1-5 are added at 20ppm in crude oil containing 25% water.
TABLE 2
The drag reduction ratios are shown in Table 3 when commercially available EP oil drag reducers, OD-L drag reducers, and the drag reducers described in examples 1-5 are added at 20ppm in crude oil containing 25% water, 15% wax, and 3% asphaltene.
TABLE 3
Table 1 shows that the enol alpha-olefin copolymer pipeline drag reducer prepared by the method has slightly improved drag reduction effect in the pipeline transportation of common crude oil compared with the common commercially available EP oil drag reducer, but is not obvious.
Tables 2 and 3 show that the enol alpha-olefin copolymer pipeline drag reducer prepared by the method has the drag reduction effect improved by 30-50% in pipeline transportation of complex crude oil with high water content, wax content and asphaltene content compared with common commercially available EP oil product drag reducers.
The experiments are only preferred examples of the present invention and are not intended to limit the scope of the present invention. It should be noted that modifications and adaptations may occur to those skilled in the art without departing from the principles of the present invention and should be considered within the scope of the present invention.
Claims (6)
1. An enol/alpha-olefin copolymer drag reducer for pipelines, which is characterized in that the preparation method comprises the following steps:
1) adding alpha-olefin of C6-C18 into a closed container, uniformly mixing, introducing nitrogen, adding enol, adding a Ziegler-Natta main catalyst, heating for a period of time, and adding a Ziegler-Natta cocatalyst;
2) placing the closed container in a cold bath, and simultaneously carrying out ultraviolet radiation; adding a molecular weight regulator, and stopping ultraviolet radiation after a period of time to obtain a stable enol/alpha-olefin copolymer;
the mass of the Ziegler-Natta main catalyst is 0.05-5% of the total mass of the mixed enol/alpha-olefin; the Ziegler-Natta main catalyst is MgCl 2 、ZnCl 2 Or SiO 2 One or more of titanium tetrachloride, titanium trichloride, titanium tribromide, vanadium tetrachloride and zirconium tetrachloride are loaded;
in the step 1), the heating temperature is 40-60 ℃, and the heating time is 5-15 min;
the mass of the Ziegler-Natta cocatalyst is 0.1-5% of the total mass of the mixed enol/alpha-olefin; the Ziegler-Natta cocatalyst is one or a compound of more than two of triethyl aluminum, trimethyl aluminum, diethyl aluminum monochloride and diisobutyl aluminum monochloride;
in the step 2), the temperature of the cold bath is-50 to-20 ℃, and the irradiance under the ultraviolet radiation intensity of 340nm wavelength is 0.9 to 1.2W/(m) 2 Nm) and the radiation time is 15-45 min.
2. The enol/alpha-olefin copolymer pipeline drag reducer according to claim 1, wherein the alpha-olefin of C6-C18 in step 1) is one or a combination of two or more of C6 alpha-olefin, C8 alpha-olefin, C10 alpha-olefin, C12 alpha-olefin, C14 alpha-olefin, C16 alpha-olefin and C18 alpha-olefin.
3. The enol/alpha-olefin copolymer drag reducer for pipelines according to claim 1, wherein in the step 1), the mass ratio of the alpha-olefin of C6-C18 is as follows: the enol is 1: 6-2: 5.
4. the enol/α -olefin copolymer pipeline drag reducer according to claim 1, wherein in step 1), the enol is one or a combination of two or more of 2-butenol, 3-buten-2-ol, 2-methyl-3-buten-2-ol, 1, 5-hexadiene-3, 4-diol, 2-hexenol, 3-hexenol, 1-hexen-3-ol and 5-hexen-1-ol.
5. The enol/alpha-olefin copolymer pipeline drag reducer according to claim 1, wherein in the step 2), the mass of the molecular weight regulator is 0.02 to 0.3 percent of the total mass of the mixed enol/alpha-olefin; the molecular weight regulator is one or a compound of more than two of dodecyl mercaptan, 1, 3-propanedithiol, 2, 3-dimercaptopropanol, phenol, acetic acid, isopropanol, 1, 3-dimethyl butyl sodium xanthate and diisopropyl disulfide xanthate.
6. Use of any of the enol/α -olefin copolymer pipeline drag reducing agents of claims 1 to 5 in the transportation of aqueous crude oil and complex crude oil in a gathering pipeline.
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| CN106632784A (en) * | 2016-10-27 | 2017-05-10 | 段恒宇 | Preparation method of ethylene/alpha-olefin copolymer, and application of ethylene/alpha-olefin copolymer in pipeline transmission |
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| US6815011B2 (en) * | 2000-11-27 | 2004-11-09 | Energy & Environmental International, L.C. | Alpha olefin monomer partitioning agents for drag reducing agents and methods of forming drag reducing agents using alpha olefin monomer partitioning agents |
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| CN102274701A (en) * | 2010-06-11 | 2011-12-14 | 中国石油天然气股份有限公司 | Surfactant and preparation and application thereof |
| CN106632784A (en) * | 2016-10-27 | 2017-05-10 | 段恒宇 | Preparation method of ethylene/alpha-olefin copolymer, and application of ethylene/alpha-olefin copolymer in pipeline transmission |
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