CN100371404C - Wax deposition resistant coating for oil pipeline - Google Patents
Wax deposition resistant coating for oil pipeline Download PDFInfo
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- CN100371404C CN100371404C CNB2006100128369A CN200610012836A CN100371404C CN 100371404 C CN100371404 C CN 100371404C CN B2006100128369 A CNB2006100128369 A CN B2006100128369A CN 200610012836 A CN200610012836 A CN 200610012836A CN 100371404 C CN100371404 C CN 100371404C
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- wax deposition
- resistant coating
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Abstract
The present invention relates to a wax deposition preventing coating for inner surfaces of oil delivery pipelines in the processes of crude oil exploitation and pipeline gathering and transportation, which comprises 20% to 50% of modified polyurethanes, 5% to 30% of polyvinylidene fluoride, 5% to 20% of epoxy resins, 2% to 20% of molybdenum disulfide and 2% to 10% of cerium fluoride. The wax deposition preventing coating of the present invention has the advantages of low surface energy, high wax deposition preventing efficiency, high bond strength with bottom materials, corrosion resistance and oil resistance, can also be used for solving the problems of the wax deposition prevention of the inner walls of oil storage and refining equipment, the corrosion prevention and the dirt sticking prevention of press rollers of paper making machines, the dirt prevention and the algae prevention of dirt preventing, algae preventing, and building coatings of ships, or racing boats, or submarines, etc.
Description
Technical field
The present invention relates to a kind of Wax deposition resistant coating, be mainly used in oil pipeline internal surface in Oil extraction and the defeated process of pipeline collection is carried out the processing of anti-caking wax coating.
Background technology
The crude oil that China produces be mostly high sticking, easily coagulate, crude oil that wax content is high, general wax content is 15%～25%, some in addition reach more than 40%.For high wax content oil, in the exploitation and storage and transport process of oil, because conditions such as temperature, pressure change, wax and colloid can be separated out from crude oil in a large number, be deposited on the inwall of the sucker rod surface of downhole hardware and oil pipeline and oil storage container, the wax deposition phenomenon is serious.Aspect Oil extraction, reduce the fuel-displaced ability of oil well, reduce the oil pumper life-span; To increase the crude oil flow resistance aspect the crude oil accumulating, and cause the pipeline net sectional area to reduce even blocking pipe, reduce oil transportation and store oil ability, waste energy.Nearly tens dollars of the financial losses that wax deposition in annual in the world because crude production, the transportation and wax deposit cause.
Crude oil in China output be to carry more than 65% by oil pipeline, for preventing wax precipitation frozen plug oil pipeline, reduce the crude oil flow resistance, way commonly used is to adopt to carry, add methods such as chemical agent and top coat by the station heating along the line.
The present most of oil pipelines of China adopt the heating delivery technology.Can facilitate the respective change of wax crystalline form attitude structure in the crude oil by heating, thereby reach the purpose of improving the crude oil low-temperature fluidity.But this method fuel consumption is big, facility investment and overheads height, and the difficulty that restarts after shutdown, the annual crude oil that only is used to heat conveying and burns just reaches the hundreds of thousands of ton.
Sticking at height, easily coagulate, add chemical modification agents such as a certain amount of pour point depressant, viscosity reduction flow improver, wax crystal modifier in the high wax content oil, can change wax crystalline form attitude and structure in the crude oil, thereby reduce zero pour, apparent viscosity and the yield value of waxy crude oil, reach the purpose of improving waxy crude oil low-temperature fluidity, viscosity reduction drag reduction.Chinese patent 97105954 discloses " crude oil pyrochemistry viscosity-depression agent ", Chinese patent 98120311 discloses " a kind of viscosity reducer for crude oil ", Chinese patent 02116293 discloses " flow improver for crude oil and preparation method thereof ", Chinese patent 02123728 discloses " crude oil flowability improver " etc., these patents all are to adopt various tensio-active agents to carry out composite, wax, colloid emulsification in the crude oil are disperseed, thereby reach the purpose of viscosity reduction, pour point depression, anti-wax deposition.Can improve wax deposition and flowability problem in the carried of crude oil process though in crude oil, add a certain amount of chemical agent, after wax and colloid emulsification are disperseed, bring very big trouble to following process such as the separation of crude oil, refinings again.
Chinese patent 02123553 discloses " tubing that contains resistance-reducing water-repelling inner coating ", be to scribble the undercoat that contains nano titanium oxide at the steel pipe inwall, this coating can not directly stop the deposition of wax, but need after stopping conveying, utilize the irradiation of UV-light to remove organic impurity such as deposition of wax.This technology is not suitable for the oil pipeline condition, can't use in oil pipeline.
Summary of the invention
The purpose of this invention is to provide a kind of Wax deposition resistant coating for oil pipeline, this coating is prevented wax deposition efficient height, anti-strong acid, highly basic, and salt tolerant, oil resistant, corrosion-resistant, ambient cure is with ground caking ability height, easy construction.
In order to achieve the above object, the present invention is a bonding system with the modified polyurethane, is main anti-wax deposition component with the polyvinylidene difluoride (PVDF), adds mineral filler molybdenumdisulphide and cerium fluoride, forms the Wax deposition resistant coating for oil pipeline of self-vulcanizing.Wax deposition resistant coating for oil pipeline of the present invention comprises the component of following quality percentage composition:
Modified polyurethane 20%～50%
Polyvinylidene difluoride (PVDF) 5%～30%
Resins, epoxy 5%～20%
Molybdenumdisulphide 2%～20%
Cerium fluoride 2%～10%
Solvent 10%～40%.
Modified polyurethane wherein is to be polymerized by hydroxy-end capped polydimethylsiloxane and polyurethane prepolymer.
The solvent that uses is the combination that a kind of or youngster in toluene, dimethylbenzene, acetone, the hexanaphthene plants.The mineral filler molybdenumdisulphide that adds and the granularity of cerium fluoride are 0.1～10 μ m.
Can also add an amount of flow agent and defoamer in coating, usually, flow agent adopts butyl polyacrylate, and defoamer adopts different tridecanol.
The know-why of Wax deposition resistant coating of the present invention mainly is based on: the wax deposition phenomenon of oil pipeline is except being subjected to this important factor of crude oil temperature influences, and factors such as the tube wall temperature difference, water content in crude oil and flow velocity, pipe surface character also have bigger influence to the wax deposition of oil pipeline.The surface free energy of oil pipeline inwall plays absolute effect to wax and gelationus adhesion, and the wax crystalline substance sticks to the oil pipeline inner wall surface under the adsorptive power effect, and constantly deposits, and this adsorptive power size depends on the surface wettability of tube wall and wax crystalline substance.The wettability of body surface changes with the different of its surface coating layer character with hydrophobic/oleophobic property, as long as form one deck coat on body surface, these character on surface is changed.The present invention considers from the angle that changes the oil pipeline surface wettability, at the wear-resisting antiseized coat of oil pipeline coated inner wall one deck, to change the surface property of inner-walls of duct, make and be in nonwetting state between institute's transporting fluid and the inner-walls of duct, form oleophobic surface, to reduce and the adhesion of wax intergranular, prevent the deposition of wax on inner-walls of duct of from crude oil, separating out.In addition, coat has also reduced the interaction force between inner-walls of duct and the crude oil, make the crude oil that flows form the part slippage at tube wall surface, thereby can obviously reduce on-way resistance, save the oil transportation energy consumption of long distance oil pipeline, even the high-load bituminous matter viscous crude of high viscosity is heated at normal temperatures or suitably carry out normal pipe-line transportation under the condition and become possibility.
The concrete preparation method of Wax deposition resistant coating is: according to above-mentioned quality percentage composition proportioning, with solvent modified polyurethane is dissolved earlier, be heated to 50 ℃～60 ℃, add polyvinylidene difluoride (PVDF), Resins, epoxy, molybdenumdisulphide and cerium fluoride successively, stir 3～8h, be chilled to room temperature, obtain Wax deposition resistant coating of the present invention.
The material modification urethane that uses be by hydroxy-end capped polydimethylsiloxane and polyurethane prepolymer in dimethylbenzene and/or acetone solvent, polyreaction forms under organotin catalysts and promotor effect.Wherein, contain mass percent in the polyurethane prepolymer and be 5～20% isocyanic ester, the content of vulcabond free monomer is 2～5%; Hydroxy-end capped polydimethylsiloxane molecular weight is not more than 5000.The organotin catalysts that adopts is dibutyl tin dilaurate, dibutyl tin acetate or monobutyl-tin-trichloride etc., and promotor is Diisopropyl azodicarboxylate or triethylamine.
Concrete method of modifying is: polyurethane prepolymer is added in the solvent, be heated to 60～80 ℃, slowly drip hydroxy-end capped polydimethylsiloxane earlier, be added drop-wise to organotin catalysts and promotor in the solution fast again after adding, reaction 3～6h, cooling obtains flaxen modified polyurethane product.
The modified polyurethane that obtains is the many block types multipolymer that is alternately rearranged by polydimethylsiloxane block and polyurethane blocks.This multipolymer is after film forming, polydimethylsiloxane block in the molecular structure tends to the surface aggregation orientation, and polyurethane blocks is towards internal layer, so just makes the mechanical property such as sticking power, hardness, curing speed of co-polymer membrane improve, and thermotolerance also is improved.Simultaneously, the surface of co-polymer membrane presents low surface energy, and minimum is 17mN/m
2, viscosity is 400～700mPas.
The present invention adopts hydroxy-end capped polydimethylsiloxane--modified urethane, and is bonding system with this modified polyurethane, adds materials such as polyvinylidene difluoride (PVDF), Resins, epoxy, molybdenumdisulphide and cerium fluoride and makes Wax deposition resistant coating for oil pipeline.Utilize the interaction and the synergistic effect of each component in the coating, make coating possessed low, the anti-wax deposition efficient height of ambient cure, surface energy, with over-all propertieies such as ground cohesive strength height, corrosion-resistant, oil resistant; Coating uses technology simple, can construct easy construction at normal temperatures and pressures; Spray pressure is 0.25Mpa, and coating cohesive force, resistance to impact shock and snappiness reach pre-provisioning request; The coated material physical and chemical performance is stable, the envrionment conditions that can bear oil pipeline.
The anti-wax deposition effect of coating of the present invention is obvious, and after oil pipeline used, period of removing the wax became 9 months by 3 months, and anti-wax deposition efficient can reach more than 60%.
Coating of the present invention also can be applicable to solve the anti-wax deposition of oil storage, refining equipment inwall; Pickup is prevented in the pressure roller protection against corrosion of weaving loom, paper machine; Antifouling, the anti-algae of steamer, racing boat or submarine and the problems such as antifouling, anti-algae of building coating.
Embodiment
Embodiment 1
Get in 50Kg polyurethane prepolymer, the 25Kg dimethylbenzene adding reactor, be warming up to 65 ℃, slowly add hydroxy-end capped polydimethylsiloxane 15Kg, the reinforced time is controlled at about 30min, after adding, be added dropwise to 1Kg dibutyl tin dilaurate and 1Kg Diisopropyl azodicarboxylate more fast, behind the insulation reaction 4h, be cooled to 20 ℃, obtain flaxen modified polyurethane product.
Embodiment 2
Get in 50Kg polyurethane prepolymer, the 25Kg acetone adding reactor, be warming up to 65 ℃, slowly add hydroxy-end capped polydimethylsiloxane 15Kg, the reinforced time is controlled at about 30min, after adding, be added dropwise to 1Kg monobutyl-tin-trichloride and 1Kg triethylamine more fast, behind the insulation reaction 4h, be cooled to 20 ℃, obtain flaxen modified polyurethane product.
Embodiment 3
Getting the 30Kg modified polyurethane drops in the reactor, add 20Kg dimethylbenzene, 10Kg acetone, be warming up to 60 ℃, under 500 rev/mins rotating speed, add 20Kg polyvinylidene difluoride (PVDF), 10Kg Resins, epoxy, 3Kg molybdenumdisulphide and 5Kg cerium fluoride successively, stirred 3 hours, be chilled to room temperature, add 1Kg flow agent and 1Kg defoamer, obtain the 100Kg Wax deposition resistant coating.
Embodiment 4
Getting the 25Kg modified polyurethane drops in the reactor, add 20Kg acetone, be warming up to 50 ℃, under 500 rev/mins rotating speed, add 30Kg polyvinylidene difluoride (PVDF), 15Kg Resins, epoxy, 5Kg molybdenumdisulphide and 3Kg cerium fluoride successively, stirred 3 hours, be chilled to room temperature, add 1Kg flow agent and 1Kg defoamer, obtain the 100Kg Wax deposition resistant coating.
Embodiment 5
Getting the 40Kg modified polyurethane drops in the reactor, add 15Kg hexanaphthene, 10Kg acetone, be warming up to 55 ℃, under 500 rev/mins rotating speed, add 25Kg polyvinylidene difluoride (PVDF), 5Kg Resins, epoxy, 3Kg molybdenumdisulphide and 2Kg cerium fluoride successively, stirred 3 hours, and be chilled to room temperature, obtain the 100Kg Wax deposition resistant coating.
Embodiment 6
Get the 35Kg modified polyurethane, the 20Kg polyvinylidene difluoride (PVDF), 15Kg Resins, epoxy, 6Kg molybdenumdisulphide, 4Kg cerium fluoride and 20Kg hexanaphthene prepare the 100Kg Wax deposition resistant coating according to embodiment 3 methods.
Embodiment 7
Get the 40Kg modified polyurethane, the 10Kg polyvinylidene difluoride (PVDF), 5Kg Resins, epoxy, 4Kg molybdenumdisulphide, the 4Kg cerium fluoride, 20Kg toluene, 15Kg acetone and 1Kg flow agent, the 1Kg defoamer prepares the 100Kg Wax deposition resistant coating according to embodiment 3 methods.
Embodiment 8
Get the 45Kg modified polyurethane, the 10Kg polyvinylidene difluoride (PVDF), 15Kg Resins, epoxy, 4Kg molybdenumdisulphide, the 4Kg cerium fluoride, 20Kg dimethylbenzene and 1Kg flow agent, the 1Kg defoamer prepares the 100Kg Wax deposition resistant coating according to embodiment 3 methods.
Under the condition of 25 ℃ of temperature, relative humidity 50%, the Wax deposition resistant coating that embodiment 3 is prepared carries out performance test, and experimental result is as follows:
| Sequence number | Interventions Requested | Technical indicator | Assay | The method of inspection |
| 1 | Solid part, and % (105 ℃, 2h) | Be not less than 50 | 52 | GB1721 |
| 2 | Set time | Room temperature, surface drying 2h | Room temperature, surface drying 2h | GB1728 |
| 3 | Hardness | 0.5～0.6 | 0.54 | GB1730 |
| 4 | Sticking power, MPa | Be not less than 10 | 11 | GB1720 |
| 5 | Shock strength, cm | Be not less than 50 | 56 | GB1732 |
| 6 | Snappiness, mm | ≤3 | 1 | GB1731 |
| 7 | Salt fog resistance (3.5%NaCl) | 100h | Qualified | GB1771 |
| 8 | Moisture-proof heat (47 ℃, RH 95%) | 48h | Qualified | GB1740 |
| 9 | Oil-proofness (transformer oil) | The 48h coating does not have efflorescence, and is wrinkle resistant, non-foaming, do not come off, and do not ftracture | Qualified | GB1739 |
Claims (7)
1. Wax deposition resistant coating for oil pipeline comprises the component of following quality percentage composition:
Modified polyurethane 20%～50%
Polyvinylidene difluoride (PVDF) 5%～30%
Resins, epoxy 5%～20%
Molybdenumdisulphide 2%～20%
Cerium fluoride 2%～10%
With
Solvent 10%～40%,
Wherein, described modified polyurethane is the many block types multipolymer that is alternately rearranged by polydimethylsiloxane block and polyurethane blocks.
2. Wax deposition resistant coating for oil pipeline according to claim 1 is characterized in that described solvent is one or more the combination in toluene, dimethylbenzene, acetone, the hexanaphthene.
3. Wax deposition resistant coating for oil pipeline according to claim 1 is characterized in that described modified polyurethane is to be polymerized by hydroxy-end capped polydimethylsiloxane and polyurethane prepolymer.
4. Wax deposition resistant coating for oil pipeline according to claim 3, it is characterized in that described modified polyurethane be by hydroxy-end capped polydimethylsiloxane and polyurethane prepolymer in dimethylbenzene and/or acetone solvent, under organotin catalysts and promotor effect, polyreaction forms.
5. Wax deposition resistant coating for oil pipeline according to claim 4 is characterized in that described organotin catalysts is dibutyl tin dilaurate, dibutyl tin acetate or monobutyl-tin-trichloride.
6. Wax deposition resistant coating for oil pipeline according to claim 4 is characterized in that described promotor is Diisopropyl azodicarboxylate or triethylamine.
7. the preparation method of the described Wax deposition resistant coating for oil pipeline of claim 1, it is characterized in that according to above-mentioned quality percentage composition proportioning, with the modified polyurethane dissolution with solvents, be heated to 50 ℃～60 ℃, add polyvinylidene difluoride (PVDF), Resins, epoxy, molybdenumdisulphide and cerium fluoride successively, stir 3h, be chilled to room temperature, obtain coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100128369A CN100371404C (en) | 2006-06-13 | 2006-06-13 | Wax deposition resistant coating for oil pipeline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100128369A CN100371404C (en) | 2006-06-13 | 2006-06-13 | Wax deposition resistant coating for oil pipeline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1865370A CN1865370A (en) | 2006-11-22 |
| CN100371404C true CN100371404C (en) | 2008-02-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2006100128369A Expired - Fee Related CN100371404C (en) | 2006-06-13 | 2006-06-13 | Wax deposition resistant coating for oil pipeline |
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| CN104565680A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Anticorrosion waxing-preventive composite pipe and manufacturing method thereof |
| CN103788853B (en) * | 2014-01-21 | 2016-04-27 | 江苏大学 | The preparation method of the super two open coat of a kind of urethane/molybdenumdisulphide |
| CN104403536A (en) * | 2014-11-19 | 2015-03-11 | 上海应用技术学院 | Anti-waxing coating for oil pipelines |
| CN104710772A (en) * | 2015-03-13 | 2015-06-17 | 西安华油兴科技术开发有限公司 | Novel anti-shearing drag reducing agent and preparing method thereof |
| CN104910806B (en) * | 2015-07-07 | 2017-12-12 | 北京天恒盛通科技发展有限公司 | A kind of preparation method of oil pipeline Wax proofing oleogel coating and its coating |
| CN106700677A (en) * | 2016-12-28 | 2017-05-24 | 广东石油化工学院 | Low transmitting molybdenum disulfide composite coating and preparation method thereof |
| CN109423207A (en) * | 2017-07-18 | 2019-03-05 | 北京泽马新技术有限公司 | Environmentally friendly transparent anti-corrosion Wax deposition resistant coating and preparation method |
| CN109423162A (en) * | 2017-07-18 | 2019-03-05 | 北京泽马新技术有限公司 | Crude oil pipeline Wax deposition resistant coating and coating production |
| CN115232495A (en) * | 2022-08-30 | 2022-10-25 | 电子科技大学 | Method for preventing asphalt adhesion and application |
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