CN1216098C - Emulsion liquor of alpha-olefin drag-reducing polymer, its preparation method and production equipment - Google Patents
Emulsion liquor of alpha-olefin drag-reducing polymer, its preparation method and production equipment Download PDFInfo
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- CN1216098C CN1216098C CN 03109631 CN03109631A CN1216098C CN 1216098 C CN1216098 C CN 1216098C CN 03109631 CN03109631 CN 03109631 CN 03109631 A CN03109631 A CN 03109631A CN 1216098 C CN1216098 C CN 1216098C
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Abstract
The present invention relates to an emulsifying compound of an alpha-olefin resistance reducing polymer, which is used for the resistance reduction of an oil transportation pipeline, and a preparation method and production equipment thereof. The emulsifying compound is formed by mixing liquid carriers comprising alpha-olefin resistance reducing polymer and liquid carriers comprising organic hydrocarbon, oil soluble ester or ether. In the preparation method, firstly, the alpha-olefin resistance reducing polymer and the organic hydrocarbon substance are added into a high-temperature and high-pressure reaction kettle which is then pressurized to 2 to 10MPa; After the materials are heated to 160 to 280DEG C while stirring, the materials are kept for 5 to 48 hours. The ester substance or the ether substance is added to be stirred for 0.5 to 5 hours by continuously maintaining original temperature and pressure. The production equipment of the emulsifying compound is formed by adding a high pressure charging device on the high-temperature and high-pressure reaction kettle.
Description
Relate to the field
The present invention is the drag reduction that is used for oil product through pipelines.The composition and the tubing system field that relate to macromolecular compound.
Background technology
Friction resistance when flowing in pipeline in order to reduce oil product cuts down the consumption of energy or increases throughput rate, will add flow improver usually in pipeline.Extensively adopt effective alpha-olefin extra high molecular polymer flow improver at present both at home and abroad.But when producing poly-alpha-olefin drag reduction agent owing to the employing solution polymerization process, the viscosity of products therefrom is high, even surpasses 50000 centipoises.Therefore, bring very big difficulty for the injection of flow improver; And when adopting mass polymerization to produce poly-alpha-olefin drag reduction agent, products therefrom is the viscoelastic solid material, can't inject oil pipeline, must pass through postprocessing working procedures again, it is become have mobile liquid product the ability practical application.For this reason, people make the approach of alpha-olefin extra high molecular polymer flow improver liquid stateization always in research.Successively developed the post-treating method of two kinds of drag reducer polymerization things the nineties in eighties of last century.First method is the method that high molecular polymer is separated from polymeric reaction product (seeing United States Patent (USP) U.S.Patent 5,376,697,1994 years) at the development of solution polymerization method.Concrete grammar is that the solution polymerization product is handled by a kind of special device, polymkeric substance is precipitated out from solution, under suitable temperature, dry then, put into the environment that is lower than the polymer glass temperature, under the condition that solid dispersions such as calcium stearate is arranged exist, wear into the powder of certain fineness, make paste liquid with water, alcohol, Liniment, tensio-active agent, suspension agent, thickening material, sterilant, defoamer etc. by stirring then.Second method is (to see patent U.S.Patent 5 at the method for directly polymeric reaction product being made paste liquid with water, alcohol, Liniment, tensio-active agent, suspension agent, thickening material, sterilant, defoamer etc. by stirring again after pulverizing under the condition of ultralow temperature of bulk polymerization method development, 449,732, nineteen ninety-five; U.S.Patent 5,504,132,1996 years; U.S.Patent 5,539,044,1996 year; WO97/01582,1997; U.S.Patent 5,733,953,1998 years; WO98/1658,1998; CN1233271A, 1999).The flow improver that above-mentioned two kinds of methods obtain has advantages such as polymer concentration is higher relatively, injection technology is simple, but they contain the non-dissolubility dispersion agent of solid, can exert an influence to processed oil character, simultaneously product leaves standstill less stable, just the caked phenomenon of layering and polymer poly can occur after placing certain hour, use to the production scene and bring inconvenience.
Summary of the invention
The objective of the invention is to invent a kind of product and leave standstill excellent stability and can be impurity band inlet pipe oil transportation product such as solid dispersion, water, alcohol, do not influence oil property, be specially adapted to the emulsification flow improver and preparation method thereof and the production equipment of the alpha-olefin frictional reducing polymer of products pipeline.
The emulsification flow improver of alpha-olefin frictional reducing polymer of the present invention is with common to add the flow improver of chemical additive by the alpha-olefin extra high molecular polymer different, but alpha-olefin extra high molecular polymer and the oil soluble ester class or the liquid carrier mixed together formed of ether material that are insoluble to by organic hydrocarbon, alpha-olefin extra high molecular polymer are wherein formed.Here the alpha-olefin extra high molecular polymer of indication refers to molecular weight above 10
6, and be non-crystalline type and oil-soluble alpha-olefinic polymer.Organic hydrocarbon material in the liquid carrier is diesel oil, gasoline, benzene,toluene,xylene, hexane, heptane, octane, hexanaphthene or their mixture.And ester class or ether material are glyceryl monostearates, mix stearin, single tripalmitin, mix tripalmitin, olein, glycerin fatty acid ester, the Diethylene Glycol SUNSOFT Q-182S, the Diethylene Glycol mono-laurate, diethylene glycol monostearate, Isopropyl myristate, Triglycerol Caprylate-Caprate class and heptyl phenol polyethenoxy ether, heptyl phenol polyethenoxy ether, the hexyl phenol polyethenoxy ether, hexyl phenol polyethenoxy ether, polyoxyethylene octylphenol ether, the octyl phenol polyethenoxy ether, polyoxyethylene nonylphenol ether, nonyl phenol poly-oxypropylene ether, Brij, the oleyl alcohol polyethenoxy ether.The proportioning of this emulsification is: the weight ratio of alpha-olefin extra high molecular polymer in mixture is 10～40%, and the weight ratio of liquid carrier in mixture is 40～90%; To account for the weight ratio of liquid carrier be 40～80% to the organic hydrocarbon material in the liquid carrier, and the weight ratio that ester class or ether material account for liquid carrier is 20～60%.Among the present invention, oil soluble ester class or ether material that the alpha-olefin extra high molecular polymer is insoluble to wherein make alpha-olefin extra high molecular polymer microparticle surfaces charged, perhaps form film on the polymer particles surface, to stop alpha-olefin extra high molecular polymer particulate in the organic hydrocarbon solvent, to be in contact with one another, take place coalescent, thereby effectively reduce the apparent viscosity of product and leave standstill stability.
The preparation method of this alpha-olefin extra high molecular polymer emulsification: earlier alpha-olefin extra high molecular polymer and organic hydrocarbon material are added high-temperature high-pressure reaction kettle in proportion, sealed reactor, (progressively heat up while stirring under 2～10MPa) at certain pressure, make the temperature of mixture system reach 160～280 ℃, and kept 5～48 hours, to wherein adding ester class or ether material, the temperature stirring that continues to keep original got final product in 0.5～5 hour again.The pressurization here is to adopt nitrogen pressure.And when adding ester class or ether material, be under high pressure that keeps having reached and hot conditions, to add.Therefore just particular requirement has been proposed its production equipment.
The production equipment of producing this alpha-olefin frictional reducing polymer emulsification by above preparation method adopts high-temperature high-pressure reaction kettle commonly used obviously just can not meet the demands.It also must have reinforced device under the cover High Temperature High Pressure except reaction kettle body 10, well heater 11, thermal insulation layer 12, kettle cover 8, king bolt 7, stirring rake 13, temperature-measuring casing 14, thermopair 18, whipping appts 19, tensimeter 15, pressurization mouth 16 and the blasting piece device 17 of high-temperature high-pressure reaction kettle commonly used.The easiest, effective means is to install a cover high pressure charging device on high-temperature high-pressure reaction kettle commonly used now again additional.It is concrete to constitute is to be solded into a pipe 9 at the bottom of can leading to still in punching on the kettle cover 8 of autoclave, and the tube head kettle cover 8 outside connects valve 6, adds material container 5 backs and up connects valve 2 and opening for feed 1 by Y-tube, toward laterally connecing valve 4 and pressurization mouth 3.Owing to be under condition of high voltage, so used valve 2,4 and 6, add material container 5 and pipe 9 all should be high voltage bearing here.This High Temperature High Pressure feeding device in use, the valve 4 of pressurization mouth 3 is closed in the pressurization of can heating of the valve 6 of elder generation under the closing containers 5, reactor, heat in reaction and to open the valve 2 reinforced (ester class or ether material) of dog-house 1 before or after the pressurization, add the valve 2 of closing dog-house 1 after good.Treat and need open the valve 4 and container 5 lower valves 6 of pressurization mouth 3 when reactor is reinforced, pressurization can add Polycondensation Reactor and Esterification Reactor by pipe 9 by material.
Description of drawings
Fig. 1 alpha-olefin frictional reducing polymer emulsification production equipment pie graph
1-opening for feed 2-valve wherein
3-pressurization mouthful 4-valve
5-adds material container 6-valve
7-king bolt 8-kettle cover
9-pipe 10-kettle
11-well heater 12-thermal insulation layer
13-stirring rake 14-temperature-measuring casing
15-tensimeter 16-pressurizes mouthful
17-blasting piece device 18-thermopair
The 19-whipping appts
Concrete enforcement
Embodiment 1:
The extra high molecular polymer of the high alpha-olefin that mass polymerization is obtained and dimethylbenzene add high-temperature high-pressure reaction kettle, pressure maintains 8MPa, heat up while stirring progressively, make temperature reach 250 ℃ and kept 36 hours, in reactor, add olein, continue under the condition that keeps former pressure and temperature, to stir 5 hours.Wherein the ratio of the extra high molecular polymer of high alpha-olefin in mixture accounts for 35%, and the ratio of dimethylbenzene in mixture accounts for 45%, and the ratio of olein in mixture accounts for 20%.So just can obtain comprising the paste-like liquid drag reducer product of the extra high molecular polymer of high alpha-olefin, viscosity is 3000 centipoises, can inject oil pipeline by simple medicine system.
Embodiment 2:
The extra high molecular polymer of the high alpha-olefin that mass polymerization is obtained, diesel oil and hexanaphthene add high-temperature high-pressure reaction kettle, pressure maintains 2MPa, heat up while stirring progressively, make temperature reach 180 ℃ and kept 5 hours, in reactor, add nonyl phenol poly-oxypropylene ether, continue under the condition that keeps former pressure and temperature, to stir 1 hour.Wherein the ratio of the extra high molecular polymer of high alpha-olefin in mixture accounts for 10%, and the ratio of diesel oil in mixture accounts for 25%, and the ratio of hexanaphthene in mixture accounts for 20%, and the ratio of nonyl phenol poly-oxypropylene ether in mixture accounts for 45%.So just can obtain comprising the paste-like liquid drag reducer product of the extra high molecular polymer of high alpha-olefin, viscosity is 1800 centipoises, can inject oil pipeline by simple medicine system.
Embodiment 3:
The extra high molecular polymer of the high alpha-olefin that mass polymerization is obtained and octane add high-temperature high-pressure reaction kettle, pressure maintains 5MPa, heat up while stirring progressively, make temperature reach 230 ℃ and kept 16 hours, in reactor, add Triglycerol Caprylate-Caprate, continue under the condition that keeps former pressure and temperature, to stir 3 hours.Wherein the ratio of the extra high molecular polymer of high alpha-olefin in mixture accounts for 25%, and the ratio of octane in mixture accounts for 45%, and the ratio of Triglycerol Caprylate-Caprate in mixture accounts for 30%.So just can obtain comprising the paste-like liquid drag reducer product of the extra high molecular polymer of high alpha-olefin, viscosity is 2400 centipoises, can inject oil pipeline by simple medicine system.
Flow improver product with this prescription and its special method make leaves standstill excellent stability, leave standstill the time several months layering all can not occur and be agglomerated into the piece phenomenon, and viscosity is lower than 3000 centipoises, can inject oil pipeline with injected system easily.Also do not have simultaneously impurity band inlet pipe oil transportation product such as solid dispersion, water, alcohol, therefore not only can be used for crude oil pipeline, the drag reduction that also can be used for various product pipelines increases defeated.
Claims (8)
1. an oil pipeline is in order to the alpha-olefin frictional reducing polymer emulsification of drag reduction, comprise the alpha-olefin extra high molecular polymer, it is characterized in that adopting the alpha-olefin extra high molecular polymer and the oil soluble ester class or the liquid carrier mixed together formed of ether material that are insoluble to wherein by organic hydrocarbon material and alpha-olefin extra high molecular polymer form.
2. alpha-olefin frictional reducing polymer emulsification according to claim 1 is characterized in that the weight ratio of alpha-olefin extra high molecular polymer in mixture is 10～40%, and the weight ratio of liquid carrier in mixture is 40～90%.
3. according to claim 1,2 described alpha-olefin frictional reducing polymer emulsifications, it is characterized in that the organic hydrocarbon material is diesel oil, gasoline, benzene,toluene,xylene, hexane, heptane, octane, hexanaphthene or their mixture in the liquid carrier, its weight ratio in liquid carrier is 40～80%.
4. according to claim 1,2 described alpha-olefin frictional reducing polymer emulsifications, it is characterized in that ester class and ether material in the liquid carrier are glyceryl monostearates, mix stearin, single tripalmitin, mix tripalmitin, olein, glycerin fatty acid ester, the Diethylene Glycol SUNSOFT Q-182S, the Diethylene Glycol mono-laurate, diethylene glycol monostearate, Isopropyl myristate, Triglycerol Caprylate-Caprate class and heptyl phenol polyethenoxy ether, heptyl phenol polyethenoxy ether, the hexyl phenol polyethenoxy ether, hexyl phenol polyethenoxy ether, polyoxyethylene octylphenol ether, the octyl phenol polyethenoxy ether, polyoxyethylene nonylphenol ether, nonyl phenol poly-oxypropylene ether, Brij, the oleyl alcohol polyethenoxy ether, its weight ratio in liquid carrier is 20～60%.
5. the preparation method of an alpha-olefin frictional reducing polymer emulsification as claimed in claim 1, it is characterized in that earlier alpha-olefin extra high molecular polymer and organic hydrocarbon material being added high-temperature high-pressure reaction kettle, sealing is forced into 2～10MPa, progressively heat up while stirring, after reaching 160～280 ℃, kept 5～48 hours, to wherein adding ester class or ether material, the temperature and pressure that continues to keep original stirred 0.5～5 hour again.
6. the preparation method of alpha-olefin frictional reducing polymer emulsification according to claim 5 is characterized in that adopting nitrogen pressure.
7. production equipment of producing the described alpha-olefin frictional reducing polymer of claim 1 emulsification with the described preparation method of claim 5, the reaction kettle body [10] that comprises high-temperature high-pressure reaction kettle, well heater [11], thermal insulation layer [12], kettle cover [8], king bolt [7], stirring rake [13], thermopair [18], whipping appts [19], tensimeter [15], pressurization mouthful [16] and blasting piece device [17], it is characterized in that in high-temperature high-pressure reaction kettle, installing additional again a cover high pressure charging device, it is to go up punching at high-temperature high-pressure reaction kettle lid [8] to be solded into a pipe [9] at the bottom of leading to still, tube head outside kettle cover [8] connects valve [6], add material container [5] back and up connect valve [2] by Y-tube, opening for feed [1] is toward laterally connecing valve [4] and pressurization mouthful [3].
8. the production equipment of alpha-olefin frictional reducing polymer emulsification according to claim 7 is characterized in that three valves [2], [4], [6] all adopt high-pressure valve, adds material container [5] and pipe [9] is high pressure resistant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03109631 CN1216098C (en) | 2003-04-10 | 2003-04-10 | Emulsion liquor of alpha-olefin drag-reducing polymer, its preparation method and production equipment |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03109631 CN1216098C (en) | 2003-04-10 | 2003-04-10 | Emulsion liquor of alpha-olefin drag-reducing polymer, its preparation method and production equipment |
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| Publication Number | Publication Date |
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| CN1536010A CN1536010A (en) | 2004-10-13 |
| CN1216098C true CN1216098C (en) | 2005-08-24 |
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| CN 03109631 Expired - Lifetime CN1216098C (en) | 2003-04-10 | 2003-04-10 | Emulsion liquor of alpha-olefin drag-reducing polymer, its preparation method and production equipment |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8916626B2 (en) * | 2008-07-31 | 2014-12-23 | Lubrizol Specialty Products, Inc. | Drag reducing copolymers for cold fluid applications |
| RU2648079C1 (en) * | 2017-05-24 | 2018-03-22 | Общество с ограниченной ответственностью "МИРРИКО" | Method for obtaining a reagent to reduce the hydrodynamic resistance of a turbulent flow of liquid hydrocarbons in pipelines |
| CN110577819B (en) * | 2018-06-11 | 2022-10-11 | 广东粤首新科技有限公司 | Drag reducer and preparation method and application thereof |
| CN108980621B (en) * | 2018-08-17 | 2020-06-19 | 中国石油大学胜利学院 | Polymer drag reducer swelling treatment method for shortening drag reducer onset time |
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Effective date of registration: 20211110 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: Intercontinental building, 16 ande Road, Dongcheng District, Beijing 100724 Patentee before: PETROCHINA Co.,Ltd. |
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Granted publication date: 20050824 |