CN116407967A - A kind of olefin mixing gas distribution device and method - Google Patents
A kind of olefin mixing gas distribution device and method Download PDFInfo
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Abstract
Description
技术领域technical field
本发明涉及一种烯烃混合配气装置及方法,特别涉及一种烯烃混合配气装置及使用该装置混合烯烃的方法,属于化工领域合成树脂催化剂及新产品技术中的聚乙烯催化剂、工艺及新产品技术。The invention relates to an olefin mixing gas distribution device and method, in particular to an olefin mixing gas distribution device and a method for mixing olefins using the device, belonging to the synthetic resin catalyst in the chemical industry and the polyethylene catalyst, process and new product technology. product technologies.
背景技术Background technique
2020年,中国聚乙烯市场需求量达3800万吨,国内产能达2300万吨/年,进口量达1800万吨,高端产品主要依赖进口。随着高品质聚乙烯产品需求的快速增长,聚乙烯市场竞争愈来愈激烈,催化剂的专用化和高端化已成为趋势。淤浆聚合工艺反应压力较低、操作条件易于控制、产品性能好,是我国HDPE重要的生产技术之一。目前,国内淤浆工艺HDPE产能为750万吨/年,需催化剂为300吨/年。近年来,国内聚烯烃生产装置不断扩大,新产品开发成为生产企业的发展关键,研究烯烃聚合反应,尤其是烯烃共聚合反应成为技术攻关的核心。烯烃聚合过程是烯烃单体在固体催化剂颗粒上进行聚合反应,生成的聚合物复制了催化剂的颗粒形态,除颗粒尺寸不同程度地放大外,其粒型、粒度分布和堆积密度均与催化剂的颗粒形态直接相关。In 2020, China's polyethylene market demand will reach 38 million tons, the domestic production capacity will reach 23 million tons per year, and the import volume will reach 18 million tons. High-end products mainly rely on imports. With the rapid growth of demand for high-quality polyethylene products, the competition in the polyethylene market has become increasingly fierce, and the specialization and high-end of catalysts have become a trend. The slurry polymerization process has low reaction pressure, easy control of operating conditions, and good product performance. It is one of the important production technologies of HDPE in my country. At present, the domestic slurry process HDPE production capacity is 7.5 million tons/year, and the catalyst required is 300 tons/year. In recent years, domestic polyolefin production facilities have continued to expand, new product development has become the key to the development of production enterprises, and research on olefin polymerization, especially olefin copolymerization, has become the core of technological research. The olefin polymerization process is that olefin monomers are polymerized on solid catalyst particles, and the resulting polymer replicates the particle shape of the catalyst. Except that the particle size is enlarged to varying degrees, its particle shape, particle size distribution and bulk density are similar to those of the catalyst particles. form is directly related.
中国专利CN201811144109.7公开了一种用于配气的气体混合装置,其包括罐体、底板、四组支腿和搅拌电机;包括四组左支撑杆、四组右支撑杆、冷却箱、加热箱、左上隔板、左下隔板、右上隔板、右下隔板、多组左换热管、多组右换热管、加热盘管和冷却盘管;还包括固定圈、左第一支杆、左第二支杆、右第一支杆、右第二支杆、半圆柱、半螺杆、调节螺纹套管、上限位夹板、下限位夹板和卡板,固定圈固定套装在罐体外壁的上侧,调节螺纹套管的外部交错设置有防滑齿纹;该发明涉及的气体混合装置主要用于气体的混合,未涉及α-烯烃的混合配气,尤其是不同液态α-烯烃的混合。Chinese patent CN201811144109.7 discloses a gas mixing device for gas distribution, which includes a tank body, a bottom plate, four sets of legs and a stirring motor; four sets of left support rods, four sets of right support rods, a cooling box, a heating Box, upper left partition, lower left partition, upper right partition, lower right partition, multiple sets of left heat exchange tubes, multiple sets of right heat exchange tubes, heating coils and cooling coils; also includes fixed ring, left first branch Rod, left second support rod, right first support rod, right second support rod, half cylinder, half screw, adjusting threaded sleeve, upper limit splint, lower limit splint and clamping plate, fixed ring fixed on the outer wall of the tank The upper side of the adjustment threaded sleeve is provided with anti-skid staggered lines; the gas mixing device involved in this invention is mainly used for gas mixing, and does not involve the mixing and distribution of α-olefins, especially the mixing of different liquid α-olefins .
中国专利CN201911425957.X公开了一种粘稠流体混合和气体分散专用搅拌装置,其包括上部的驱动机构(1)、盛装介质的搅拌釜、由驱动机构伸入釜内的轴(2)以及安装定位于轴(2)下端的搅拌器(3),在搅拌器(3)下方配置气体分布器(4),通过搅拌器(3)的专门设计配合其下方的气体分布器(4),既可以提高气液传质能力,又可以加强流体的混合效率,解决了高粘度介质混合和气体分散的问题,适用于粘稠性物料的通风搅拌发酵过程,同样也适用于加氢反应、氧化反应等其它气液反应过程,使其具有高效的混合性能及气体分散传质性能;该发明针对高粘度介质混合和气体分散的问题设计气体分布器,未涉及α-烯烃的混合配气。Chinese patent CN201911425957.X discloses a special stirring device for viscous fluid mixing and gas dispersion, which includes an upper driving mechanism (1), a stirring tank containing a medium, a shaft (2) extending into the tank from the driving mechanism, and an installation The stirrer (3) located at the lower end of the shaft (2), and the gas distributor (4) is arranged under the stirrer (3), and the special design of the stirrer (3) cooperates with the gas distributor (4) below it, both It can improve the gas-liquid mass transfer capacity, and can enhance the mixing efficiency of the fluid. It solves the problems of high-viscosity medium mixing and gas dispersion. It is suitable for the ventilation and stirring fermentation process of viscous materials, and it is also suitable for hydrogenation and oxidation reactions. And other gas-liquid reaction processes, so that it has efficient mixing performance and gas dispersion mass transfer performance; the invention designs a gas distributor for the problems of high-viscosity medium mixing and gas dispersion, and does not involve the mixing and distribution of α-olefins.
中国专利CN202022158024.3公开了一种标准混合气体制备装置,其包括制备腔,所述制备腔顶部中间位置处固定设置有正反转电机,所述正反转电机输出轴端部传动连接有转轴,所述转轴顶部固定设置有主动齿轮,且所述转轴底部固定设置有三组搅拌叶,所述制备腔内腔两侧均设置有转杆。本实用新型通过正反转电机正转带动搅拌叶以及两个转杆转动,进而带动对应位置的活动板缓慢向上移动,将制备腔内腔两侧的气体压入至混合腔内,搅拌叶实现对进入的气体搅拌混合,正反转电机反转时将制备腔内腔中部的气体再次吸入中混合腔内搅拌混合,调节正反转电机正反转,从而通过混合腔以及搅拌叶实现对制备腔内腔的气体不断混合,混合速率较快,混合效果较好;该发明主要用于标准混合气体的制备技术领域,未涉及α-烯烃的混合配气,尤其是不同液态α-烯烃的混合。Chinese patent CN202022158024.3 discloses a standard mixed gas preparation device, which includes a preparation chamber, a forward and reverse motor is fixed at the middle position on the top of the preparation chamber, and a rotating shaft is connected to the end of the output shaft of the forward and reverse motor , the top of the rotating shaft is fixedly provided with a driving gear, and the bottom of the rotating shaft is fixedly provided with three sets of stirring blades, and both sides of the inner cavity of the preparation chamber are provided with rotating rods. The utility model drives the stirring blade and the two rotating rods to rotate through the positive and negative rotation of the motor, and then drives the movable plate at the corresponding position to move upward slowly, and presses the gas on both sides of the inner cavity of the preparation chamber into the mixing chamber, and the stirring blade realizes Stir and mix the incoming gas, when the forward and reverse motor reverses, the gas in the middle of the preparation chamber is sucked into the middle mixing chamber again for stirring and mixing, and the forward and reverse motor is adjusted, so that the preparation can be realized through the mixing chamber and the stirring blade The gas in the cavity is continuously mixed, the mixing rate is faster, and the mixing effect is better; this invention is mainly used in the technical field of preparation of standard mixed gases, and does not involve the mixing and distribution of α-olefins, especially the mixing of different liquid α-olefins .
在聚合反应过程中,不同烯烃在聚合反应体系中均匀分布成为了技术难点。现有的淤浆法烯烃聚合评价装置评价乙烯与α-烯烃共聚合时,乙烯单体在聚合反应釜的顶部加入,乙烯气体在一定温度和压力条件下溶解到分散剂中,共聚单体单独加入至分散剂中,尤其是室温下呈液态的共聚单体加入时通常采用一次性加入或者分批次加入,因此乙烯与α-烯烃的混合效果较差,共聚单体在现有的评价体系中分布不均匀,这种评价试验的聚合工艺与淤浆法工业生产装置的工艺不同,淤浆法工业生产装置聚合反应过程中乙烯和共聚单体经过预混合后自反应釜的底部加入,因此现有的淤浆聚合评价试验装置评价催化剂的活性不准确,聚合物的组成与工业生产装置产品存在一定差距,无法真实反映催化剂的性能,不能为催化剂的淤浆中试聚合工艺研究提供有效数据支撑。During the polymerization process, the uniform distribution of different olefins in the polymerization system has become a technical difficulty. When the existing slurry method olefin polymerization evaluation device evaluates the copolymerization of ethylene and α-olefin, ethylene monomer is added at the top of the polymerization reactor, ethylene gas is dissolved into the dispersant under certain temperature and pressure conditions, and the comonomer alone When added to the dispersant, especially comonomers that are liquid at room temperature are usually added at one time or in batches, so the mixing effect of ethylene and α-olefins is poor, and the comonomers in the existing evaluation system Inhomogeneous distribution in the medium, the polymerization process of this evaluation test is different from the process of the slurry method industrial production device. During the polymerization reaction of the slurry method industrial production device, ethylene and comonomer are added from the bottom of the reactor after pre-mixing, so The existing slurry polymerization evaluation test device is inaccurate in evaluating the activity of the catalyst, and there is a certain gap between the composition of the polymer and the product of the industrial production device, which cannot truly reflect the performance of the catalyst, and cannot provide effective data for the research on the slurry pilot polymerization process of the catalyst support.
发明内容Contents of the invention
为解决现有技术存在的问题,本发明提供一种烯烃混合配气装置及方法,不同α-烯烃共聚单体经本发明的烯烃混合配气装置充分混合,使得混合气的组成更加均匀,有利于提高共聚合物的组分均一性。In order to solve the problems existing in the prior art, the present invention provides an olefin mixing gas distribution device and method. Different α-olefin comonomers are fully mixed through the olefin mixing gas distribution device of the present invention, so that the composition of the mixed gas is more uniform, and there is It is beneficial to improve the component uniformity of the copolymer.
为达上述目的,本发明提供一种烯烃混合配气装置,该烯烃混合配气装置包括:配气罐、导流环、分布板、静态混合器、烯烃进料口以及循环动力单元。配气罐的顶部设有原料入口、混合气体出口、循环出口,底部设有循环入口;导流环设于配气罐内部,并与配气罐底部的循环入口连接;分布板设于配气罐内部,并位于导流环的上方;静态混合器与配气罐顶部的循环出口和配气罐底部的循环入口连接;烯烃进料口设于静态混合器与循环出口之间;循环动力单元设于静态混合器与循环入口之间。To achieve the above purpose, the present invention provides an olefin mixing and gas distribution device, which includes: a gas distribution tank, a deflector ring, a distribution plate, a static mixer, an olefin feed port and a cycle power unit. The top of the gas distribution tank is provided with a raw material inlet, a mixed gas outlet, and a circulation outlet, and the bottom is provided with a circulation inlet; the guide ring is set inside the gas distribution tank and connected to the circulation inlet at the bottom of the gas distribution tank; Inside the tank and above the guide ring; the static mixer is connected to the circulation outlet on the top of the gas distribution tank and the circulation inlet at the bottom of the gas distribution tank; the olefin feed port is set between the static mixer and the circulation outlet; the circulation power unit It is located between the static mixer and the circulation inlet.
于一实施例中,还包括色谱,设于配气罐顶部。In one embodiment, a chromatograph is also included, which is arranged on the top of the gas distribution tank.
于一实施例中,还包括加热装置,设于配气罐的内部;加热装置包括水浴加热设备、蒸汽加热设备、油浴加热设备、电加热设备和光波加热设备中的至少一种。In one embodiment, a heating device is also included inside the gas distribution tank; the heating device includes at least one of water bath heating equipment, steam heating equipment, oil bath heating equipment, electric heating equipment and light wave heating equipment.
于一实施例中,还包括加热装置,设于配气罐的外壁;加热装置包括电加热带和电加热套中的至少一种。In one embodiment, a heating device is also included, which is arranged on the outer wall of the gas distribution tank; the heating device includes at least one of an electric heating belt and an electric heating jacket.
于一实施例中,还包括温度检测口、压力检测口和放料口,温度检测口和压力检测口设于配气罐顶部,放料口设于配气罐底部。In one embodiment, it also includes a temperature detection port, a pressure detection port and a material discharge port, the temperature detection port and the pressure detection port are located on the top of the gas distribution tank, and the material discharge port is located on the bottom of the gas distribution tank.
于一实施例中,循环动力单元为泵或压缩机。In one embodiment, the cycle power unit is a pump or a compressor.
于一实施例中,原料入口为第一原料或氮气入口,用于加入第一原料或进行氮气吹扫。In one embodiment, the raw material inlet is the first raw material or the nitrogen gas inlet, which is used for adding the first raw material or nitrogen purging.
于一实施例中,烯烃进料口为第二原料入口。In one embodiment, the olefin feed inlet is the second raw material inlet.
于一实施例中,第一原料和第二原料为α-烯烃,包括乙烯、丙烯、1-丁烯、4-甲基-1-戊烯、1-己烯和1-辛烯中的至少一种。In one embodiment, the first raw material and the second raw material are alpha-olefins, including at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene A sort of.
本发明还提供一种烯烃混合配气方法,该方法采用上述烯烃混合配气装置,该方法包括以下步骤:The present invention also provides a method for mixing and distributing olefins. The method uses the above-mentioned device for mixing and distributing olefins. The method includes the following steps:
步骤S1:将第一原料通过配气罐顶部的原料入口输入烯烃混合配气装置;Step S1: Input the first raw material into the olefin mixing gas distribution device through the raw material inlet on the top of the gas distribution tank;
步骤S2:将第二原料通过烯烃进料口输入静态混合器;烯烃混合配气装置内的第一原料从循环出口输出并进入静态混合器,第一原料与第二原料在静态混合器中进行第一次混合,得到第一混合料;Step S2: Input the second raw material into the static mixer through the olefin feed port; the first raw material in the olefin mixing and gas distribution device is output from the circulation outlet and enters the static mixer, and the first raw material and the second raw material are mixed in the static mixer. Mix for the first time to obtain the first mixture;
步骤S3:第一混合料通过循环动力单元经循环入口输入烯烃混合配气装置,第一混合料经导流环分散并经分布板进行第二次混合,得到第二混合料;Step S3: the first mixed material is input into the olefin mixing and gas distribution device through the circulation power unit through the circulation inlet, the first mixed material is dispersed through the guide ring and mixed for the second time through the distribution plate to obtain the second mixed material;
步骤S4:第二混合料经色谱分析测试混合结果;若混合结果合格,则第二混合料从混合气体出口输出,进入下游工艺;若混合结果不合格,则返回步骤S2,第二混合料从循环出口输出并输入静态混合器重新进行混合。Step S4: The mixing result of the second mixture is tested by chromatographic analysis; if the mixing result is qualified, the second mixture is output from the mixed gas outlet and enters the downstream process; if the mixing result is unqualified, return to step S2, and the second mixture is from The loop exits and enters the static mixer for remixing.
本发明的烯烃混合配气装置,能够用于不同烯烃共聚单体的充分混合,使得到的混合气的组成更加均匀,有利于提高共聚合物的组分均一性;并且,本发明得到的混合气能够自反应釜底部的搅拌桨上的气体出口分散到淤浆体系中,从而提高了聚合单体在淤浆体系中的浓度,加大了聚合单体与催化剂接触量,更接近淤浆法工业生产装置的聚合环境,提高了淤浆法乙烯聚合评价试验装置评价催化剂活性的准确性,可为淤浆法中试聚合装置提供基础数据,大幅提高中试聚合装置的效率、降低成本,对淤浆法中试装置运行、聚合工艺开发和生产装置技术服务具有重要的指导意义。The olefin mixing gas distribution device of the present invention can be used for the sufficient mixing of different olefin comonomers, so that the composition of the obtained mixed gas is more uniform, which is conducive to improving the component homogeneity of the copolymer; and, the mixed gas obtained in the present invention The gas can be dispersed into the slurry system from the gas outlet on the stirring paddle at the bottom of the reactor, thereby increasing the concentration of the polymerized monomer in the slurry system and increasing the contact amount between the polymerized monomer and the catalyst, which is closer to the slurry method The polymerization environment of the industrial production device improves the accuracy of the evaluation test device for the evaluation of catalyst activity in the slurry method ethylene polymerization, and can provide basic data for the pilot polymerization device of the slurry method, greatly improving the efficiency of the pilot polymerization device and reducing costs. The operation of the slurry pilot plant, the development of the polymerization process and the technical service of the production plant have important guiding significance.
附图说明Description of drawings
图1为本发明的烯烃混合配气装置一实施例的结构示意图。Figure 1 is a schematic structural view of an embodiment of an olefin mixing and gas distribution device of the present invention.
其中,附图标记:Among them, reference signs:
配气罐1Gas distribution tank 1
循环动力单元2
色谱3
分布板4
导流环5Guide ring 5
原料入口6Raw material entrance 6
混合气体出口7Mixed gas outlet 7
循环出口8
温度检测口9
压力检测口10
底部设有循环入口11The bottom is equipped with a
放料口12
加热装置13
静态混合器14
烯烃进料口15
具体实施方式Detailed ways
以下结合附图对本发明的烯烃混合配气装置及方法作进一步阐述。The olefin mixing and gas distribution device and method of the present invention will be further described below in conjunction with the accompanying drawings.
请参照图1,图1为本发明的烯烃混合配气装置一实施例的结构示意图,本发明的烯烃混合配气装置包括配气罐1、导流环5、分布板4、静态混合器14、烯烃进料口15以及循环动力单元2。Please refer to Fig. 1, Fig. 1 is a structural schematic diagram of an embodiment of the olefin mixing gas distribution device of the present invention, the olefin mixing gas distribution device of the present invention includes a gas distribution tank 1, a guide ring 5, a
配气罐1用于对原料进行混合配气,该原料包括至少两种α-烯烃,α-烯烃例如但不限于乙烯、丙烯、1-丁烯、4-甲基-1-戊烯、1-己烯和1-辛烯中的至少二种组成的混合物。配气罐1的顶部设有色谱3、原料入口6、混合气体出口7、循环出口8、温度检测口9、压力检测口10。配气罐1的底部设有循环入口11和放料口12。The gas distribution tank 1 is used to mix and distribute the raw materials, which include at least two α-olefins, such as but not limited to ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1 -A mixture of at least two of hexene and 1-octene. The top of the gas distribution tank 1 is provided with a
原料入口6为第一原料或氮气入口,用于加入第一原料或进行氮气吹扫。第一原料可以为单一物质,也可以为混合物,例如第一原料为乙烯、丙烯、1-丁烯、4-甲基-1-戊烯、1-己烯和1-辛烯中的至少一种,也可以为乙烯、丙烯、1-丁烯、4-甲基-1-戊烯、1-己烯和1-辛烯中的至少二种组成的混合物。The raw material inlet 6 is the first raw material or nitrogen gas inlet, used for adding the first raw material or nitrogen purging. The first raw material can be a single substance or a mixture, for example, the first raw material is at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene It can also be a mixture of at least two of ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.
混合气体出口7为配制完成的混合气体出口,用于将混合气体输送至下游的烯烃共聚合装置或进行取样。The mixed gas outlet 7 is the prepared mixed gas outlet, which is used to deliver the mixed gas to a downstream olefin copolymerization device or to take samples.
循环出口8用于输出循环的烯烃至循环管线,优选地,循环管线的外部设有保温材料。The
温度检测口9用于检测配气罐1的温度,便于控制液态烯烃全部转化为气体状态。The
压力检测口10用于检测配气罐1的压力,便于控制液态烯烃全部转化为气体状态,同时满足下游的烯烃共聚合装置的压力使用范围。The
色谱3用于在线测量配气罐1中气体组份及其含量,确保得到的混合气体满足试验要求。
作为优选地,配气罐1还设有加热装置13,热装置13可以设置于配气罐1的内部或外壁。当热装置13设置于配气罐1的内部时,加热装置13包括水浴加热设备、蒸汽加热设备、油浴加热设备、电加热设备和光波加热设备中的至少一种。当加热装置13设于配气罐1的外壁时;加热装置13包括电加热带和电加热套中的至少一种。Preferably, the gas distribution tank 1 is also provided with a
烯烃进料口15设于静态混合器14与循环出口8之间,烯烃进料口15为第二原料入口,其用于加入需要混合的第二原料,第二原料优选为烯烃,包括乙烯、丙烯、1-丁烯、4-甲基-1-戊烯、1-己烯和1-辛烯中的至少一种,最优选为液态烯烃。The
静态混合器14设于烯烃进料口15和循环动力单元2之间,用于将来自配气罐1的第一原料和由烯烃进料口15加入的第二原料进行第一次混合,得到第一混合料。The
循环动力单元2设于静态混合器14与循环入口11之间,用于为循环混合烯烃提供循环动力,循环动力单元2例如但不限于为泵或压缩机。The
循环入口11用于输入第一混合料至配气罐1。The
放料口12用于清除剩余物料或吹扫配气罐1。The
导流环5设于配气罐1内部,并与配气罐1底部的循环入口11连接;导流环5用于分散循环动力单元2输送来的第一混合料,能够提高混合效果。The guide ring 5 is arranged inside the gas distribution tank 1 and is connected to the
分布板4设于配气罐1内部,并位于导流环5的上方;分布板4用于混合流环5分散的第一混合料,分布板4的结构优选使低于混合料更加无序的分布形式,以此提高混合效果。第一混合料经导流环5分散并经分布板4进行第二次混合,得到第二混合料。The
本发明的烯烃混合配气装置在使用时,首先根据原料的物理性质,设定温度和压力,将第一原料通过配气罐1顶部的原料入口6输入烯烃混合配气装置,加热装置13加热至设定的温度,将第二原料通过烯烃进料口15输入静态混合器14,烯烃混合配气装置内的第一原料从循环出口8输出并进入静态混合器14,第一原料与第二原料在静态混合器14中进行第一次混合,得到第一混合料;第一混合料通过循环动力单元2经循环入口11输入烯烃混合配气装置,第一混合料经导流环5分散并经分布板4进行第二次混合,得到第二混合料;第二混合料经色谱3分析测试混合结果。若混合结果合格,则第二混合料从混合气体出口7输出,进入下游烯烃聚合装置进行共聚合反应;若混合结果不合格,则第二混合料从循环出口8输出并输入静态混合器14重新进行混合,循环动力单元2为物料的循环提供动力。When the olefin mixing gas distribution device of the present invention is in use, firstly, according to the physical properties of the raw material, the temperature and pressure are set, and the first raw material is input into the olefin mixing gas distribution device through the raw material inlet 6 at the top of the gas distribution tank 1, and the
本发明提供的烯烃混合配气方法采用上述烯烃混合配气装置,该方法包括以下步骤:The olefin mixed gas distribution method provided by the present invention adopts the above-mentioned olefin mixed gas distribution device, and the method includes the following steps:
步骤S1:将第一原料通过配气罐顶部的原料入口输入烯烃混合配气装置;Step S1: Input the first raw material into the olefin mixing gas distribution device through the raw material inlet on the top of the gas distribution tank;
步骤S2:将第二原料通过烯烃进料口输入静态混合器;烯烃混合配气装置内的第一原料从循环出口输出并进入静态混合器,第一原料与第二原料在静态混合器中进行第一次混合,得到第一混合料;Step S2: Input the second raw material into the static mixer through the olefin feed port; the first raw material in the olefin mixing and gas distribution device is output from the circulation outlet and enters the static mixer, and the first raw material and the second raw material are mixed in the static mixer. Mix for the first time to obtain the first mixture;
步骤S3:第一混合料通过循环动力单元经循环入口输入烯烃混合配气装置,第一混合料经导流环分散并经分布板进行第二次混合,得到第二混合料;Step S3: the first mixed material is input into the olefin mixing and gas distribution device through the circulation power unit through the circulation inlet, the first mixed material is dispersed through the guide ring and mixed for the second time through the distribution plate to obtain the second mixed material;
步骤S4:第二混合料经色谱分析测试混合结果;若混合结果合格,则第二混合料从混合气体出口输出,进入下游工艺;若混合结果不合格,则返回步骤S2,第二混合料从循环出口输出并输入静态混合器重新进行混合。Step S4: The mixing result of the second mixture is tested by chromatographic analysis; if the mixing result is qualified, the second mixture is output from the mixed gas outlet and enters the downstream process; if the mixing result is unqualified, return to step S2, and the second mixture is from The loop exits and enters the static mixer for remixing.
以下对本发明的实施例作详细说明:本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和过程,但本发明的保护范围不限于下述的实施例,下列实施例中未注明具体条件的实验方法,通常按照常规条件。The embodiments of the present invention are described in detail below: the present embodiment is implemented under the premise of the technical solution of the present invention, and detailed implementation methods and processes are provided, but the protection scope of the present invention is not limited to the following embodiments, the following The experimental method that does not indicate specific condition in the embodiment, generally according to routine condition.
原料或设备来源:Source of raw material or equipment:
评价分析方法:Evaluation analysis method:
聚合活性通过如下方法进行计算:Polymerization activity was calculated by the following method:
聚合活性的单位为g PE/(g Cat·h)。The unit of polymerization activity is g PE/(g Cat·h).
实施例1:Example 1:
将乙烯和丙烯通过原料入口加入到配气罐中,按照乙烯与丙烯摩尔比为49/1的比例在30℃条件下配制混合气,配好混合气待用。Add ethylene and propylene into the gas distribution tank through the raw material inlet, prepare a mixed gas at 30°C according to the ratio of ethylene to propylene molar ratio of 49/1, and prepare the mixed gas for use.
使用配好的混合气评价Z-N催化剂,其具体步骤如下:Use the prepared mixed gas to evaluate the Z-N catalyst, and the specific steps are as follows:
将氮气从气体进料口加入2L聚合反应釜至表压为0.3MPa,通过放空及抽真空口将聚合反应釜抽真空,反复置换8次,然后通入氮气至表压为0MPa;打开放空口,将0.8L分散剂正己烷从催化剂进料口加入聚合反应釜;关闭放空口,将搅拌转速调至200r/min,利用温度控制系统将聚合反应釜温度升至85℃;降低搅拌转速调至50r/min,通过催化剂加料口用0.2L分散剂正己烷将助催化剂三乙基铝和10mg Z-N催化剂冲入聚合反应釜,三乙基铝加入量为Al/Ti(摩尔)=100;将搅拌装置的转速调至200r/min;在聚合反应釜内压力的基础上通过气体入口加入0.2MPa的氢气,再加入1.0MPa乙烯和丙烯组成的混合气至反应压力,开始聚合反应;在反应压力条件下反应3h后,停止加入乙烯;利用温度控制系统将聚合反应釜降温至20℃,打开放空口将反应釜内气体放空,加入氮气置换5次,打开出料口放出反应产物,分离分散剂正己烷后得到聚合物产品。试验结果见表1。Add nitrogen into the 2L polymerization reactor from the gas feed port until the gauge pressure is 0.3MPa, evacuate the polymerization reactor through the vent and vacuum port, and replace it repeatedly 8 times, then feed nitrogen gas until the gauge pressure is 0MPa; open the vent , put 0.8L dispersant n-hexane into the polymerization reactor from the catalyst feed port; close the vent, adjust the stirring speed to 200r/min, use the temperature control system to raise the temperature of the polymerization reactor to 85°C; reduce the stirring speed to 50r/min, with 0.2L dispersant n-hexane, co-catalyst triethylaluminum and 10mg Z-N catalyst are rushed into the polymerization reactor through the catalyst feeding port, and the addition of triethylaluminum is Al/Ti (mol)=100; Adjust the rotation speed of the device to 200r/min; add 0.2MPa of hydrogen through the gas inlet on the basis of the internal pressure of the polymerization reactor, and then add a mixture of 1.0MPa ethylene and propylene to the reaction pressure to start the polymerization reaction; After lowering the reaction for 3 hours, stop adding ethylene; use the temperature control system to lower the temperature of the polymerization reactor to 20°C, open the vent to vent the gas in the reactor, add nitrogen to replace it for 5 times, open the outlet to release the reaction product, and separate the dispersant. The polymer product is obtained after alkane. The test results are shown in Table 1.
实施例2:Example 2:
采用与实施例1相同的方法评价Z-N催化剂,区别在于按照乙烯与丙烯摩尔比为48/2的比例在30℃条件下配制混合气,具体实验条件及实验结果示于表1中。The same method as in Example 1 was used to evaluate the Z-N catalyst, except that the mixed gas was prepared at 30° C. according to the molar ratio of ethylene and propylene of 48/2. The specific experimental conditions and experimental results are shown in Table 1.
实施例3:Example 3:
采用与实施例1相同的方法评价Z-N催化剂,区别在于按照乙烯与1-丁烯摩尔比为49/1的比例在60℃条件下配制混合气,具体实验条件及实验结果示于表1中。The same method as in Example 1 was used to evaluate the Z-N catalyst, except that the mixed gas was prepared at 60°C according to the molar ratio of ethylene to 1-butene of 49/1. The specific experimental conditions and experimental results are shown in Table 1.
实施例4:Example 4:
采用与实施例1相同的方法评价Z-N催化剂,区别在于按照乙烯与1-丁烯摩尔比为48/2的比例在60℃条件下配制混合气,具体实验条件及实验结果示于表1中。The same method as in Example 1 was used to evaluate the Z-N catalyst, except that the mixed gas was prepared at 60°C according to the molar ratio of ethylene to 1-butene of 48/2. The specific experimental conditions and experimental results are shown in Table 1.
实施例5:Example 5:
采用与实施例1相同的方法评价Z-N催化剂,区别在于按照乙烯与1-己烯摩尔比为49/1的比例在85℃条件下配制混合气,具体实验条件及实验结果示于表1中。The same method as in Example 1 was used to evaluate the Z-N catalyst, except that the mixed gas was prepared at 85°C according to the ratio of ethylene to 1-hexene molar ratio of 49/1. The specific experimental conditions and experimental results are shown in Table 1.
实施例6:Embodiment 6:
采用与实施例1相同的方法评价Z-N催化剂,区别在于按照乙烯与1-己烯摩尔比为48/2的比例在85℃条件下配制混合气,具体实验条件及实验结果示于表1中。The same method as in Example 1 was used to evaluate the Z-N catalyst, except that the mixed gas was prepared at 85°C according to the ratio of ethylene to 1-hexene molar ratio of 48/2. The specific experimental conditions and experimental results are shown in Table 1.
对比例1:Comparative example 1:
采用与实施例1相同的方法评价Z-N催化剂,区别在于采用现有混合配气装置结构不同,本对比例的混合配气装置为设有加热单元的配气罐,其内部不存在导流环、分布板,也没有静态混合器和循环动力单元,具体实验条件及实验结果示于表1中。The same method as in Example 1 is used to evaluate the Z-N catalyst, the difference is that the structure of the existing hybrid gas distribution device is different, and the hybrid gas distribution device of this comparative example is a gas distribution tank provided with a heating unit, and there is no guide ring, Distributor plate, no static mixer and circulation power unit, the specific experimental conditions and experimental results are shown in Table 1.
对比例2:Comparative example 2:
采用与对比例1相同的方法评价Z-N催化剂,区别在于按照乙烯与丙烯摩尔比为48/2的比例在30℃条件下配制混合气,具体实验条件及实验结果示于表1中。The same method as Comparative Example 1 was used to evaluate the Z-N catalyst, except that the mixed gas was prepared at 30°C according to the ratio of ethylene to propylene molar ratio of 48/2. The specific experimental conditions and experimental results are shown in Table 1.
对比例3:Comparative example 3:
采用与对比例1相同的方法评价Z-N催化剂,区别在于按照乙烯与1-丁烯摩尔比为49/1的比例在60℃条件下配制混合气,具体实验条件及实验结果示于表1中。The same method as Comparative Example 1 was used to evaluate the Z-N catalyst, except that the mixed gas was prepared at 60°C according to the molar ratio of ethylene to 1-butene of 49/1. The specific experimental conditions and experimental results are shown in Table 1.
对比例3:Comparative example 3:
采用与对比例1相同的方法评价Z-N催化剂,区别在于按照乙烯与1-丁烯摩尔比为48/2的比例在60℃条件下配制混合气,具体实验条件及实验结果示于表1中。The same method as Comparative Example 1 was used to evaluate the Z-N catalyst, except that the mixed gas was prepared at 60°C according to the molar ratio of ethylene to 1-butene of 48/2. The specific experimental conditions and experimental results are shown in Table 1.
对比例5:Comparative example 5:
采用与对比例1相同的方法评价Z-N催化剂,区别在于按照乙烯与1-己烯摩尔比为49/1的比例在85℃条件下配制混合气,具体实验条件及实验结果示于表1中。The same method as Comparative Example 1 was used to evaluate the Z-N catalyst, except that the mixed gas was prepared at 85°C according to the ratio of ethylene to 1-hexene molar ratio of 49/1. The specific experimental conditions and experimental results are shown in Table 1.
对比例6:Comparative example 6:
采用与对比例1相同的方法评价Z-N催化剂,区区别在于按照乙烯与1-己烯摩尔比为48/2的比例在85℃条件下配制混合气,具体实验条件及实验结果示于表1中。The same method as Comparative Example 1 was used to evaluate the Z-N catalyst. The difference is that the mixed gas was prepared at 85°C according to the molar ratio of ethylene and 1-hexene of 48/2. The specific experimental conditions and experimental results are shown in Table 1. .
表1实施例和对比例的实验条件及实验结果The experimental condition and experimental result of table 1 embodiment and comparative example
由表1中数据可知,与现有混合配气装置相比,在相同的配气温度和配气比例条件下,本发明的烯烃混合配气装置得到的混合气的组成更加均匀,本发明的烯烃混合配气装置实现了烯烃共聚单体的预混合,其用于后续的聚烯烃催化剂评价时,能够更准确地评价聚烯烃催化剂的活性,大幅提高中试聚合装置的使用效率和装置运行安全性。As can be seen from the data in Table 1, compared with the existing mixed gas distribution device, under the same gas distribution temperature and gas distribution ratio conditions, the composition of the mixed gas obtained by the olefin mixed gas distribution device of the present invention is more uniform, and the present invention The olefin mixing and gas distribution device realizes the premixing of olefin comonomers, which can more accurately evaluate the activity of polyolefin catalysts when it is used in the subsequent evaluation of polyolefin catalysts, and greatly improve the use efficiency and operation safety of the pilot polymerization device sex.
以上所述仅是本发明的优选实施方式,应当说明:对本技术领域的普通技术人员而言,在不脱离本发明的前提下,还可以做出若干改进,这些改进也应视为本发明的保护范围。The above description is only a preferred embodiment of the present invention, it should be noted that for those of ordinary skill in the art, without departing from the premise of the present invention, some improvements can also be made, and these improvements should also be regarded as the invention. protected range.
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