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CN108980621B - Polymer drag reducer swelling treatment method for shortening drag reducer onset time - Google Patents

Polymer drag reducer swelling treatment method for shortening drag reducer onset time Download PDF

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CN108980621B
CN108980621B CN201810942000.1A CN201810942000A CN108980621B CN 108980621 B CN108980621 B CN 108980621B CN 201810942000 A CN201810942000 A CN 201810942000A CN 108980621 B CN108980621 B CN 108980621B
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polymer
drag
drag reducer
reaction kettle
kettle
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CN108980621A (en
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代晓东
刘焕荣
李雷
刘飞
王余宝
李敬文
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Shandong Institute Of Petroleum And Chemical Engineering
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China University of Petroleum Beijing
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17DPIPE-LINE SYSTEMS; PIPE-LINES
    • F17D1/00Pipe-line systems
    • F17D1/08Pipe-line systems for liquids or viscous products
    • F17D1/16Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention relates to a swelling treatment method for a polymer drag reducer, which is used for shortening the onset time of the drag reducer. The technical scheme comprises the following steps: firstly, shearing polymer solid, and placing the polymer solid in a reaction kettle; secondly, filling carbon dioxide into the reaction kettle to enable the reaction kettle to reach a supercritical state; thirdly, after the polymer is swelled, removing carbon dioxide in the kettle and taking out a sample; fourthly, weighing, putting into a freezing barrel, and treating at low temperature; fifthly, transferring the mixture into a crusher for coarse crushing and grinding; and sixthly, adding an isolating agent, and performing ball milling and mixing to obtain the slurry oil drag reducer product with quick response. The beneficial effects are that: according to the invention, the polymer is treated by the supercritical fluid before low-temperature crushing, so that the swelling effect is generated, then low-temperature crushing and grinding are carried out, and the requirements of full isolation and suspension processes are met.

Description

用于缩短减阻剂起效时间的聚合物减阻剂溶胀处理方法Swelling treatment method of polymer drag reducer for shortening the onset time of drag reducer

技术领域technical field

本发明涉及一种输油管道减阻输送、减阻剂生产和后处理技术领域,特别涉及一种用于缩短减阻剂起效时间的聚合物减阻剂溶胀处理方法。The invention relates to the technical field of drag reduction and transportation of oil pipelines, drag reducer production and post-treatment, in particular to a swelling treatment method for a polymer drag reducer for shortening the onset time of the drag reducer.

背景技术Background technique

输油管道添加减阻剂能够在不添加增输设备的条件下增加管道输量,或者降低输油管线的运行压力而不降低输送能力,在管道运行工艺标准中,已形成完善的添加减阻剂输送工艺规范。商品油品减阻剂是分子量在六百万以上的聚α烯烃浆状产品,通过注入系统,经一定时间溶解在油品中,通过分子链的弹性变形传递能量,降低了油品流动中摩擦能量损失,表观现象是减小流动阻力减小,进而实现了减阻增输。Adding drag reducers to oil pipelines can increase pipeline throughput without adding additional transportation equipment, or reduce the operating pressure of oil pipelines without reducing transportation capacity. Process specification. The commercial oil drag reducer is a polyalphaolefin slurry product with a molecular weight of more than 6 million. It is dissolved in the oil after a certain period of time through the injection system, and transmits energy through the elastic deformation of the molecular chain, reducing the friction in the oil flow. Energy loss, the apparent phenomenon is to reduce the flow resistance and reduce the resistance, thereby realizing the reduction of the resistance and the increase of the output.

目前商业应用本体聚合制备减阻聚α烯烃初始状态为粘弹性固体,直接将其作为减阻剂使用,会由于聚α烯烃颗粒自身的粘弹性极其容易粘连成团,难以稳定分散,给减阻剂的注入带来困难,而且在油品中,因聚α烯烃颗粒相互粘连成团,直接导致减阻剂颗粒溶解速度下降,减阻效率降低,甚至还会造成管道堵塞。因此聚α烯烃必须经过后处理使其成为流体状态,以便于应用。通常,减阻聚合物的后处理是将超低温研磨得到的聚合物颗粒悬浮分散在水基、醇基或油基的悬浮液中,悬浮态减阻剂可以更快速的溶解于油品中,起到减阻效果。其中油基悬浮液包含植物油、杀菌剂、紫外线吸收剂等组分,加入减阻颗粒后,通过高速搅拌形成乳化态减阻剂悬浮液。At present, the initial state of drag-reducing polyalphaolefin prepared by commercial bulk polymerization is viscoelastic solid, and it is directly used as drag reducing agent. Due to the viscoelasticity of polyalphaolefin particle itself, it is extremely easy to stick and form agglomerates, which is difficult to stably disperse, and it is difficult to stably disperse and reduce drag. The injection of the drag reducing agent brings difficulties, and in the oil product, because the polyalphaolefin particles stick to each other and form agglomeration, the dissolution rate of the drag reducing agent particles is directly reduced, the drag reduction efficiency is reduced, and even the pipeline is blocked. Therefore, polyalphaolefins must be post-treated to bring them into a fluid state for ease of application. Usually, the post-treatment of the drag reducing polymer is to suspend and disperse the polymer particles obtained by ultra-low temperature grinding in a water-based, alcohol-based or oil-based suspension. The suspended drag reducing agent can be dissolved in the oil more quickly. to the drag reduction effect. The oil-based suspension contains vegetable oil, bactericide, ultraviolet absorber and other components. After adding drag-reducing particles, an emulsified drag-reducing agent suspension is formed by high-speed stirring.

在实际应用中,这种浆状减阻剂悬浮液注入油品管道以后,到可以观测到减阻现象(下游站场的进站压力)需要经过60分钟以上的时间,这是由于经后处理的减阻剂悬浮液进入管道中的油品以后,其后处理过程中添加的各种组分逐渐从粉碎后聚α烯烃颗粒表面剥离,聚α烯烃接触石油组分后不断的溶胀、溶解,直至最后完全溶解分散到油品中,这一过程持续的时间造成了减阻剂悬浮液加入后实现减阻效果需要一定的时间。针对目前聚α烯烃减阻剂悬浮液应用中存在的分散时间问题,在原有的后处理悬浮体系制备工艺的基础上加入超临界CO2、甲醇或甲苯,调整工艺参数,通过超临界CO2、甲醇或甲苯对聚α烯烃的溶胀作用,用以缩短减阻剂悬浮液在油品中的分散溶解的时间,实现快速起效的目的。In practical applications, it takes more than 60 minutes to observe the drag reduction phenomenon (the entry pressure of the downstream station) after the slurry-like drag reducer suspension is injected into the oil pipeline. After the suspension of the drag reducing agent enters the oil in the pipeline, the various components added in the post-processing process are gradually peeled off from the surface of the pulverized polyalphaolefin particles, and the polyalphaolefin continues to swell and dissolve after contacting the petroleum components. Until it is completely dissolved and dispersed into the oil at the end, the duration of this process results in that it takes a certain amount of time to achieve the drag reduction effect after the drag reducer suspension is added. In view of the current dispersion time problem in the application of polyalphaolefin drag reducer suspension, supercritical CO2 , methanol or toluene is added on the basis of the original post-treatment suspension system preparation process, and the process parameters are adjusted to pass supercritical CO2 , The swelling effect of methanol or toluene on polyalphaolefin is used to shorten the dispersion and dissolution time of the drag reducer suspension in the oil, and to achieve the purpose of rapid onset.

发明内容SUMMARY OF THE INVENTION

本发明的目的就是针对现有技术存在的上述缺陷,提供一种用于缩短减阻剂起效时间的聚合物减阻剂溶胀处理方法。The object of the present invention is to provide a method for swelling treatment of a drag reducer for shortening the onset time of the drag reducer in view of the above-mentioned defects in the prior art.

本发明提到的一种用于缩短减阻剂起效时间的聚合物减阻剂溶胀处理方法,其技术方案是包括以下制备步骤:A kind of polymer drag reducing agent swelling treatment method for shortening the onset time of drag reducing agent mentioned in the present invention, its technical scheme comprises the following preparation steps:

第一步,将干燥的块状减阻聚合物固体剪碎成5cm见方小块,称量标记后将其置于耐压保温反应釜中密封;In the first step, the dry block-shaped drag-reducing polymer solid is cut into small pieces of 5cm square, and after weighing and marking, it is placed in a pressure-resistant thermal insulation reaction kettle and sealed;

第二步,在反应釜中充入二氧化碳,并在30 min内控制反应温度在设定温度-10-30℃,待温度稳定后再次充入二氧化碳到实验设定压力,该压力大于该二氧化碳在设定温度时的临界压力,使釜内的二氧化碳流体达到超临界状态,并保持4~12h;In the second step, the reaction kettle was filled with carbon dioxide, and the reaction temperature was controlled within 30 min at the set temperature of -10-30°C. After the temperature was stabilized, carbon dioxide was filled again to the experimental set pressure, which was greater than the carbon dioxide Set the critical pressure at the temperature to make the carbon dioxide fluid in the kettle reach the supercritical state, and keep it for 4~12h;

第三步,待块状减阻聚合物发生溶胀后,卸去釜内二氧化碳并取出样品,2min之内称量样品重量,并记录,比较溶胀前后重量变化;The third step, after the bulk drag-reducing polymer swells, remove the carbon dioxide in the kettle and take out the sample, weigh the sample within 2 minutes, and record, and compare the weight change before and after swelling;

第四步,将超临界流体溶胀处理后的块状减阻聚合物称量后放入冷冻桶中,然后充入液氮至淹没所述块状减阻聚合物,保持10~30 min,待液氮蒸发后,再按照与块状减阻聚合物质量比1:10-3:10加入液态二氧化碳保持5~20min;In the fourth step, the bulk drag-reducing polymer swollen by the supercritical fluid is weighed and placed in a freezing bucket, and then filled with liquid nitrogen until the bulk drag-reducing polymer is submerged, and kept for 10-30 min. After the liquid nitrogen is evaporated, liquid carbon dioxide is added according to the mass ratio of 1:10-3:10 to the bulk drag-reducing polymer for 5~20min;

第五步,将低温处理过的块状减阻聚合物立即转入破碎机进行粗碎,然后转移至球磨机,按照与聚合物质量比1:10-1:20加入研磨助剂在低于-40℃下进行研磨;The fifth step, the block drag-reducing polymer treated at low temperature is immediately transferred to a crusher for coarse crushing, and then transferred to a ball mill, and grinding aids are added in a mass ratio of 1:10-1:20 to the polymer at a level below - Grinding at 40°C;

第六步,一边研磨一边向球磨机中加入聚合物质量的20%的隔离剂,经过一段时间的球磨和混合后,经筛分后制得经溶胀处理的表面粘附隔离剂的减阻聚合物细粉干剂,可直接分散于悬浮体系中得到起效快的浆状油品减阻剂产品。The sixth step, adding 20% of the polymer mass of the release agent to the ball mill while grinding, after a period of ball milling and mixing, and sieving to obtain the swollen surface-adhering resistance-reducing polymer of the release agent The fine powder dry agent can be directly dispersed in the suspension system to obtain a fast-acting slurry oil drag reducer product.

本发明提到的第二种用于缩短减阻剂起效时间的聚合物减阻剂溶胀处理方法,包括以下制备步骤:The second kind of polymer drag reducing agent swelling treatment method for shortening the onset time of drag reducing agent mentioned in the present invention comprises the following preparation steps:

第一步,将干燥的块状减阻聚合物固体剪碎成5cm见方小块,称量标记后将其置于耐压保温反应釜中密封;In the first step, the dry block-shaped drag-reducing polymer solid is cut into small pieces of 5cm square, and after weighing and marking, it is placed in a pressure-resistant thermal insulation reaction kettle and sealed;

第二步,在反应釜中充入甲醇,并在30 min内控制反应温度在设定温度-10-30℃,待温度稳定后再次充入甲醇到实验设定压力,该压力大于该甲醇在设定温度时的临界压力,使釜内的甲醇流体达到超临界状态,并保持4~12h;In the second step, the reaction kettle was filled with methanol, and the reaction temperature was controlled within 30 min at the set temperature of -10-30 °C. After the temperature was stabilized, methanol was filled again to the experimental set pressure, which was greater than the methanol at Set the critical pressure at the temperature to make the methanol fluid in the kettle reach the supercritical state, and keep it for 4~12h;

第三步,待块状减阻聚合物发生溶胀后,卸去釜内甲醇并取出样品,2min之内称量样品重量,并记录,比较溶胀前后重量变化;The third step, after the bulk drag-reducing polymer swells, remove the methanol in the kettle and take out the sample, weigh the sample within 2 minutes, and record, and compare the weight change before and after swelling;

第四步,将超临界流体溶胀处理后的块状减阻聚合物称量后放入冷冻桶中,然后充入液氮至淹没所述块状减阻聚合物,保持10~30 min,待液氮蒸发后,再按照与块状减阻聚合物质量比1:10-3:10加入液态甲醇保持5~20min;In the fourth step, the bulk drag-reducing polymer swollen by the supercritical fluid is weighed and placed in a freezing bucket, and then filled with liquid nitrogen until the bulk drag-reducing polymer is submerged, and kept for 10-30 min. After the liquid nitrogen evaporates, add liquid methanol according to the mass ratio of 1:10-3:10 to the bulk drag-reducing polymer for 5~20min;

第五步,将低温处理过的块状减阻聚合物立即转入破碎机进行粗碎,然后转移至球磨机,按照与聚合物质量比1:10-1:20加入研磨助剂在低于-40℃下进行研磨;The fifth step, the block drag-reducing polymer treated at low temperature is immediately transferred to a crusher for coarse crushing, and then transferred to a ball mill, and grinding aids are added in a mass ratio of 1:10-1:20 to the polymer at a level below - Grinding at 40°C;

第六步,一边研磨一边向球磨机中加入聚合物质量的20%的隔离剂,经过一段时间的球磨和混合后,经筛分后制得经溶胀处理的表面粘附隔离剂的减阻聚合物细粉干剂,可直接分散于悬浮体系中得到起效快的浆状油品减阻剂产品。The sixth step, adding 20% of the polymer mass of the release agent to the ball mill while grinding, after a period of ball milling and mixing, and sieving to obtain the swollen surface-adhering resistance-reducing polymer of the release agent The fine powder dry agent can be directly dispersed in the suspension system to obtain a fast-acting slurry oil drag reducer product.

本发明提到的第三种用于缩短减阻剂起效时间的聚合物减阻剂溶胀处理方法,包括以下制备步骤:The third kind of polymer drag reducing agent swelling treatment method for shortening the onset time of drag reducing agent mentioned in the present invention comprises the following preparation steps:

第一步,将干燥的块状减阻聚合物固体剪碎成5cm见方小块,称量标记后将其置于耐压保温反应釜中密封;In the first step, the dry block-shaped drag-reducing polymer solid is cut into small pieces of 5cm square, and after weighing and marking, it is placed in a pressure-resistant thermal insulation reaction kettle and sealed;

第二步,在反应釜中充入甲苯,并在30 min内控制反应温度在设定温度-10-30℃,待温度稳定后再次充入甲苯到实验设定压力,该压力大于该甲苯在设定温度时的临界压力,使釜内的甲苯流体达到超临界状态,并保持4~12h;In the second step, the reaction kettle was filled with toluene, and the reaction temperature was controlled within 30 min at the set temperature of -10-30°C. After the temperature was stabilized, toluene was filled again to the experimental set pressure, which was greater than the toluene at Set the critical pressure at the temperature to make the toluene fluid in the kettle reach the supercritical state, and keep it for 4~12h;

第三步,待块状减阻聚合物发生溶胀后,卸去釜内甲苯并取出样品,2min之内称量样品重量,并记录,比较溶胀前后重量变化;In the third step, after the bulk drag-reducing polymer swells, remove the toluene in the kettle and take out the sample, weigh the sample within 2 minutes, record it, and compare the weight change before and after swelling;

第四步,将超临界流体溶胀处理后的块状减阻聚合物称量后放入冷冻桶中,然后充入液氮至淹没所述块状减阻聚合物,保持10~30 min,待液氮蒸发后,再按照与块状减阻聚合物质量比1:10-3:10加入液态甲苯保持5~20min;In the fourth step, the bulk drag-reducing polymer swollen by the supercritical fluid is weighed and placed in a freezing bucket, and then filled with liquid nitrogen until the bulk drag-reducing polymer is submerged, and kept for 10-30 min. After the liquid nitrogen evaporates, add liquid toluene according to the mass ratio of 1:10-3:10 to the bulk drag-reducing polymer for 5~20min;

第五步,将低温处理过的块状减阻聚合物立即转入破碎机进行粗碎,然后转移至球磨机,按照与聚合物质量比1:10-1:20加入研磨助剂在低于-40℃下进行研磨;The fifth step, the block drag-reducing polymer treated at low temperature is immediately transferred to a crusher for coarse crushing, and then transferred to a ball mill, and grinding aids are added in a mass ratio of 1:10-1:20 to the polymer at a level below - Grinding at 40°C;

第六步,一边研磨一边向球磨机中加入聚合物质量的20%的隔离剂,经过一段时间的球磨和混合后,经筛分后制得经溶胀处理的表面粘附隔离剂的减阻聚合物细粉干剂,可直接分散于悬浮体系中得到起效快的浆状油品减阻剂产品。The sixth step, adding 20% of the polymer mass of the release agent to the ball mill while grinding, after a period of ball milling and mixing, and sieving to obtain the swollen surface-adhering resistance-reducing polymer of the release agent The fine powder dry agent can be directly dispersed in the suspension system to obtain a fast-acting slurry oil drag reducer product.

优选的,上述的研磨助剂是淀粉、硬脂酸酐或硬脂酸钙其中的一种。Preferably, the above-mentioned grinding aid is one of starch, stearic anhydride or calcium stearate.

优选的,上述的隔离剂是硬脂酸钙、硬脂酸铝、滑石粉或针状石蜡其中的一种。Preferably, the above-mentioned release agent is one of calcium stearate, aluminum stearate, talc or acicular paraffin.

本发明的有益效果是:本发明通过在块状减阻聚合物低温粉碎之前通过超临界流体进行处理,使聚合物产生一定的溶胀效果,再进行低温粉碎和研磨,并通过研磨助剂和隔离剂使粉状聚合物能到达到充分隔离和悬浮工艺的要求,该处理方法能够缩短减阻剂在油品中的溶胀、溶解和分散时间,使其能够更加快速的显示出减阻增输效果。The beneficial effects of the present invention are as follows: in the present invention, the bulk drag-reducing polymer is processed by supercritical fluid before low-temperature pulverization, so that the polymer has a certain swelling effect, and then the low-temperature pulverization and grinding are carried out. The agent can make the powdery polymer meet the requirements of sufficient isolation and suspension process. This treatment method can shorten the swelling, dissolution and dispersion time of the drag reducer in the oil, so that it can show the effect of drag reduction and transmission more quickly. .

附图说明Description of drawings

附图1是本发明的旋转圆盘测试系统的结构示意图;Accompanying drawing 1 is the structural representation of the rotating disk test system of the present invention;

上图中:恒温水浴槽1、联轴器2、扭矩传感器3、调速电机4、数据采集卡5、计算机6、样品槽7、下支撑板8、支撑杆9、上支撑板10。In the above picture: constant temperature water bath 1, coupling 2, torque sensor 3, speed regulating motor 4, data acquisition card 5, computer 6, sample tank 7, lower support plate 8, support rod 9, upper support plate 10.

具体实施方式Detailed ways

以下结合附图对本发明的优选实施例进行说明,应当理解,此处所描述的优选实施例仅用于说明和解释本发明,并不用于限定本发明。The preferred embodiments of the present invention will be described below with reference to the accompanying drawings. It should be understood that the preferred embodiments described herein are only used to illustrate and explain the present invention, but not to limit the present invention.

实施例1:本发明提到的一种用于缩短减阻剂起效时间的聚合物减阻剂颗粒溶胀处理方法,其制备方法如下:Embodiment 1: a kind of polymer drag reducing agent particle swelling treatment method for shortening the onset time of drag reducing agent mentioned in the present invention, its preparation method is as follows:

首先将干燥的块状减阻聚合物固体剪碎成5cm见方小块,称量1 kg,将其置于耐压保温反应釜中密封;然后在反应釜中充入CO2,达到6.0MPa,再30 min内控制温度在10 ℃,之后再次充入CO2到设定压力7.5MPa(10℃时CO2临界压力7.2MPa),此时釜内的CO2为超临界,并保持12 h;待聚合物发生溶胀后,卸去釜内CO2并取出样品,2min之内称量标记样品重量为1.123 kg;将溶胀处理后的减阻聚合物放入冷冻桶中,然后充入液氮至淹没聚合物,保持30min,待液氮蒸发后,再按照与聚合物质量比3:10加入液态CO2保持20min;然后立即转入破碎机进行粗碎,在移至球磨机,按照与聚合物质量比1:10加入淀粉研磨助剂,并全程保持在-40℃以下;研磨同时,向球磨机中加入聚合物质量的20%的硬脂酸钙隔离剂,经筛分后制得经溶胀处理的表面粘附隔离剂的减阻聚合物细粉干剂。First, cut the dry bulk drag-reducing polymer solid into 5 cm square pieces, weigh 1 kg, and place them in a pressure-resistant thermal insulation reaction kettle to seal; then fill the reaction kettle with CO 2 to reach 6.0 MPa, The temperature was controlled at 10 °C for another 30 min, and then the CO 2 was recharged to the set pressure of 7.5 MPa (the critical pressure of CO 2 at 10 ° C was 7.2 MPa). At this time, the CO 2 in the kettle was supercritical and kept for 12 h; After the polymer swells, remove the CO2 in the kettle and take out the sample, and weigh the marked sample within 2 minutes to be 1.123 kg; put the swollen drag-reducing polymer into a freezing barrel, and then fill it with liquid nitrogen to 1.123 kg. Submerge the polymer and keep it for 30min. After the liquid nitrogen evaporates, add liquid CO 2 according to the mass ratio of the polymer to 3:10 and keep it for 20min; Add starch grinding aid at a ratio of 1:10 and keep it below -40°C throughout the process; at the same time of grinding, add 20% of the polymer mass of calcium stearate separator to the ball mill, and after sieving, the swollen treated Drag reducing polymer fine powder dry agent for surface adhesion release agent.

实施例2:本发明提到的一种用于缩短减阻剂起效时间的聚合物减阻剂颗粒溶胀处理方法,其制备方法如下:Embodiment 2: a kind of polymer drag reducing agent particle swelling treatment method for shortening the onset time of drag reducing agent mentioned in the present invention, its preparation method is as follows:

首先将干燥的块状减阻聚合物固体剪碎成5cm见方小块,称量1 kg,将其置于耐压保温反应釜中密封;然后在反应釜中充入CO2,达到2.0MPa,再30 min内控制温度在-10 ℃,之后再次充入CO2到设定压力4.0MPa(10℃时CO2临界压力4.5MPa),此时釜内的CO2为超临界,并保持4 h;待聚合物发生溶胀后,卸去釜内CO2并取出样品,2min之内称量标记样品重量为1.086kg;将溶胀处理后的减阻聚合物放入冷冻桶中,然后充入液氮至淹没聚合物,保持10 min,待液氮蒸发后,再按照与聚合物质量比1:10加入液态CO2保持5min;然后立即转入破碎机进行粗碎,在移至球磨机,按照与聚合物质量比1:20加入淀粉研磨助剂,并全程保持在-40℃以下;研磨同时,向球磨机中加入聚合物质量的20%的硬脂酸钙隔离剂,经筛分后制得经溶胀处理的表面粘附隔离剂的减阻聚合物细粉干剂。First, cut the dry bulk drag-reducing polymer solid into 5 cm square pieces, weigh 1 kg, and place them in a pressure-resistant thermal insulation reaction kettle to seal; then fill the reaction kettle with CO 2 to reach 2.0 MPa, The temperature was controlled at -10 °C for another 30 min, and then CO 2 was recharged to the set pressure of 4.0 MPa (the critical pressure of CO 2 at 10 ° C was 4.5 MPa). At this time, the CO 2 in the kettle was supercritical and kept for 4 h. ; After the polymer is swollen, remove the CO2 in the kettle and take out the sample, and weigh the marked sample within 2 minutes to be 1.086kg; put the swollen drag-reducing polymer into the freezing barrel, and then fill it with liquid nitrogen To submerge the polymer, keep it for 10 min. After the liquid nitrogen evaporates, add liquid CO 2 according to the mass ratio of the polymer to 1:10 and keep it for 5 min; Add starch grinding aids in a mass ratio of 1:20, and keep it below -40°C throughout the process; at the same time, add 20% of the polymer mass of calcium stearate separator to the ball mill, and sieve to obtain swollen Dry powder of drag reducing polymer fine powder for treated surface adhesion release agent.

实施例3:本发明提到的一种用于缩短减阻剂起效时间的聚合物减阻剂颗粒溶胀处理方法,其制备方法如下:Embodiment 3: a kind of polymer drag reducing agent particle swelling treatment method for shortening the onset time of drag reducing agent mentioned in the present invention, its preparation method is as follows:

首先将干燥的块状减阻聚合物固体剪碎成5cm见方小块,称量1 kg,将其置于耐压保温反应釜中密封;然后在反应釜中充入甲醇,达到0.1MPa,再30 min内控制温度在0 ℃,之后再次充入甲醇到设定压力0.1MPa(10℃时甲醇临界压力0.003MPa),此时釜内的甲醇为超临界,并保持4 h;待聚合物发生溶胀后,卸去釜内甲醇(注意回收甲醇)并取出样品,2min之内称量标记样品重量为1.026kg;将溶胀处理后的减阻聚合物放入冷冻桶中,然后充入液氮至淹没聚合物,保持10 min,待液氮蒸发后,再按照与聚合物质量比1:10加入甲醇保持5min;然后立即转入破碎机进行粗碎,在移至球磨机,按照与聚合物质量比1:10加入硬脂酸酐研磨助剂,并全程保持在-40℃以下;研磨同时,向球磨机中加入聚合物质量的20%的硬脂酸铝隔离剂,经筛分后制得经溶胀处理的表面粘附隔离剂的减阻聚合物细粉干剂。First, cut the dry block-shaped drag-reducing polymer solid into 5cm square pieces, weigh 1 kg, and place them in a pressure-resistant thermal insulation reaction kettle to seal; then fill the reaction kettle with methanol to reach 0.1MPa, and then The temperature was controlled at 0 °C for 30 min, and then the methanol was refilled to the set pressure of 0.1 MPa (the critical pressure of methanol at 10 °C was 0.003 MPa). At this time, the methanol in the kettle was supercritical and kept for 4 h; After swelling, remove the methanol in the kettle (pay attention to the recovery of methanol) and take out the sample. The weight of the marked sample is weighed to 1.026kg within 2 minutes; Submerge the polymer and keep it for 10 min. After the liquid nitrogen evaporates, add methanol according to the mass ratio of the polymer at 1:10 and keep it for 5 min; then immediately transfer it to the crusher for coarse crushing, and then move it to the ball mill. Add stearic anhydride grinding aid at 1:10, and keep it below -40°C throughout the whole process; at the same time, add 20% of the polymer mass of aluminum stearate separator to the ball mill, and sieve to obtain a swollen treated The surface adhesion release agent of the drag reducing polymer fine powder dry agent.

实施例4:本发明提到的一种用于缩短减阻剂起效时间的聚合物减阻剂颗粒溶胀处理方法,其制备方法如下:Embodiment 4: a kind of polymer drag reducing agent particle swelling treatment method for shortening the onset time of drag reducing agent mentioned in the present invention, its preparation method is as follows:

首先将干燥的块状减阻聚合物固体剪碎成5cm见方小块,称量1 kg,将其置于耐压保温反应釜中密封;然后在反应釜中充入甲醇,达到0.1MPa,再30 min内控制温度在30 ℃,之后再次充入甲醇到设定压力0.2MPa(10℃时甲醇临界压力0.02MPa),此时釜内的甲醇为超临界,并保持12 h;待聚合物发生溶胀后,卸去釜内甲醇(注意回收甲醇)并取出样品,2min之内称量标记样品重量为1.053kg;将溶胀处理后的减阻聚合物放入冷冻桶中,然后充入液氮至淹没聚合物,保持30 min,待液氮蒸发后,再按照与聚合物质量比3:10加入甲醇保持20min;然后立即转入破碎机进行粗碎,在移至球磨机,按照与聚合物质量比1:20加入硬脂酸酐研磨助剂,并全程保持在-40℃以下;研磨同时,向球磨机中加入聚合物质量的20%的硬脂酸铝隔离剂,经筛分后制得经溶胀处理的表面粘附隔离剂的减阻聚合物细粉干剂。First, cut the dry block-shaped drag-reducing polymer solid into 5cm square pieces, weigh 1 kg, and place them in a pressure-resistant thermal insulation reaction kettle to seal; then fill the reaction kettle with methanol to reach 0.1MPa, and then The temperature was controlled at 30 °C within 30 min, and then the methanol was recharged to the set pressure of 0.2 MPa (the critical pressure of methanol at 10 °C was 0.02 MPa). At this time, the methanol in the kettle was supercritical and kept for 12 h; After swelling, remove the methanol in the kettle (pay attention to the recovery of methanol) and take out the sample, and weigh the marked sample within 2 minutes to be 1.053kg; put the swollen drag-reducing polymer into a freezing barrel, and then fill it with liquid nitrogen to 1.053kg. Submerge the polymer and keep it for 30 min. After the liquid nitrogen evaporates, add methanol according to the mass ratio of 3:10 to the polymer and keep it for 20 min; then immediately transfer it to the crusher for coarse crushing, and then move it to the ball mill. Add stearic anhydride grinding aid at 1:20, and keep it below -40°C throughout the whole process; at the same time, add 20% of the polymer mass of aluminum stearate separator to the ball mill, and sieve to obtain a swollen treated The surface adhesion release agent of the drag reducing polymer fine powder dry agent.

实施例5:本发明提到的一种用于缩短减阻剂起效时间的聚合物减阻剂颗粒溶胀处理方法,其制备方法如下:Embodiment 5: a kind of polymer drag reducing agent particle swelling treatment method for shortening the onset time of drag reducing agent mentioned in the present invention, its preparation method is as follows:

首先将干燥的块状减阻聚合物固体剪碎成5cm见方小块,称量1 kg,将其置于耐压保温反应釜中密封;然后在反应釜中充入甲苯,达到0.1MPa,再30 min内控制反应温度在0℃,之后再次充入甲苯到设定压力0.1MPa(10℃时甲苯临界压力0.001MPa),此时釜内的甲苯为超临界,并保持4 h;待聚合物发生溶胀后,卸去釜内甲苯(注意回收甲苯)并取出样品,2min之内称量标记样品重量为1.167kg;将溶胀处理后的减阻聚合物放入冷冻桶中,然后充入液氮至淹没聚合物,保持10 min,待液氮蒸发后,再按照与聚合物质量比1:10加入甲苯保持5min;然后立即转入破碎机进行粗碎,在移至球磨机,按照与聚合物质量比1:20加入硬脂酸钙研磨助剂,并全程保持在-40℃以下;研磨同时,向球磨机中加入聚合物质量的20%的滑石粉隔离剂,经筛分后制得经溶胀处理的表面粘附隔离剂的减阻聚合物细粉干剂。First, cut the dry block drag-reducing polymer solid into 5 cm square pieces, weigh 1 kg, and place it in a pressure-resistant thermal insulation reaction kettle to seal; then fill the reaction kettle with toluene to reach 0.1 MPa, and then The reaction temperature was controlled at 0 °C within 30 min, and then toluene was recharged to the set pressure of 0.1 MPa (the critical pressure of toluene at 10 °C was 0.001 MPa). At this time, the toluene in the kettle was supercritical and kept for 4 h; After swelling, remove the toluene in the kettle (pay attention to the recovery of toluene) and take out the sample, weigh the marked sample within 2 minutes to 1.167kg; put the swollen drag-reducing polymer into the freezing barrel, and then fill it with liquid nitrogen To submerge the polymer, keep it for 10 minutes, after the liquid nitrogen evaporates, add toluene according to the mass ratio of the polymer at 1:10 and keep it for 5 minutes; Add calcium stearate grinding aid at a ratio of 1:20, and keep it below -40°C throughout the process; at the same time of grinding, add 20% talcum powder release agent of the polymer mass to the ball mill, and after sieving, the swollen treated The surface adhesion release agent of the drag reducing polymer fine powder dry agent.

实施例6:本发明提到的一种用于缩短减阻剂起效时间的聚合物减阻剂颗粒溶胀处理方法,其制备方法如下:Embodiment 6: a kind of polymer drag reducing agent particle swelling treatment method for shortening the onset time of drag reducing agent mentioned in the present invention, its preparation method is as follows:

首先将干燥的块状减阻聚合物固体剪碎成5cm见方小块,称量1 kg,将其置于耐压保温反应釜中密封;然后在反应釜中充入甲苯,达到0.1MPa,再30 min内控制反应温度在30℃,之后再次充入甲苯到设定压力0.1MPa(10℃时甲苯临界压力0.005MPa),此时釜内的甲苯为超临界,并保持12 h;待聚合物发生溶胀后,卸去釜内甲苯(注意回收甲苯)并取出样品,2min之内称量标记样品重量为1.206kg;将溶胀处理后的减阻聚合物放入冷冻桶中,然后充入液氮至淹没聚合物,保持10 min,待液氮蒸发后,再按照与聚合物质量比3:10加入甲苯保持5min;然后立即转入破碎机进行粗碎,在移至球磨机,按照与聚合物质量比1:10加入硬脂酸钙研磨助剂,并全程保持在-40℃以下;研磨同时,向球磨机中加入聚合物质量的20%的针状石蜡隔离剂,经筛分后制得经溶胀处理的表面粘附隔离剂的减阻聚合物细粉干剂。First, cut the dry block drag-reducing polymer solid into 5 cm square pieces, weigh 1 kg, and place it in a pressure-resistant thermal insulation reaction kettle to seal; then fill the reaction kettle with toluene to reach 0.1 MPa, and then The reaction temperature was controlled at 30 °C within 30 min, and then toluene was recharged to the set pressure of 0.1 MPa (the critical pressure of toluene at 10 °C was 0.005 MPa). At this time, the toluene in the kettle was supercritical and kept for 12 h; After swelling, remove the toluene in the kettle (pay attention to the recovery of toluene) and take out the sample, weigh the marked sample weight within 2 minutes to 1.206kg; put the swollen drag-reducing polymer into the freezing barrel, and then fill it with liquid nitrogen To submerge the polymer, keep it for 10 min. After the liquid nitrogen evaporates, add toluene according to the mass ratio of the polymer to 3:10 and keep it for 5 min; Add calcium stearate grinding aid at a ratio of 1:10, and keep it below -40°C throughout the process; at the same time, add 20% of the polymer mass of acicular paraffin separator to the ball mill, and sieve to obtain a swollen Dry powder of drag reducing polymer fine powder for treated surface adhesion release agent.

溶胀后减阻剂干剂的悬浮方法Suspension method of drag reducer dry agent after swelling

减阻聚合物细粉干剂首先需要经过分散至悬浮液中,才可进行相关性能测试。The drag-reducing polymer fine powder dry agent needs to be dispersed into the suspension first, and then the relevant performance test can be carried out.

称取现有溶胀处理后的聚α烯烃细粉,按照悬浮液35%的质量比加入到悬浮液(悬浮体系根据需要可分为油基、水基和醇基)中,按500r/min搅拌60min,形成稳定的浆状减溶胀处理的聚α烯烃颗粒油品减阻剂悬浮溶液。Weigh the polyalphaolefin fine powder after the existing swelling treatment, add it to the suspension according to the mass ratio of 35% of the suspension (the suspension system can be divided into oil-based, water-based and alcohol-based according to needs), and stir at 500 r/min. For 60 min, a stable slurry-like swell-reducing treated polyalphaolefin particle oil drag reducing agent suspension solution was formed.

效果测试(实验测试减阻剂浓度25ppm)Effect test (experimental test drag reducer concentration 25ppm)

(1)测试标准和方法(1) Test standards and methods

标准“输油管道减阻剂减阻效果室内测试方法SY/T6578-2009”要求“用柴油或其他非极性溶剂配制成聚合物浓度为1g/L的溶液”,该溶液是先将浆状减阻剂均匀分散到溶剂中,然后再配置到测试实验浓度,并由氮气鼓泡分散一段时间。该评价方法中减阻剂在进入测试环道内已实现充分分散混合,用以表征该发明中减阻剂的减阻效果。实际测试过程中,通过改变氮气鼓泡分散时间,评测稳态减阻效果,来判定减阻剂的起效时间的差异。The standard "Indoor Test Method for Drag Reduction Effect of Oil Pipeline Drag Reducing Agents SY/T6578-2009" requires "to prepare a solution with a polymer concentration of 1 g/L with diesel oil or other non-polar solvents". The resist is uniformly dispersed in the solvent, and then configured to the test experimental concentration, and dispersed by nitrogen bubbling for a period of time. In this evaluation method, the drag reducing agent has been fully dispersed and mixed in the test loop to characterize the drag reducing effect of the drag reducing agent in the present invention. In the actual test process, the difference in the onset time of the drag reducer was determined by changing the nitrogen bubbling dispersion time and evaluating the steady-state drag reduction effect.

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(2)现场添加减阻剂是存在分散起效时间和分散距离,故本实验根据实际工况,采用旋转圆盘系统(参照附图1),旋转圆盘测试系统包括恒温水浴槽1、联轴器2、扭矩传感器3、调速电机4、数据采集卡5、计算机6、样品槽7、下支撑板8、支撑杆9、上支撑板10,其中,所述下支撑板8的一侧通过支撑杆9连接上支撑板10,在下支撑板8上安装恒温水浴槽1,恒温水浴槽1上安设样品槽7;在上支撑板10上安设调速电机4,调速电机4下部连接联轴器2和扭矩传感器3,且扭矩传感器3通过数据线连接到数据采集卡5,并进一步连接到计算机6。(2) There is a dispersion onset time and dispersion distance when the drag reducing agent is added on site, so this experiment adopts a rotating disc system (refer to Figure 1) according to the actual working conditions. The rotating disc test system includes a constant temperature water bath 1, a connecting Shaft 2, torque sensor 3, speed regulating motor 4, data acquisition card 5, computer 6, sample tank 7, lower support plate 8, support rod 9, upper support plate 10, wherein one side of the lower support plate 8 Connect the upper support plate 10 through the support rod 9, install the constant temperature water bath 1 on the lower support plate 8, install the sample tank 7 on the constant temperature water bath 1; install the speed regulating motor 4 on the upper supporting plate 10, and the lower part of the speed regulating motor 4 The coupling 2 and the torque sensor 3 are connected, and the torque sensor 3 is connected to the data acquisition card 5 through a data cable, and further connected to the computer 6 .

使用时,首先考察起效时间的差异。可以调变圆盘转速,改变流体雷诺数,通过扭矩传感器采集的数据计算流体阻力,有加剂前后流动阻力的变化计算减阻率,通过不同时间减阻效果的差距,可以反映出减阻剂起效时间的区别。When using, first examine the difference in onset time. The speed of the disc can be adjusted, the Reynolds number of the fluid can be changed, the fluid resistance can be calculated through the data collected by the torque sensor, and the drag reduction rate can be calculated based on the change of the flow resistance before and after adding the agent. difference in onset time.

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Figure 994641DEST_PATH_IMAGE002

经过环道测试和旋转圆盘测试,比较市售减阻剂和各实施例减阻剂减阻性能起效时间可以看出:在环道测试中,市售减阻剂30min和10min鼓泡分散后减阻性能有很大的差别,说明该减阻剂需要经过较长的时间溶胀和分散才能展现出减阻效果。6个实施例样品的30min和10min分散后中减阻性能差别不大,可以证明该发明的溶胀处理方法能有效降低减阻剂起效时间。在旋转圆盘测试中,6个实施例的样品的减阻起效时间均为超过15min,而市售产品为30min,进一步说明,本发明可以大大降低减阻剂的起效时间。After the loop test and the rotating disc test, comparing the onset time of the drag reducing performance of the drag reducer on the market and each example, it can be seen that: in the loop test, the commercially available drag reducer was bubbled and dispersed for 30min and 10min. There is a great difference in the post drag reduction performance, indicating that the drag reducer needs to swell and disperse for a long time to show the drag reduction effect. There is little difference in drag reduction performance between 30min and 10min dispersion of the six example samples, which can prove that the swelling treatment method of the invention can effectively reduce the onset time of drag reducer. In the rotating disc test, the drag reduction onset time of the samples of the 6 examples is more than 15min, while the commercial product is 30min, which further shows that the present invention can greatly reduce the drag reducer onset time.

本例由于添加了通过引入A流体(CO2、甲醇或甲苯),超临界条件下通过其特殊的溶解和扩散性能,可以渗入到减阻聚合物固体内,实现溶胀作用,减阻聚合物质量增加,表面积提高,在油品中的溶胀、溶解和分散过程加快,促进了减阻剂的快速起效。In this case, due to the addition of A fluid (CO 2 , methanol or toluene), under supercritical conditions, through its special dissolution and diffusion properties, it can penetrate into the solid of the drag-reducing polymer to achieve swelling and improve the quality of the drag-reducing polymer. With the increase of the surface area, the swelling, dissolution and dispersion process in the oil are accelerated, which promotes the rapid onset of the drag reducing agent.

以上所述,仅是本发明的部分较佳实施例,任何熟悉本领域的技术人员均可能利用上述阐述的技术方案加以修改或将其修改为等同的技术方案。因此,依据本发明的技术方案所进行的任何简单修改或等同置换,尽属于本发明要求保护的范围。The above are only some preferred embodiments of the present invention, and any person skilled in the art may use the technical solutions described above to modify or modify them into equivalent technical solutions. Therefore, any simple modifications or equivalent replacements made according to the technical solutions of the present invention fall within the protection scope of the present invention.

Claims (2)

1. A swelling treatment method of a polymer drag reducer for shortening the onset time of the drag reducer is characterized by comprising the following preparation steps:
firstly, cutting dry blocky anti-drag polymer solid into small blocks of 5cm square, weighing 1 kg, and placing the small blocks in a pressure-resistant heat-preservation reaction kettle for sealing; then filling methanol into the reaction kettle to reach 0.1MPa, controlling the temperature to be 0 ℃ within 30min, then filling the methanol again to the set pressure of 0.1MPa, wherein the methanol in the reaction kettle is supercritical and is kept for 4 hours; after the polymer is swelled, removing the methanol in the kettle and taking out the sample, and weighing the marked sample within 2min to obtain 1.026 kg; putting the swelled drag reduction polymer into a freezing barrel, then filling liquid nitrogen until the polymer is submerged, keeping for 10min, and after the liquid nitrogen is evaporated, adding methanol according to the mass ratio of 1:10 to the polymer and keeping for 5 min; then immediately transferring the mixture into a crusher for coarse crushing, transferring the mixture to a ball mill, adding a stearic anhydride grinding aid according to the mass ratio of the stearic anhydride grinding aid to the polymer of 1:10, and keeping the whole process at the temperature below 40 ℃ below zero; and (3) adding an aluminum stearate release agent accounting for 20% of the mass of the polymer into the ball mill during grinding, and screening to obtain the fine powder drying agent of the drag-reducing polymer with the surface adhered with the release agent after swelling treatment.
2. A swelling treatment method of a polymer drag reducer for shortening the onset time of the drag reducer is characterized by comprising the following preparation steps:
firstly, cutting dry blocky anti-drag polymer solid into small blocks of 5cm square, weighing 1 kg, and placing the small blocks in a pressure-resistant heat-preservation reaction kettle for sealing; then filling toluene into the reaction kettle to reach 0.1MPa, controlling the reaction temperature to be 0 ℃ within 30min, then filling toluene again to the set pressure of 0.1MPa, wherein the toluene in the kettle is supercritical and is kept for 4 h; after the polymer is swelled, removing the toluene in the kettle and taking out the sample, and weighing the marked sample within 2min to obtain 1.167 kg; placing the swelled drag reduction polymer into a freezing barrel, then filling liquid nitrogen until the polymer is submerged, keeping for 10min, and after the liquid nitrogen is evaporated, adding toluene according to the mass ratio of 1:10 to the polymer and keeping for 5 min; then immediately transferring the mixture into a crusher for coarse crushing, transferring the mixture to a ball mill, adding a calcium stearate grinding aid according to the mass ratio of 1:20 of the mixture to the polymer, and keeping the whole process at the temperature below 40 ℃ below zero; and (3) adding a talcum powder separant accounting for 20% of the mass of the polymer into the ball mill during grinding, and screening to obtain the anti-drag polymer fine powder dry agent with the separant adhered to the surface after swelling treatment.
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