CN100560616C - A kind of preparation method of drag reduction agent for oil product through pipelines - Google Patents
A kind of preparation method of drag reduction agent for oil product through pipelines Download PDFInfo
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- CN100560616C CN100560616C CNB2005101242140A CN200510124214A CN100560616C CN 100560616 C CN100560616 C CN 100560616C CN B2005101242140 A CNB2005101242140 A CN B2005101242140A CN 200510124214 A CN200510124214 A CN 200510124214A CN 100560616 C CN100560616 C CN 100560616C
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Abstract
The present invention relates to the preparation method of a kind of drag reduction agent for oil product through pipelines that is used for the oil product through pipelines drag reduction of organic high molecular compound and tubing system technical field.Present method follows these steps to carry out successively: earlier Primary Catalysts and promotor are added under nitrogen protection in the closed reaction vessel successively, adopt ultrasonic generator continuous oscillation 18～26 minutes; Adding polymerization single polymerization monomer under the ambient temperature conditions of nitrogen protection, vibration and-60 ℃～10 ℃ reacts; The monitoring reaction temperature adds the nitrobenzene retarder when the system temperature of reaction raises more than 3 ℃ compared with the beginning temperature of reaction; The failure of oscillations when treating that system viscosity rises to 3500～6000mpas; The vibrational frequency of ultrasonic generator is 25KHZ, and power is adjustable.System continues reaction 5～14 days after the failure of oscillations, the final purple polymkeric substance that gets.Present method easy handling is easy to control, is easy to ensure the quality of products, and resulting polymers molecular weight height, drag-reduction effect are good.
Description
Technical field
The present invention is the preparation method of a kind of drag reduction agent for oil product through pipelines of oil pipe drag reduction.Relate to organic high molecular compound and tubing system technical field.
Background technology
The drag reduction technology of oil pipeline has had very big progress in recent years, successively has to authorize or tens of the patents of application.The molecular weight of frictional reducing polymer is tending towards ultra-high molecular weight, and it is intact that the katalysis of catalyzer more becomes, and preparation method is gradually improved, and the polymerisate solid content is higher, the application at the oil pipeline scene of being more convenient for.In application on June 18th, 2003 " alpha-olefin-vinylbenzene ultra-high molecular weight drag reduction multipolymer and preparation method thereof ", adopt the polymerization single polymerization monomer of alpha-olefin-vinylbenzene ultrahigh molecular weight copolymer as our company, make and contain a spot of phenyl ring and stochastic distribution in the polymerization single polymerization monomer, improved the rigidity of this class linear polymer, avoided long molecular chain to twine, and polymerisate is the solid content height after dispersion, has improved drag reduction efficiency.But in its preparation method, still adopt traditional alr mode, make catalyst distribution inhomogeneous, rise to enough when big when system viscosity simultaneously, the poor effect that traditional alr mode stirs, and also the heat that produces is very big, can worsen polyreaction rapidly.So this patent application does not suitably suppress copolyreaction medium-chain rate of growth, has limited the molecular weight and the resistance reducing performance of multipolymer to a certain extent.
In macromolecular polymerization reaction for controls reaction speed, adding retarder is a kind of method commonly used, but in the building-up process of frictional reducing polymer, because the control of polymerization velocity and polymerization reaction heat directly influences final product performance, and the interpolation of retarder is directly connected to the generation of polymerization velocity and polymerization reaction heat, and then influence the resistance reducing performance of product, so one of skill in the art never attempted adding retarder in the drag reducing polymerization process.
Summary of the invention
The objective of the invention is to invent a kind of preparation method who makes the drag reduction agent for oil product through pipelines of drag reduction molecular weight of copolymer and drag reduction efficiency excellence.
The present invention has received polymerization single polymerization monomer to adopt alpha-olefin-vinylbenzene advantage, in the preparation method, adopt the mode of sonic oscillation to replace traditional alr mode, and according to a large amount of experiments, the opportunity and the addition of retarder have been determined to add, cause the interpolation of retarder to play positive effect-suitably suppress copolyreaction medium-chain rate of growth, rather than negative effect, and then constituted technological line of the present invention.Specifically be that present method is the same with prior art, polymerization single polymerization monomer is to derive from the alpha-olefin that contains 6～40 carbon number atoms and vinylbenzene in 80: 20～95: 5 ratio proportioning, catalyzer is Z-N System Catalyst and two kinds of catalyzer of metallocene catalyst, with the metallocene catalyst is preferred, the proportioning of polymerization single polymerization monomer and catalyzer is 1: 0.0001～1: 0.01, it is characterized in that present method follows these steps to carry out successively:
Earlier Primary Catalysts and promotor are added under nitrogen protection in the closed reaction vessel successively, adopt the ultra-sonic oscillation technology to vibrate, replace traditional alr mode, continuous oscillation 18～26 minutes mixes it;
Under the condition of nitrogen protection and vibration, add the blended polymerization single polymerization monomer, and under-60 ℃～10 ℃ envrionment temperature, react;
The monitoring reaction temperature when the system temperature of reaction raises more than 3 ℃ compared with the beginning temperature of reaction, adds retarder;
The failure of oscillations when treating that system viscosity rises to catalyzer and no longer sinks;
System continues reaction 5～14 days after the failure of oscillations, finally obtains the purple polymkeric substance.
Wherein ultrasonic generator places the reaction vessel below, and the vibrational frequency of producer is 25KHZ, and power is adjustable, and when system viscosity was lower than 1500mpa.s, hunting power was 1000w, and when viscosity was higher than 1500mpa.s, hunting power was adjusted to 1800w;
For the controlled polymerization speed of response, add nitrobenzene matters as retarder, the interpolation concentration in whole system is 10
7～-5MolL
-1By the viscosity that is contained in the viscometer detection architecture in the closed reaction vessel, the failure of oscillations when system viscosity rises to catalyzer and no longer sinks gets final product the failure of oscillations when promptly viscosity rises to 3500～6000mpas in the reaction process.
Present method one is to adopt ultra-sonic oscillation to replace traditional alr mode, avoids raising owing to stirring the extra system temperature that causes when system viscosity is enough big, worsens polyreaction; The 2nd, the district has added an amount of retarder on the exothermic heat of reaction peak, can suppress the rate of growth of chain, makes it slowly carry out chainpropagation reposefully, just can obtain more excellent molecular weight and resistance reducing performance.
Embodiment
Embodiment. with this example explanation concrete enforcement of the present invention.Selecting a volume for use is 1 cubic metre airtight logical nitrogen reaction vessel, and thermometer and viscometer are installed in this reaction vessel.Get 64 milliliters of 1-hexene hydrocarbon, 16 milliliters of vinylbenzene, cyclopentadienyl titanium dichloride 0.005g (1 μ mole), 2.5 milliliters of MAO (toluene solution 10mmol/L), oil of mirbane 8*10
-7Mol.In closed reaction vessel, fill earlier nitrogen before the beginning, air drain clean after, Yi Bian start the ultrasonic generator starting oscillation on one side fill nitrogen continuously.The first step adds cyclopentadienyl titanium dichloride in the closed reaction vessel earlier after formally beginning, and adds the back and then adds MAO more inward, adds from MAO to pick up counting, and continuous oscillation 20 minutes mixes cyclopentadienyl titanium dichloride and MAO; Second step, continue vibration and fill under the condition of nitrogen and add after freezing to 0 ℃ to closed reaction vessel polymerization single polymerization monomer-blended 1-oneself-alkene and vinylbenzene reacts; In the 3rd step, after beginning to react, the temperature in the monitoring reaction container when the temperature in the reaction vessel rises to 3 ℃, adds oil of mirbane at any time; The 4th step, the viscosity of monitoring reaction container internal reaction system, when the viscometer indicator value reaches 4000mpa.s, the failure of oscillations; In the 5th step, after the failure of oscillations, system continues reaction 6 days, obtains the purple polymkeric substance at last.The flow improver product made of polymkeric substance is on probation through certain crude oil pipeline thus, only injects the flow improver product of 15PPm in crude oil pipeline, just reaches 31% drag-reduction effect, improves 9% than existing flow improver effect.
Therefore present method is with common polymerization unit, and technical process is also simpler, is convenient to operation, is convenient to control, is easy to ensure the quality of products the polymerized product excellent performance.
Claims (5)
1. the preparation method of a drag reduction agent for oil product through pipelines, comprise and to derive from the alpha-olefin that contains 6～40 carbon number atoms and styrene polymerization monomer in 80: 20～95: 5 ratio, polymerization under the catalysis of transistion metal compound Primary Catalysts and promotor, wherein the ratio of catalyzer and polymerization single polymerization monomer is 0.0001: 1～0.01: 1, it is characterized in that the preparation method follows these steps to carry out successively:
Earlier Primary Catalysts and promotor are added in the closed reaction vessel under nitrogen protection successively, vibrate with ultrasonic generator, continuous oscillation 18～26 minutes mixes it;
Under the condition of nitrogen protection and vibration, add the blended polymerization single polymerization monomer, and under-60 ℃～10 ℃ envrionment temperature, react;
The monitoring reaction temperature when the system temperature of reaction raises more than 3 ℃ compared with the beginning temperature of reaction, adds retarder;
The failure of oscillations when treating that system viscosity rises to catalyzer and no longer sinks;
System continues reaction 5～14 days after the failure of oscillations, the final purple polymkeric substance that gets.
2. the preparation method of a kind of drag reduction agent for oil product through pipelines according to claim 1, it is characterized in that ultrasonic generator places the reaction vessel below, the vibrational frequency of producer is 25KHZ, power is adjustable, when system viscosity is lower than 1500mPa.s, hunting power is 1000w, and when viscosity was higher than 1500mPa.s, hunting power was adjusted to 1800w.
3. the preparation method of a kind of drag reduction agent for oil product through pipelines according to claim 1 is characterized in that retarder selects nitrobenzene matters.
4. the preparation method of a kind of drag reduction agent for oil product through pipelines according to claim 3 is characterized in that the interpolation concentration of described retarder in whole system is 10
-7Mol/L～10
-5Mol/L.
5. the preparation method of a kind of drag reduction agent for oil product through pipelines according to claim 1 is characterized in that described system viscosity is to be detected by the viscometer that is installed in the reaction vessel, stops concussion when viscosity reaches 3500～6000mpas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101242140A CN100560616C (en) | 2005-11-29 | 2005-11-29 | A kind of preparation method of drag reduction agent for oil product through pipelines |
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| CNB2005101242140A CN100560616C (en) | 2005-11-29 | 2005-11-29 | A kind of preparation method of drag reduction agent for oil product through pipelines |
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| Publication Number | Publication Date |
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| CN1978474A CN1978474A (en) | 2007-06-13 |
| CN100560616C true CN100560616C (en) | 2009-11-18 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328397B (en) * | 2007-06-20 | 2011-04-20 | 中国石油天然气股份有限公司 | Electronic donor of crude oil pipeline drag reducer and preparation thereof |
| CN101418077B (en) * | 2007-10-25 | 2011-05-25 | 中国石油天然气股份有限公司 | Method for preparing polyolefin cladding oil pipe drag reduction polymer microcapsule powder |
| CN101735366B (en) * | 2009-12-17 | 2011-09-14 | 中国石油化工股份有限公司 | Complex electron donor for drag reducer polymerization |
| CN102453297B (en) * | 2010-10-28 | 2013-10-16 | 中国石油天然气股份有限公司 | Supermolecular polymer drag reduction agent for oil products and preparation method thereof |
| CN105440193B (en) * | 2015-12-25 | 2018-01-16 | 胜利油田胜利化工有限责任公司 | Suspension polymerisation prepares drag reduction agent for oil product through pipelines |
-
2005
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| CN1978474A (en) | 2007-06-13 |
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Effective date of registration: 20211105 Address after: Room 08-10, 6 / F, block a, No. 5, Dongtucheng Road, Chaoyang District, Beijing 100013 Patentee after: National Petroleum and natural gas pipeline network Group Co.,Ltd. Address before: 100011 Beijing city Dongcheng District No. 16 Andrew intercontinental building Patentee before: PETROCHINA Co.,Ltd. |
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