CN103012641A - Preparation method of organic-silicon-containing drag reducer for oil product delivery - Google Patents

Preparation method of organic-silicon-containing drag reducer for oil product delivery Download PDF

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CN103012641A
CN103012641A CN 201210594399 CN201210594399A CN103012641A CN 103012641 A CN103012641 A CN 103012641A CN 201210594399 CN201210594399 CN 201210594399 CN 201210594399 A CN201210594399 A CN 201210594399A CN 103012641 A CN103012641 A CN 103012641A
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drag
copolymer
drag reducing
reduction
baby
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CN 201210594399
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Chinese (zh)
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李建生
刘炳光
王少杰
刘彦峰
宋戴炜
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天津市职业大学
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Abstract

The invention discloses a preparation method of an organic-silicon-containing drag reducer for oil product delivery. The preparation method is characterized by taking 90%-99% of alpha-olefin by weight with the carbon number of C8-C18 and 1%-10% of active vinyl silicane by weight as copolymerization materials, adding Ziegler-Natta catalyst for copolymerization to obtain a drag-reduction copolymer, grinding the drag-reduction copolymer to drag-reduction copolymer fine powder under 120 meshes at low temperature, adding water, surfactant and other auxiliaries and carrying out mixing, thus forming a stable drag reducer suspension product. The preparation method has the advantages of starting with the molecular structure design of the alpha-olefin drag-reduction copolymer, copolymerizing and introducing little active vinyl organic silicon groups into poly-alpha-olefin drag-reduction copolymer molecules, synthesizing the drag-reduction copolymer with an amorphous state, good oil solubility, high brittle temperature, high drag reduction efficiency and shearing resistance through copolymerization, and thus solving the problems that the existing drag reducer is high in low-temperature grinding cost, coagulates and cakes easily in storage, and has no resistance to shearing.

Description

—种含有机硅的油品输送减阻剂的制备方法 - preparation of drag reducing agents silicone-containing oil seed delivery

技术领域 FIELD

[0001] 本发明涉及ー种油品输送减阻剂的制备方法,特别是将こ烯基硅氧烷基团共聚引入a-烯烃减阻聚合物分子中,共聚合成非晶态、油溶性好、容易粉碎加工、减阻率高和抗剪切的油品输送减阻剂的方法,属于石油化工领域。 [0001] The present invention relates to a method of transporting oil seed ー DRA, in particular the alkenyl siloxane group ko incorporated a- olefin copolymer drag reducing polymer molecules, synthetic amorphous copolymer, soluble in oils , pulverization processing is easy, and a method of high shear drag of oil delivery DRA, belongs to petrochemical field.

背景技术 Background technique

[0002] 减阻剂是ー种广泛用于原油、成品油管道输送的化学添加剤,微量加入湍流态流动的油品中可使湍流转化为层流,大大降低管路系统的摩擦阻力,迅速而经济地扩大输油管道流量和降低输送泵能耗,提高输油管道运行的安全系数。 [0002] The drag reducing agent is widely used in oil seed ー, Ji added chemical products pipeline transport, was added trace turbulent state can flow in the oil layer is converted to a turbulent flow, greatly reduce the frictional resistance of the piping system, the rapid the economic expansion of the pipeline pump flow and reduce transport energy consumption, improve the safety factor pipeline operation. 国内外减阻剂的市场发展很快,已应用于海上和陆地几百条输油管道,不仅大大提高油品的管道增输能力,而且经济效益十分可观。 Domestic and international market development DRA soon, it has been used in hundreds of offshore and onshore pipelines, pipeline throughput increasing not only greatly improve the ability of the oil, but also economic benefits are substantial. 我国对进口原油的依存度达50%以上,进ロ原油的长距离管道输送消耗大量减阻剂,需要不断扩大减阻剂生产规模和降低減阻剂生产成本。 Our dependence on imported crude oil of more than 50%, ro crude oil into the long-distance pipeline transportation consume large amounts of drag reducing agents, need to continue to expand production scale and reduce production costs DRA DRA.

[0003] エ业实际应用中减阻效果显著的减阻剂是分子量在300万-3000万的长碳链a_烯烃聚合物(C6-C18)。 [0003] Ester Co., practical application of the drag reduction significant drag reducing agent having a molecular weight of 300 to 30 million a_ long chain olefin polymer (C6-C18). エ业上通常先将a-烯烃在齐格勒-纳塔(Ziegler-Natta)催化剂作用下本体聚合制得减阻聚合物,然后将减阻聚合物在液氮冷冻条件下低温粉碎成 Ester typically the first sector a- olefins a Ziegler - Natta catalyst under (Ziegler-Natta) polymerization of bulk drag reducing polymer drag reducing polymer is then pulverized to a low temperature under liquid nitrogen refrigerated conditions

0. 5mm左右的减阻聚合物微粒,再将其加入含有分散剂和稳定剂的水溶液,搅拌混合制成低粘度的减阻聚合物悬浮液。 About 0. 5mm drag reducing polymer particles, and then added an aqueous solution containing a dispersant and a stabilizer, stirring and mixing the drag reducing polymer made of low viscosity suspension.

[0004] 减阻剂生产需要在无水、无氧和低温等苛刻条件下进行,目前国内外只有3-5家公司能够エ业化生产油品输送减阻剂。 [0004] The drag reducing agent needs to be produced under severe conditions of dry, oxygen-free and low temperature, at home and abroad can be only 3-5 company Ester oil production industry conveying DRA. 现有减阻剂产品存在的主要问题ー是生产成本高,在一定程度上限制其广泛应用;ニ是减阻剂悬浮液在贮存过程中容易凝聚结胶,产品贮存期短和质量不够稳定;三是抗剪切性能差,在长距离输送中需要分段添加补充消耗的减阻齐U。 The main problem with existing products ー drag reducing agent is high production costs, limiting its wide application to a certain extent; ni drag reducing agent suspension is likely to agglomerate during storage gumming, short shelf life and quality of the product is not stable enough; Third robust shear properties, it is necessary to add drag reduction supplemental segments aligned in the long-range transport consumed in U.

[0005] 针对减阻剂生产成本过高问题,可以从降低原料成本和降低粉碎加工成本等几方面入手。 [0005] DRA high production costs for the problem, starting from the lower raw material costs and reduced tooling costs aspects pulverization. 通常较长碳链a-烯烃和苯こ烯价格相对低廉,中国专利CN102504057 (2012-06-20)和美国专利US2003/0069330 (2003-04-10)公开将较短碳链a-烯烃或苯こ烯与长碳链a-烯烃混合共聚以降低原料成本和改进产品性能。 Usually longer carbon chain a- olefin and alkenyl benzene ko relatively inexpensive, Chinese Patent No. CN102504057 (2012-06-20) and U.S. Patent No. US2003 / 0069330 (2003-04-10) discloses a short carbon chain a- olefin or phenyl ko long carbon chain alkylene a- olefin comonomer mixture to reduce raw material costs and improve product performance. 减阻聚合物低温粉碎时需要消耗大量的液氮冷冻剂,粉碎加工成本占减阻剂生产总成本的50%以上,中国专利CN101386665 (2009-03-18)公开在减阻聚合物粉碎加工时采用低温空气冷冻以降低粉碎加工成本。 When the drag reducing polymer is need to consume a large amount of liquid nitrogen cryogenic grinding agents, grinding processing costs more than 50% of the total cost of production DRA, Chinese patent CN101386665 (2009-03-18) discloses the pulverization of drag reducing polymer low temperature refrigeration to decrease pulverization air processing costs. 针对减阻剂悬浮液容易凝聚结胶问题,中国专利CN101544766 (2009-09-30)和中国专利CN101418077 (2009-04-29)公开采用掺入隔离剂或包覆减阻聚合物微粒的解决方法。 For drag reducing agent suspension is easily aggregated gumming problems, Chinese patent CN101544766 (2009-09-30) and Chinese Patent No. CN101418077 (2009-04-29) discloses a method using solution coating incorporating a release agent or drag reducing polymer particles . 为解决抗剪切和溶解性问题,美国专利US2007/0021531 (2007-01-25)专利公开将不同粒度和不同方法制备的减阻剂混合使用。 In order to solve solubility problems and shear, U.S. Patent No. US2007 / 0021531 (2007-01-25) Patent discloses a drag reducing agent prepared in different particle sizes and different mix methods. 但现有技术未能从根本上解决减阻剂生产高成本和产品质量不理想的问题。 However, the prior art failed to resolve DRA production costs and product quality is not ideal problem fundamentally.

发明内容 SUMMARY

[0006] 本发明的目的是从a -烯烃减阻聚合物分子结构设计入手,将少量活性こ烯基有机硅基团共聚引入a-烯烃减阻聚合物分子中,共聚合成非晶态、油溶性好、脆化温度高、减阻率高和抗剪切的减阻聚合物,以解决现有减阻剂低温粉碎加工成本高、贮存过程中容易凝聚结胶和不耐剪切的问题。 [0006] The object of the present invention from a - olefin drag reducing polymer molecular structure design from the start, a small amount of active ko alkenyl copolymerizable organic silicon group is introduced a- olefin drag reducing polymer molecules, synthetic amorphous copolymer, oil soluble, high brittle temperature and shear rate of drag reduction of drag reducing polymer solution prior to cryogenic grinding drag reducer high processing costs, likely to agglomerate during storage problems of gumming and shear intolerance.

[0007] 本发明思路基于长期减阻剂研究开发中总结的减阻聚合物分子结构、低温粉碎加エ性能、产品减阻性能和抗剪切性能之间的相互关系。 Thinking [0007] The present invention is based on research and development of the molecular structure of a drag reducing polymer DRA summarized long, cryogenic grinding plus Ester relationship between performance, the product performance and shear drag reduction performance. 将少量低分子量的柔性有机硅基团通过共聚反应引入聚a -烯烃减阻聚合物分子中,可望改善减阻聚合物综合性能。 The small amount of low molecular weight organic silicon group by a flexible copolymerization poly introducing a - olefin drag reducing polymer molecules, it is expected to improve overall performance of drag reducing polymer.

[0008] 实验发现较短碳链的a -辛烯聚合物为油溶性和减阻性能良好的凝胶,缺点是低温粉碎加工困难,低温粉碎过程中液氮消耗量极大,减阻剂悬浮液容易凝聚结胶。 [0008] It was found that a short carbon chain - octene and oil-soluble polymer is a good drag reduction properties of the gel, the disadvantage is difficult cryogenic grinding process, the consumption of liquid nitrogen cryogenic grinding process significantly, DRA suspension gumming solution easily aggregated.

[0009] 较长碳链的a -十二烯聚合物为油溶性和减阻性能较差的硬树脂,其减阻性能差的主要原因是在聚合过程中形成了结晶态聚合物分子,结晶态聚合物在油品中只是溶胀,不能溶解形成聚合物溶液。 [0009] carbon chains longer a - dodecene and oil-soluble polymer is poor drag reducing properties of hard resin, which is mainly due to the difference between drag reduction performance of a crystalline polymer molecules formed during polymerization, the crystalline polymer only swollen state in the oil can not be dissolved to form a polymer solution. [0010] 不同碳链长度的a-烯烃共聚可形成无规共聚物、交替共聚物和嵌段共聚物,共聚物性能在很大程度上取决于共聚物原料的性质和组成。 [0010] different carbon chain lengths a- olefin copolymer may form random copolymers, alternating copolymers and block copolymers, copolymers performance depends largely on the nature and composition of the raw material copolymer. 理想的减阻聚合物在分子结构上应当是无规共聚物,主体分子结构应主要由刚性的较长碳链a-烯烃分子构成,宏观上表现为刚性分子,有利于低温粉碎加工;减阻聚合物分子结构的某些结点应由柔性的较短碳链分子构成,从而提高其抗剪切性能,微观上成为聚合物分子溶解的切入点,有利于提高其油溶性。 Ideal drag reducing polymer molecular structure should be a random copolymer, the molecular structure of the body to be mainly composed of a rigid long carbon chain a- olefin molecules, molecules showed macroscopically rigid, cryogenic grinding facilitate processing; drag reduction some nodes polymer molecular structure should be flexible shorter carbon chain molecules, thus increasing its shear resistance, become solubilized polymer molecules microscopically entry point, will help improve their oil solubility. 将こ烯基有机硅基团与a-烯烃共聚,使a-烯烃更容易形成无规共聚物,改善长碳链的a -十二烯聚合物的溶解性能。 Dodecene solubility of the polymer - the organic silicon group ko alkenyl a- olefin copolymerizable with the a- olefin random copolymer formed more easily, improving the long carbon chains a.

[0011] 本发明实施中采用的a-烯烃是エ业级原料,使用前无需进一歩脱水预处理。 a- olefin employed in the embodiment of the invention [0011] This is Ester industry grade materials, before use into a ho without dehydration pretreatment. 因为本发明中活性こ烯基硅烷不仅作为聚合原料,而且同时作为a-烯烃原料的脱水剂,a_烯烃中的少量水分可与活性こ烯基硅烷反应除去,从而简化聚合エ艺条件和稳定了聚合物性能。 Since the present invention are not only active ko alkenyl silane as a polymerization raw material, but at the same time as a dehydrating agent a- olefin feedstock, olefins A_ small amount of moisture can be removed by reaction with the active ko alkenyl silane, thereby simplifying the polymerization process conditions and stability Ester the polymer properties.

[0012] 本发明思路已在大量实验中得到验证,本发明采取的技术方案是: [0012] The idea of ​​the present invention have been confirmed in many experiments, the present invention takes the following technical solution:

[0013] (I)将重量百分数为90% -99%的碳数为C8-C18的a-烯烃与重量百分数为1% -10%的活性こ烯基硅烷混合装入聚合瓶中,密封放入冰柜中冷冻到-5°C以下;可采用的活性こ稀基娃烧包括こ稀基ニ甲氧基娃烧、こ稀基ニこ氧基娃烧、こ稀基ニ异丙氧基娃烧、こ稀基ニ(2-甲氧基こ氧基)娃烧、こ稀基ニこ酸氧基娃烧、こ稀基_■甲氧基甲基娃烧、丙稀基ニ甲氧基娃烧、丙稀基ニこ氧基娃烧等。 [0013] (I) the weight percentage of 90% -99% of a- olefin with a carbon number of C8-C18 weight percentage of 1% to 10% of active ko alkenyl silane mixture charged polymerization bottle, sealing the discharge into the freezer and frozen to -5 ° C or less; dilute base can be an active baby ko ko burning lean group comprising Ni baby burn methoxy, ni ko ko-yl group dilute baby burn, ko diluted ni isopropoxy group Wa burning, ko group dilute Ni (2-methoxy-ko yloxy) fired baby, Ni ko ko-yl dilute acid group baby burn, ■ _ ko dilute methoxymethyl group baby burn, methoxy propenyl ni baby burn, propenyl group Wa ni ko burning and the like.

[0014] (2)用注射器向聚合瓶中加入Ziegler-Natta催化剂引发聚合反应,催化剂加入量以重量计为a-烯烃:三氯化钛:ー氯ニこ基铝=1500 :1:3; [0014] (2) with a syringe to the polymerization flask was added a polymerization Ziegler-Natta catalyst to initiate the reaction, the catalyst is added in an amount of a- olefin weight: Titanium trichloride: Ni ko ー chloro group Al = 1500: 1: 3;

[0015] (3)当聚合反应在振荡下进行至反应溶液粘度达到催化剂不再下沉后,使其在-10°C -15°c下静置反应24小时,在室温下继续反应48小时以上,至共聚物由凝胶状完全变为弹性体或硬树脂状; [0015] (3) When the polymerization reaction is carried out until the viscosity of the reaction solution reaches the catalyst no longer sinking the reaction allowed to stand at -10 ° C -15 ° c 24 hours with shaking, the reaction was continued at room temperature for 48 hours or more, to become completely gelled copolymer composed of a hard elastomer or resinous;

[0016] (4)从聚合瓶中取出减阻共聚物,加入液氮冷冻剂,并在硬脂酸钙和亚甲基ニ硬脂酰胺分散剂存在下,用低温粉碎机将其粉碎至120目以下,过筛分离分散剂和粗共聚物,得到减阻共聚物细粉末; [0016] (4) polymerization bottle was removed from the drag reducing copolymer, a refrigerant of liquid nitrogen, in the presence of Ni and stearamide dispersants calcium stearate, and methylene, cryogenic grinding it to the pulverizer 120 mesh or less, and screened separating the crude copolymer dispersant, the copolymer obtained drag reducing fine powder;

[0017] (5)将重量百分数为0. 2%的增稠剂羧甲基纤维素和重量百分数为0. 3%的表面活性剂十二烷基磺酸钠溶在蒸馏水中,再加入重量百分数为20%的防冻剂丙ニ醇和重量百分数为0.1 %的防腐剂邻苯基苯酹;[0018] (6)将粉碎的减阻共聚物以重量百分数为40%加入以上水溶液,搅拌均匀后形成稳定的减阻剂悬浮液产品。 [0017] (5) The weight percentage of 0.2% carboxymethyl cellulose and thickening agent was 0.3% by weight percent of the surfactant sodium dodecyl sulfate was dissolved in distilled water, then add weight after [0018] (6) the pulverized drag reducing copolymer in weight percent aqueous solution of more than 40%, uniform stirring; 20% percent antifreeze propan ni alcohol percentage of 0.1% by weight of o-phenylphenol preservative sprinkle forming a stable suspension of drag reducing agent product.

[0019] 减阻剂低温粉碎加工性能采用将聚合物在低温粉碎机中粉碎到120目以下所消耗液氮重量与减阻聚合物重量之比评价。 [0019] DRA cryogenic grinding processability of the polymer using pulverized to 120 mesh in the following cryogenic mill consumed than liquid nitrogen Evaluation of weight drag reducing polymer by weight.

[0020] 减阻剂溶解性能采用将低温粉碎到120目以下的减阻聚合物样品,在常温和搅拌下在0#柴油中溶解形成重量百分数为0.1 %聚合物溶液的情况评价。 [0020] The dissolution properties of drag reducing agents using the cryogenic grinding drag reducing polymer sample to 120 mesh or less, evaluated percentage of 0.1% by weight polymer solution was dissolved in diesel # 0 is formed at room temperature and with stirring.

[0021] 减阻性能采用减阻率进行定量评价,建立ー套减阻剂环道评价装置。 [0021] The drag reducing drag reduction performance quantitatively evaluated using established sets of loop evaluation apparatus ー drag reducing agents. 測定0#柴油中加入IOX 10_6减阻剂前后,通过直径12mm不锈钢管道时两端压カ传感器处的压差,按下式计算减阻剂的减阻率。 0 # diesel measured before and after the addition of drag reducing agent IOX 10_6, 12mm diameter stainless steel tubing through both ends of the pressure at the differential pressure sensor ka, drag reduction of drag reducing agents is calculated as follows.

[0022] DR% = —— X100% ⑶ [0022] DR% = - X100% ⑶

AP 0 AP 0

[0023] 式中A Pc1-未加減阻剂时管道两端摩阻压降,Pa When [0023] wherein A Pc1- not added DRA ends of the pipe friction pressure drop, Pa

[0024] A Pde-加入减阻剂后管道两端摩阻压降,Pa [0024] After the addition of drag reducing agent A Pde- frictional pressure pipe ends, Pa

[0025] 减阻剂抗剪切性能采用将含有10 X 10_6减阻剂的0#柴油用离心泵循环剪切10分钟,再測定其减阻率,通过剪切前后减阻率的变化评价。 [0025] DRA shear resistance using diesel # 0 containing 10 X 10_6 DRA shearing centrifugal pump cycle 10 minutes, the rate of drag reduction was measured by varying the shear rate before and after the evaluation of drag reduction.

[0026] 减阻剂悬浮液稳定性评价采用观察记录新制备减阻剂悬浮液产品保持良好流动性,不发生凝聚结胶的时间天数。 [0026] Stability Evaluation DRA suspension was observed and recorded using drag reducing agent suspension freshly prepared products maintain good fluidity, agglomeration time gumming does not occur for several days.

[0027] 本发明简化了a -烯烃聚合エ艺,并使聚a _烯烃减阻聚合物的性质发生实质性改变,有益效果体现在: [0027] The present invention simplifies the a - olefin polymerization Ester arts, nature and poly olefin drag reducing polymer _ A change substantially, reflected in the beneficial effects:

[0028] (I)本发明减阻共聚物低温脆化温度高,粉碎加工容易,液氮消耗和成本降低; [0028] (I) a high drag reducing copolymer of the present invention, the low-temperature embrittlement temperature, pulverized easy processing, reduce costs and consumption of liquid nitrogen;

[0029] (2)本发明含有机硅的减阻共聚物油溶性增强和减阻率提高; [0029] (2) silicone-containing copolymer of an oil-soluble drag reducing drag and enhancing the rate of increase of the present invention;

[0030] (3)本发明含有机硅的减阻剂抗剪切性能和贮存稳定性提高。 [0030] (3) drag reducing agent of the present invention the silicone-containing shear resistance and storage stability.

具体实施方式 detailed description

[0031] 实施例1 [0031] Example 1

[0032] 将10. Og聚合级TiCl3加入新蒸懼过的IOOml己烧溶剂中制成主催化剂悬浮液;将ー氯ニこ基铝50ml加入新蒸馏过的150ml己烷溶剂中制成助催化剂溶液。 [0032] The TiCl3 was added 10. Og of freshly distilled polymerization grade fear had been burned IOOml main solvent to prepare a catalyst suspension; the Ni ko ー yl aluminum chloride was added 150ml of hexane 50ml freshly distilled solvent to prepare a cocatalyst solution.

[0033] 在聚合瓶中加入重量百分比95%的a-辛烯和5%的こ烯基三こ氧基硅烷共500g作为聚合原料,在冰柜中冷冻到_5°C以下。 [0033] As the polymerization raw materials were 500g, chilled to _5 ° C in a freezer in the polymerization bottle was added 95% by weight of a- octene and 5% tri ko ko alkenyl silane. 用注射器吸取三氯化钛催化剂和ー氯ニこ基铝助催化剂,使其混合活化30秒,再加入盛有a-烯烃的聚合瓶中,摇匀。 Syringe with titanium trichloride catalyst and Ni ko ー chloro group cocatalyst activated to mix for 30 seconds, then add polymerization bottle filled with a- olefin shake. 催化剂加入的重量比为a-烯烃:三氯化钛:ー氯ニこ基铝=1500 :1 : 3。 The catalyst was added a- olefin weight ratio of: titanium trichloride: Ni ko ー chloro group Al = 1500: 1: 3. 当烯烃混合物预聚合至反应溶液粘度达到催化剂不再下沉后,在-10°C _15°C下静置反应24小吋,然后将其在常温下继续反应48小时以上,至共聚物完全由凝胶状变为弾性体或硬树脂状。 When the olefin prepolymerization mixture to the reaction solution viscosity is no longer sinking the catalyst, the reaction was allowed to stand at 24 inch -10 ° C _15 ° C, then reaction was continued for 48 hours at room temperature to complete the copolymer Tan gel becomes hard or resinous properties. 从聚合瓶中取出减阻共聚物,加入液氮冷冻剂,在硬脂酸钙和亚甲基ニ硬脂酰胺分散剂存在下,用低温粉碎机将其粉碎至120目以下,过筛分离分散剂和粗共聚物,得到减阻共聚物细粉末,消耗约其8倍重量的液氮冷冻剂。 Drag reducing copolymer taken out from the polymerization flask, the refrigerant of liquid nitrogen, and calcium stearate in methylene ni stearamide the presence of a dispersant, which cryogenic mill pulverized to 120 mesh or less, the dispersion was separated sieved the crude agent and a copolymer, a copolymer obtained fine drag reducing powder, liquid nitrogen cryogen consumption of about 8 times its weight. 称取Ig减阻共聚物细粉末,常温和搅拌下加入lOOOmlO#柴油中,10分钟内减阻共聚物全部溶解,并形成粘稠的胶体溶液。 Weigh Ig drag reducing copolymer fine powder, and added with stirring at room temperature lOOOmlO # diesel, over 10 minutes drag reducing copolymer dissolved, and forming a viscous colloidal solution. 将减阻共聚物以有效浓度10X10_6加入0#柴油中,在温度25°C下进行减阻性能评价,减阻率为52.4%。 The drag reducing copolymer is added at an effective concentration 10X10_6 0 # diesel, drag reduction performance evaluation carried out at a temperature of 25 ° C, was 52.4% drag reduction. 用离心泵循环剪切10分钟后,减阻率变为30. 8%。 After 10 minutes of shear using a centrifugal pump cycle, drag reduction ratio becomes 30.8%. 将重量百分比为0. 2%的增稠剂羧甲基纤维素和重量百分比为0. 3%的表面活性剂十二烷基磺酸钠溶解在蒸馏水中,再加入重量百分比为20%的防冻剂丙ニ醇和重量百分比为0. 1%的防腐剂邻苯基苯酚。 The weight percentage of 0.2% carboxymethyl cellulose and thickening agent was 0.3% by weight of the surfactant sodium dodecyl sulfate was dissolved in distilled water, was added 20% by weight of antifreeze ni agent propan alcohol 0.1% by weight of o-phenylphenol preservatives. 将减阻共聚物粉末以重量百分比为40%加入以上水溶液,搅拌均匀后形成固含量40%的稳定减阻剂悬浮液成品,在常温下贮存300天以上仍保持良好流动性,未出现凝聚结胶现象。 The drag reducing copolymer powder 40% weight percent aqueous solution was added the above, to form a solid content of 40% stabilized drag reducing agent suspension after mixing the finished, more than 300 days storage still maintain a good fluidity at room temperature, the junction does not occur agglomeration plastic phenomenon.

[0034] 实施例2 [0034] Example 2

[0035] 在聚合瓶中加入重量百分比20%的a-辛烯、75%的a-十二烯和5%的こ烯基三こ氧基硅烷共500g作为聚合原料,按照实施例1同样エ艺条件进行实验,减阻聚合物实验评价结果见表I。 [0035] In the polymerization bottle was added 20% by weight of a- octene, dodecene a- 75% and 5% tri ko ko alkenyl silane co 500g as a polymerization starting material, the same as in Example 1 Ester the process conditions for experiments evaluation results are shown in Table I. drag reducing polymer 减阻聚合物低温粉碎加工消耗约5倍重量的液氮,在0#柴油中10 X 10_6浓度下减阻率42. 2%,剪切后减阻率31. 4%,减阻剂悬浮液稳定300天以上。 Cryogenic grinding drag reducing polymer processing consume about 5 times the weight of nitrogen, 0 # diesel 10 X 10_6 drag reduction at a concentration of 42.2%, 31.4% drag reduction after shear, drag reducing agent suspension stable for at least 300 days.

[0036] 实施例3 [0036] Example 3

[0037] 在聚合瓶中加入重量百分比20%的a -十二烯和5%的こ烯基三こ氧基硅烷共500g作为聚合原料。 [0037] In the polymerization bottle was added 20% by weight of a - dodecene and 5% tri ko ko alkenyl silane starting material as a polymerization co 500g. 按照实施例1同样エ艺条件进行实验,减阻聚合物实验评价结果见表I。 1 Ester same process conditions as in Example experiment, drag reducing polymer experimental evaluation results shown in Table I. 减阻聚合物低温粉碎加工消耗约5倍重量的液氮,在0#柴油中IOX 10_6浓度下减阻率54. 6%,剪切后减阻率36. 8%,减阻剂悬浮液稳定300天以上。 Cryogenic grinding drag reducing polymer processing consume about 5 times the weight of nitrogen, the IOX 10_6 drag reduction at a concentration of 54.6% in diesel # 0, 36.8% drag reduction after shearing, stabilized drag reducing agent suspension more than 300 days.

[0038] 对照例ト3 [0038] Comparative Example 3 Suites

[0039] 在聚合瓶中分别加入a-辛烯、a -十二烯、重量分数20% a-辛烯和80%a -十二烯为聚合原料,不加入有机硅组分进行对照实验,按照实施例1相同エ艺条件进行聚合反应,减阻聚合物实验评价结果见表I。 [0039] In the polymerization bottle were added a- octene, a - dodecene, weight fraction of 20% a- octene and 80% a - dodecene polymeric material, without the addition of the silicone component performed a control experiment, 1 polymerization was carried out the same process conditions Ester embodiment, drag reducing polymer experimental evaluation results shown in Table I. 不含有机硅的聚a-烯烃减阻剂的减阻率、抗剪切性能和减阻剂悬浮液稳定性明显低于含有机硅聚a-烯烃减阻剂。 Reduction Rate silicone-free poly-a- olefin drag reducing agents, shear resistance and stability of the suspension drag reducing agents significantly lower than the silicon-containing poly-a- olefin drag reducing agent.

[0040] 表I有机硅对减阻聚合物性能的影响 [0040] TABLE I Effect of silicone on the drag reducing polymer properties

[0041] [0041]

编号丨聚合原料 聚合物液氮消溶解性能I减阻率剪切后悬浮液 No. Shu polymerizable liquid nitrogen solubility feed consumption rate after shear drag reducing polymer I suspension

外观耗量(0.1%) (%) 减阻率稳定性(倍) (%) (天) Appearance consumption (0.1%) (%) Reduction Rate stability (times) (%) (days)

实施95%Cl-辛稀+ 紫红色8 全溶52. 4 30.8 300以上 95% Cl- embodiment purple oct-8 + dilute the whole solution above 52.4 30.8 300

例I 5%こ晞基三乙弹性体氧基娃烷 Example I 5% nitrilotriacetate ko Xi elastomeric baby alkoxy group

实施95%a-十二締+ 紫红色5 全溶42.2 31.4 300以上 95% a- embodiment twelve full associative + purple solution 42.2 31.4 5 300 or more

例2 5%乙烯基三乙弹性体烷 EXAMPLE 25 percent vinyl alkyl triethylammonium elastomer

实施20%ct-辛烯+ 紫红色5 全溶54.6 36.8 300以上 20% ct- embodiment octene purple + 5 54.6 36.8 300 over the whole solution

例3 75%a-十二締+ 弹性体5%乙缔基三乙IlM:垸 Example 3 75% a- twelve associative acetate + 5% elastomer associative nitrilotriacetate IlM: embankment

[0042] [0042]

Figure CN103012641AD00071

Claims (2)

  1. 1. 一种油品输送减阻剂的制备方法,其特征是将碳数为C8-C18的α-烯烃或其混合物与活性乙烯基硅烷为共聚原料,加入Ziegler-Natta催化剂进行聚合得到减阻共聚物,主要包括以下步骤: (1)将重量百分数为90%-99%的碳数为08-(:18的α _烯烃或其混合物与重量百分数为1% -10%的活性乙烯基硅烷混合装入聚合瓶中,密封放入冰柜中冷冻到-5°C以下; (2)用注射器向聚合瓶中加入Ziegler-Natta催化剂引发聚合反应,催化剂加入量以重量计为α -烯烃:三氯化钛:一氯二乙基铝=1500 :1:3; (3)当聚合反应在振荡下进行至反应溶液粘度达到催化剂不再下沉后,使其在-10°C _15°C下静置反应24小时,在室温下继续反应48小时以上,至共聚物由凝胶状完全变为弹性体或硬树脂状; (4)从聚合瓶中取出减阻共聚物,加入液氮冷冻剂,并在硬脂酸钙和亚甲基二硬脂酰胺分散剂存在下,用低温粉 Preparation 1. A DRA oil delivery, characterized in that the C8-C18 carbon atoms in the α- olefins or mixtures thereof with an active vinyl silane copolymer as the raw material, was added Ziegler-Natta catalyst to obtain a drag reducing copolymers, mainly comprising the following steps: (1) the percentage by weight of 90% -99% of a carbon number of 08 - (: α _ olefins or mixtures thereof and 18 percent by weight 1% to 10% of the active vinyl silane hybrid polymerization bottle was charged, sealed into the freezer chilled to -5 ° C or less; (2) Ziegler-Natta catalyst to the polymerization flask was added via syringe to initiate the polymerization reaction, the catalyst is added in an amount by weight of α - olefin: three titanium chloride: diethyl aluminum chloride = 1500: 1: 3; (3) to the reaction solution reaches a viscosity not sink when the polymerization catalyst shaking, so that at -10 ° C _15 ° C the reaction was allowed to stand for 24 hours, the reaction was continued at room temperature for 48 hours or more, to become completely gelled copolymer composed of a hard elastomer or resinous; (4) removing the drag reducing copolymer from the polymerization flask, the liquid nitrogen cryogen and in the presence of calcium stearate and distearyl methylene amide dispersants, low temperature powder 机将其粉碎至120目以下,过筛分离分散剂和粗共聚物,得到减阻共聚物细粉末; (5)将重量百分数为O. 2%的增稠剂羧甲基纤维素和重量百分数为O. 3%的表面活性剂十二烷基磺酸钠溶在蒸馏水中,再加入重量百分数为20%的防冻剂丙二醇和重量百分数为O. 1%的防腐剂邻苯基苯酚,将粉碎的减阻共聚物以重量百分数为40%加入水溶液中,搅拌均匀后形成稳定的减阻剂悬浮液产品。 Machine crushed to 120 mesh or less, and screened separating the crude copolymer dispersant, obtained drag reducing copolymer fine powder; (5) the weight percent O. 2% of carboxymethyl cellulose and thickening agent by weight percent O. 3% of a surfactant sodium dodecyl sulfate was dissolved in distilled water, was added 20% weight percent and weight percent propylene glycol antifreeze O. 1% ortho-phenylphenol preservatives, pulverized drag reducing copolymer was added 40% weight percent aqueous solution of drag reducing agent to form a stable suspension of the product after mixing.
  2. 2.根据权利要求1所述油品输送减阻剂的制备方法,其特征在于所述活性乙烯基硅烧是乙稀基二甲氧基娃烧、乙稀基二乙氧基娃烧、乙稀基二异丙氧基娃烧、乙稀基二(2_甲氧基乙氧基)娃烧、乙稀基二乙酸氧基娃烧、乙稀基_■甲氧基甲基娃烧、丙稀基二甲氧基娃烧、丙稀基二乙氧基娃烧。 The production method of the oil delivery drag reducer as claimed in claim 1, wherein the active silicon burning is ethylene vinyl dimethoxy baby burn, burn baby diethoxy ethylene group, B lean burn baby diisopropoxide group, ethylene di (2_ methoxyethoxy) burning baby, baby ethylene oxy group burning diacetate, ethylene group _ ■ methoxymethyl baby burn, propenyl dimethoxy baby burn, burn propenyl diethoxy baby.
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Publication number Priority date Publication date Assignee Title
CN104214515A (en) * 2014-09-14 2014-12-17 天津市职业大学 Microencapsulated crude oil transportation drag reducer slurry and preparation method thereof

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EP0430112A2 (en) * 1989-11-28 1991-06-05 MITSUI TOATSU CHEMICALS, Inc. Syndiotactic alpha-olefin-alkenylsilane copolymer and method for preparing same
CN102408506A (en) * 2011-09-29 2012-04-11 天津市职业大学 Preparation method for oil soluble drag reducer
CN102746520A (en) * 2012-06-15 2012-10-24 中国石油化工股份有限公司 Post-treatment and preparation method for polyolefin drag reducing agent used for oil based crude oil

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0430112A2 (en) * 1989-11-28 1991-06-05 MITSUI TOATSU CHEMICALS, Inc. Syndiotactic alpha-olefin-alkenylsilane copolymer and method for preparing same
CN102408506A (en) * 2011-09-29 2012-04-11 天津市职业大学 Preparation method for oil soluble drag reducer
CN102746520A (en) * 2012-06-15 2012-10-24 中国石油化工股份有限公司 Post-treatment and preparation method for polyolefin drag reducing agent used for oil based crude oil

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104214515A (en) * 2014-09-14 2014-12-17 天津市职业大学 Microencapsulated crude oil transportation drag reducer slurry and preparation method thereof

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