CN102746520B - Post-treatment and preparation method for polyolefin drag reducing agent used for oil based crude oil - Google Patents
Post-treatment and preparation method for polyolefin drag reducing agent used for oil based crude oil Download PDFInfo
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- CN102746520B CN102746520B CN 201210202276 CN201210202276A CN102746520B CN 102746520 B CN102746520 B CN 102746520B CN 201210202276 CN201210202276 CN 201210202276 CN 201210202276 A CN201210202276 A CN 201210202276A CN 102746520 B CN102746520 B CN 102746520B
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Abstract
The invention employs a vibration method which is entirely different from the prior art. Under a condition of above-zero DEG C temperature, the drag reducing agent polymer is refined to slurry by using a vibration mill, so the finished product of the drag reducing agent used for oil based crude oil is obtained. The finished product has been successfully applied to oil pipelines and good effect is achieved. With no liquid nitrogen required in the polymer crushing process, the risk factors from the liquid nitrogen such as the injury to workers caused by low temperature, and suffocation are eliminated.
Description
Technical field
The present invention relates to a kind of polyolefine oil base crude oil flow improver aftertreatment preparation method, particularly a kind of polyolefine oil base crude oil non-low temperature preparation method of flow improver aftertreatment.
Background technology
Chemical agent for reducing fluid flow resistance is called flow improver (drag reducing agent), is called for short DRA.Flow improver is widely used in crude oil pipeline to be carried, and it is the important means that improves the pipeline circulating capacity and cut down the consumption of energy.
DRA improves the flowability of hydro carbons in pipeline, and what frictional reducing polymer was the most frequently used at present is poly-alpha olefins.Be elastomerics under this extra high molecular polymer normal temperature, and have very strong tackifying ability.
This polymkeric substance need reach good fineness and can be dissolved in rapidly in crude oil, the finished product wet goods hydro carbons, to reach drag-reduction effect.For the ease of the application of flow improver, need carry out aftertreatment to the drag reducer polymerization thing, in order to obtain having the flow improver of good fineness.
General aftertreatment preparation method adopts liquid nitrogen that polymkeric substance is cooled to the second-order transition temperature condition mostly and pulverizes, but adds the slurry that disperses to become unrestricted flow or pumping in the solvent after reaching granularity requirements.Need to add antisticking agent (or being called dispersion agent) in the pulverizing and prevent the secondary bonding, also need add tensio-active agent and stablizer when disperseing to become slurry.
Under cold condition, reach in the pulverizing of polymkeric substance of vitrifying state, liquid nitrogen is running stores fully, not only there is the loaded down with trivial details problem of accumulating, equipment all needs the precooling of long period before each start, raw material also needs cold until vitrifying, and producers' low-temperature safety and asphyxiation hazard all are the problems that this method must be noted that.
Summary of the invention
The problem that invention will solve
For eliminate liquid nitrogen to producers' injury from low temperature with Hazard Factor such as suffocate, and under non-low temperature the flow improver of the good fineness of preparation, the inventor has proposed the method for using vibration mill to carry out the flow improver aftertreatment under non-low temperature, thereby has finished the present invention.
For the scheme of dealing with problems
The invention provides a kind of polyolefine oil base crude oil with flow improver aftertreatment preparation method, it is characterized in that: under non-cold condition with vibration mill with the refinement of drag reducer polymerization thing and make slurry, obtain polyolefine oil base crude oil flow improver finished product.
Wherein said vibration mill vibrational frequency is more than the 3Hz, below the 30Hz; Amplitude is between 1mm ~ 30mm.
Preparation method of the present invention after described drag reducer polymerization thing is added vibration mill, may further comprise the steps:
1) stick together-tear step, keeping temperature of charge is 40 ℃～90 ℃, the Vibration on Start-up mill;
2) refinement-emulsifying step, keeping temperature of charge is 5 ℃～40 ℃, adds dispersion agent and emulsifying agent;
3) dilution-dispersion steps continues to add dispersion agent, obtains described polyolefine oil base crude oil flow improver finished product.
Preparation method of the present invention, wherein said drag reducer polymerization thing is selected from the group that poly-alpha olefins, sovprene, polyalkylene oxides, polysiloxane, polyacrylic ester, vinyl acetate homopolymer or multipolymer are formed.
Preparation method of the present invention is wherein sticked together-is torn in the step and can add thickening material and dispersion agent, and based on the drag reducer polymerization thing of 100 weight parts, dispersion agent is 13 ~ 60 weight parts, and thickening material is 3 ~ 30 weight parts.
Preparation method of the present invention is wherein described sticking together-tear in the step and can further add emulsifying agent and/or varsol.
Preparation method of the present invention, wherein said dispersion agent is selected from the solvent that has hydroxyl, carbonyl or ehter bond, and described thickening material is selected from natural or artificial high molecular polymer, polyose, Mierocrystalline cellulose and derivative, starch and derivative thereof.
Preparation method of the present invention, wherein in described refinement-emulsifying step, based on the drag reducer polymerization thing of 100 weight parts, the dispersion agent of interpolation is 20 ~ 70 weight parts, emulsifying agent is 10 ~ 35 weight parts.
Preparation method of the present invention, wherein in described dilution-dispersion steps, based on the drag reducer polymerization thing of 100 weight parts, the dispersion agent of interpolation is 30 ~ 170 weight parts.
Preparation method of the present invention, the polyolefine oil base crude oil that wherein obtains is 30 ~ 130 microns with the mean particle size of flow improver finished product.
The effect of invention
Adopt polyolefine oil base crude oil of the present invention flow improver aftertreatment preparation method, can be under non-cold condition with the refinement of drag reducer polymerization thing and become slurry, obtain oil base drag reducer for crude oil finished product, eliminated liquid nitrogen to producers' injury from low temperature with Hazard Factor such as suffocate, and realize providing the flow improver of good fineness under the non-low temperature.
Embodiment
The present invention under non-cold condition with vibration mill with the refinement of drag reducer polymerization thing and become slurry, for the synthesis of oil base crude oil flow improver.
" low temperature " described in the present invention refers to be lower than the temperature of the second-order transition temperature of drag reducer polymerization thing, and under this temperature, polymkeric substance can easily grind." non-low temperature " described in the present invention is the concept with respect to " low temperature ", refers to be higher than the temperature of the second-order transition temperature of drag reducer polymerization thing.
Vibration mill for the present invention's use, present method adopts mode of vibration to realize the polymkeric substance pulverizing, drive the cylindrical shell vibration by exciting source, exciting source can adopt electronic, pneumatic or hydraulic way, shaking shape can be for round or oval, be added with medium in the cylindrical shell, medium is ball, short cylindrical or other form bulks, also can be barred body.Cylindrical shell can dispose chuck, is used for heating or cooling.Pulverised form can be discontinuous or continous way, and charging process can continuously feeding or discontinuous charging.Vibrational frequency is generally more than the 3Hz, and below the 30Hz, preferred 10 ~ 20Hz, amplitude generally are between 1mm ~ 30mm, preferred 3 ~ 15mm.
Drag reducer polymerization thing described in the present invention refers to comprise hydrocarbon polymer and non-hydrocarbon polymers for the preparation of the polymkeric substance that subtracts poly-agent, can be used alone or in combination.
There is no particular limitation for drag reducer polymerization thing used in the present invention, as long as it can form polyolefine oil base crude oil flow improver (hereinafter to be referred as flow improver) after treatment.The operable drag reducer polymerization thing of the present invention can be enumerated but is not restricted to poly-alpha olefins, sovprene, polyalkylene oxides, polysiloxane, the polymkeric substance of the polymkeric substance of olefin(e) acid ester such as acrylate, vinyl acetate or multipolymer, above-mentioned polymkeric substance can be used alone or in combination.
The thickening material that the present invention uses, dispersion agent and emulsifying agent are this area reagent commonly used.Thickening material (or claiming tackifier) needs can be dissolved in the dispersion agent, and the example of thickening material includes but not limited to: polyvinyl alcohol, polyethylene wax, polyvinylpyrrolidone, acrylic resin, hydroxyl starch propionate, carboxymethyl starch, Xylo-Mucine, ethyl cellulose, cellulose acetate, zein, xanthan gum, gum arabic etc.Thickening material herein also available other industry is called the kind of tackiness agent.
Dispersion agent adopts the poor solvent of relative polymkeric substance, in principle can not dissolve polymer, and polymkeric substance is insoluble or slightly soluble in this dispersion agent.Described dispersion agent is selected from the solvent that has hydroxyl, carbonyl or ehter bond.The example of dispersion agent includes but not limited to that water, alcohol, ketone, ester, hydramine, ether etc. are used alone or as a mixture, and is pure as Virahol, propylene glycol, ethylene glycol, butanols, hexanol, octanol, polyoxyethylene glycol etc., hydramine such as trolamine, ether such as dipropylene glycol methyl ether etc.
At least need comprise a kind of water-in-oil-type tensio-active agent in the emulsifying agent, also can be by water-in-oil-type and oil-in-water-type surfactant compound.
The example of emulsifying agent includes but not limited to polyoxyethylene glycol (PEG), polyethers (poloxamer), sapn (span), tween (tween), sucrose fatty ester, mono fatty acid glycidol, the bis-fatty acid glyceride, the tri-fatty glyceride, polyglycerol fatty acid ester, Polyglycerine castor-oil plant alcohol ester, Xylitol acid anhydride mono fatty acid ester, sorbitan aliphatic ester, lipid acid and derivative thereof, stearyl alcohol, hexadecanol, semi-synthetic fatty acid ester, propylene glycol fatty acid ester, the organic acid monoglyceryl ester, Yelkin TTS, the monohydroxy-alcohol fatty acid ester, they can be used singly or in combination.
After adding the drag reducer polymerization thing in the described vibration mill, handle through sticking together-tear step, refinement-emulsifying step, three steps of dilution-dispersion steps.
Sticking together-tearing in the step, keeping temperature of charge is 40 ℃～90 ℃, makes polymkeric substance be good elasticity body state.Along with temperature raises, polymer strength reduces, and adhesion also reduces, and preferred adhesion is down to 300g/25mm.The Vibration on Start-up mill, vibration is conducive to short texture between polymer molecule.For improving adhesion, can add thickening material.Thickening material also has an opportunity to penetrate in the polymkeric substance, plays the effect of grinding aid.The addition of dispersion agent preferably can form higher system viscosity (preferably 〉=8000cp) with thickening material.This step can add emulsifying agent.For reducing the intensity of polymkeric substance, also can add varsol.The vibro-grinding time in this stage is 3 ~ 30min, preferred 7 ~ 15min.With respect to 100 weight parts resistance agent polymkeric substance, the addition of thickening material is 6 ~ 18 weight parts in this step, preferred 9 ~ 15 weight parts, more preferably 9 ~ 13 weight parts; The addition of dispersion agent is 17 ~ 40 weight parts, preferred 20 ~ 30 weight parts, more preferably 20 ~ 24 weight parts; The addition of emulsifying agent is 6 ~ 18 weight parts, preferred 9 ~ 15 weight parts, more preferably 9 ~ 13 weight parts.
In refinement-emulsifying step, prevent adhesion to improve stability by adding dispersion agent and emulsifying agent, oiliness end and polymkeric substance are affine, and water-based end and dispersion agent are affine, also can improve crush efficiency.In this step, temperature of charge is 5 ℃～40 ℃.The vibro-grinding time of this step is for being 3 ~ 30min, preferred 7 ~ 15min.With respect to 100 weight parts resistance agent polymkeric substance, the addition of dispersion agent is 30 ~ 60 weight parts in this step, preferred 35 ~ 50 weight parts, more preferably 35 ~ 42 weight parts; The addition of emulsifying agent is 15 ~ 30 weight parts, preferred 17 ~ 27 weight parts, more preferably 17 ~ 23 weight parts.
In dilution-dispersion steps, continue to add dispersion agent, and realize the particle dispersing depolymerization of secondary adhesion or reunion, obtain oil base drag reducer for crude oil finished product.In this step, temperature of charge is 5 ~ 40 ℃.The vibro-grinding time in this stage is in the 10min, in the preferred 3min.With respect to 100 weight parts resistance agent polymkeric substance, the addition of dispersion agent is 40 ~ 150 weight parts in this step, preferred 70 ~ 130 weight parts, more preferably 70 ~ 118 weight parts.
Among the present invention, the dispersion agent or the emulsifying agent that use in above-mentioned three steps can be identical or different.Preferably sticking together-tearing and using dipropylene glycol dme, butanols, water, Virahol, ethylene glycol, glycerol, ethanol, hexanol as dispersion agent in the step, class of department, tween, mono-glycerides, sucrose ester, sodium laurylsulfonate/Sodium dodecylbenzene sulfonate/sodium lauryl sulphate, sodium stearate/potassium are as emulsifying agent.Preferably make water, Virahol, ethylene glycol, butanols, dipropylene glycol dme, ethanol, hexanol as dispersion agent in refinement-emulsifying step, class of department, tween, mono-glycerides, sucrose ester, sodium laurylsulfonate/Sodium dodecylbenzene sulfonate/sodium lauryl sulphate are as emulsifying agent.Preferably in dilution-dispersion steps, use butanols, water, Virahol, ethylene glycol, dipropylene glycol dme, hexanol as dispersion agent.
Embodiment
Adopt the mode of embodiment that the present invention is explained in further detail below, but the present invention is not limited to described embodiment.
Vibration mill: dragon lifeline refining mills LVM or LRVM.
Drag reducer polymerization thing: the poly-alpha olefins that pipelines and petrochemical pipelines conveying technology company limited of Xuzhou Golden Bridge produces.
Dispersion agent: ethanol, dipropylene glycol dme
Thickening material: acrylic resin
Emulsifying agent: class of department 60, tween 80
Center particle size detection method: get 1 ~ 3g sample under 0 ~ 10 ℃ of environment, place milscale to detect the position small amount of sample, be threaded to slip with the fine setting button, reading.Repeat five times, average.
Embodiment 1
Vibration mill is heated to 60～80 ℃, and 600g drag reducer polymerization raw material is inserted, and once or progressively adds 400g ethanol and 30g acrylic resin, start 15～30min.
Vibration mill is cooled to 10～20 ℃ then, once or progressively adds class of dipropylene glycol dme 500g and 60g department 60,70g tween 80, start 20～30min, inspection center's granularity is 80～120 microns, adds 600g butanols start 3min and obtains finished product.
Embodiment 2
The leading portion that continous way is vibrated cylindrical shell is set to 60～80 ℃, and back segment is set to 10～30 ℃.600g drag reducer polymerization raw material is inserted, enter the vibration tube with helical feed, and add 300g ethanol and 30g acrylic resin continuously in leading portion; Back segment adds 700g dipropylene glycol dme, class of 60g department 60,70g tween 80, and inspection center's granularity is 80～120 microns, adds 400g butanols start 3min and obtains finished product.
Claims (11)
1. a polyolefine oil base crude oil is characterized in that with flow improver aftertreatment preparation method: under non-cold condition with vibration mill with the refinement of drag reducer polymerization thing and make slurry, obtain polyolefine oil base crude oil flow improver finished product;
After described drag reducer polymerization thing is added described vibration mill, may further comprise the steps:
1) stick together-tear step, keeping temperature of charge is 40 ℃～90 ℃, the Vibration on Start-up mill;
2) refinement-emulsifying step, keeping temperature of charge is 5 ℃～40 ℃, adds dispersion agent and emulsifying agent;
3) dilution-dispersion steps continues to add dispersion agent, obtains described polyolefine oil base crude oil flow improver finished product.
2. preparation method according to claim 1, wherein said vibration mill vibrational frequency is more than the 3Hz, below the 30Hz; Amplitude is between 1mm～30mm.
3. preparation method according to claim 1, wherein said drag reducer polymerization thing is selected from the group that poly-alpha olefins, sovprene, polyalkylene oxides, polysiloxane, polyacrylic ester, vinyl acetate homopolymer or multipolymer are formed.
4. preparation method according to claim 1 is wherein sticked together-is torn in the step and can add thickening material and dispersion agent, and based on the drag reducer polymerization thing of 100 weight parts, dispersion agent is 13～60 weight parts, and thickening material is 3～30 weight parts.
5. preparation method according to claim 4 is wherein described sticking together-tear in the step and can further add emulsifying agent and/or varsol.
6. preparation method according to claim 4, wherein said dispersion agent is selected from the solvent that has hydroxyl, carbonyl or ehter bond, and described thickening material is selected from natural or artificial high molecular polymer.
7. preparation method according to claim 4, wherein said thickening material is selected from polyose, Mierocrystalline cellulose and derivative thereof.
8. preparation method according to claim 4, wherein said thickening material is selected from starch and derivative thereof.
9. preparation method according to claim 1, wherein in described refinement-emulsifying step, based on the drag reducer polymerization thing of 100 weight parts, the dispersion agent of interpolation is 20～70 weight parts, emulsifying agent is 10～35 weight parts.
10. preparation method according to claim 1, wherein in described dilution-dispersion steps, based on the drag reducer polymerization thing of 100 weight parts, the dispersion agent of interpolation is 30～170 weight parts.
11. according to any described preparation method of claim 1-10, the polyolefine oil base crude oil that wherein obtains is 30～130 microns with the mean particle size of flow improver finished product.
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| CN103030726A (en) * | 2012-12-27 | 2013-04-10 | 天津市职业大学 | Preparation method of powdered drag reducing agent for crude oil transportation |
| CN103012641A (en) * | 2012-12-31 | 2013-04-03 | 天津市职业大学 | Preparation method of organic-silicon-containing drag reducer for oil product delivery |
| CN110397852A (en) * | 2019-07-04 | 2019-11-01 | 胜利油田方圆化工有限公司 | A kind of drag reduction water drag reducer of easy degradation |
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| CN101173049A (en) * | 2007-10-15 | 2008-05-07 | 济南倍力粉技术工程有限公司 | Method for producing polyethylene wax micro mist |
| CN101268164A (en) * | 2005-09-20 | 2008-09-17 | 贝克休斯公司 | Non-cryogenic process for granulating polymer drag reducing agents |
| CN101484556A (en) * | 2005-06-14 | 2009-07-15 | 贝克休斯公司 | Bi-or multi-modal particle size distribution to improve dragreduction polymer dissolution |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2217463Y (en) * | 1995-03-06 | 1996-01-17 | 四川联合大学 | Dynamic chemical reactor |
| CN101484556A (en) * | 2005-06-14 | 2009-07-15 | 贝克休斯公司 | Bi-or multi-modal particle size distribution to improve dragreduction polymer dissolution |
| CN101268164A (en) * | 2005-09-20 | 2008-09-17 | 贝克休斯公司 | Non-cryogenic process for granulating polymer drag reducing agents |
| CN101173049A (en) * | 2007-10-15 | 2008-05-07 | 济南倍力粉技术工程有限公司 | Method for producing polyethylene wax micro mist |
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Inventor after: Cao Danfu Inventor after: Yin Shoucheng Inventor after: Ma Yuwei Inventor after: Lin Sen Inventor after: Su Hang Inventor after: Li Hao Inventor after: Sun Rui Inventor after: Zhuang Jun Inventor after: Wang Yiran Inventor after: Yang Hui Inventor after: Cui Di Inventor after: He Tianyu Inventor after: Ni Guangdi Inventor after: Zhang Ning Inventor after: Hong Huajin Inventor after: Jiang Hesheng Inventor after: Wu Jie Inventor after: Cheng Xuxia Inventor after: Wang Dezhi Inventor after: Huang Mingbin Inventor before: Cao Danfu Inventor before: He Tianyu Inventor before: Zhang Ning Inventor before: Hong Huajin Inventor before: Jiang Hesheng |
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Free format text: CORRECT: INVENTOR; FROM: CAO DANFU HE TIANYU ZHANG NING HONG HUAJIN JIANG HESHENG TO: CAO DANFU HE TIANYU ZHANG NING HONG HUAJIN JIANG HESHENG WU JIE CHENG XUXIA WANG DEZHI HUANG MINGBIN YIN SHOUCHENG MA YUWEI LIN SEN SU HANG LI HAO SUN RUI ZHUANG JUN WANG YIRAN YANG HUI CUI DI NI GUANGDI |
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Effective date of registration: 20220208 Address after: 100029 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: State pipe network group east crude oil storage and Transportation Co.,Ltd. Patentee after: XUZHOU JINQIAO PETROCHEMICAL PIPELINE TRANSPORTATION TECHNOLOGY CO.,LTD. Patentee after: Shandong Dragon Vein Scientific Development Co.,Ltd. Address before: 100029 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: PIPELINE STORAGE AND TRANSPORT BRANCH OF CHINA PETROLEUM & CHEMICAL Corp. Patentee before: XUZHOU JINQIAO PETROCHEMICAL PIPELINE TRANSPORTATION TECHNOLOGY CO.,LTD. Patentee before: Shandong Dragon Vein Scientific Development Co.,Ltd. |