技术领域technical field
本发明涉及催化剂，具体涉及一种烯烃聚合催化剂及其制备方法和应用，该催化剂可用于石油化工、煤化工、天然气化工等石化企业中聚烯烃的工业化生产，可以但不局限适用于烯烃的气-液、气-固、气-液-固状态下的乙烯均聚或乙烯与α-烯烃共聚。The present invention relates to a catalyst, in particular to an olefin polymerization catalyst and its preparation method and application. The catalyst can be used for the industrial production of polyolefins in petrochemical enterprises such as petrochemical, coal chemical, and natural gas chemical industries. - Homopolymerization of ethylene or copolymerization of ethylene and α-olefin in liquid, gas-solid, gas-liquid-solid state.
背景技术Background technique
中国专利CN201210038761.7公开了一种烯烃聚合催化剂、制备方法和应用，该催化剂可适用于乙烯均聚或共聚，催化剂颗粒BET比表面积≥200m2/g，表现为催化剂活性高，聚合物粒度分布集中，细粉少，可适用于乙烯均聚或共聚。Chinese patent CN201210038761.7 discloses an olefin polymerization catalyst, preparation method and application. The catalyst is suitable for ethylene homopolymerization or copolymerization. The BET specific surface area of the catalyst particles is ≥200m2 /g, which is characterized by high catalyst activity and polymer particle size distribution. Concentrated, less fine powder, suitable for ethylene homopolymerization or copolymerization.
中国专利CN106543301A公开了一种高效制备低缠结聚乙烯的Ziegler-Natta催化剂的制备方法及应用，POSS能够在多孔载体孔道中组装成粒径20-100nm的微球，有效地分隔了活性点位，增大了活性中心间距，抑制了聚合过程中链交叠的发生，能够在≥60℃的聚合温度下高效地制备低缠结聚乙烯。Chinese patent CN106543301A discloses a preparation method and application of a Ziegler-Natta catalyst for the efficient preparation of low-entanglement polyethylene. POSS can be assembled into microspheres with a particle size of 20-100nm in the pores of the porous carrier, effectively separating the active sites , increases the distance between active centers, suppresses the occurrence of chain overlap during polymerization, and can efficiently prepare low-entangled polyethylene at a polymerization temperature ≥ 60 °C.
中国专利CN201511006091.0公开了一种负载型双金属聚乙烯催化剂，以及该负载型双金属聚乙烯催化剂在催化乙烯制备线性低密度聚乙烯中的应用。该负载型双金属聚乙烯催化剂可以利用乙烯为单一原料直接得到线性低密度聚乙烯。Chinese patent CN201511006091.0 discloses a supported bimetallic polyethylene catalyst and the application of the supported bimetallic polyethylene catalyst in catalyzing ethylene to prepare linear low density polyethylene. The supported bimetallic polyethylene catalyst can directly obtain linear low-density polyethylene by using ethylene as a single raw material.
中国专利CN201510623065.6公开了一种双孔硅胶载体和负载型聚乙烯催化剂及其制备方法和应用，以及一种乙烯聚合的方法。双孔硅胶载体的平均粒子直径为20-50μm，比表面积为150-600m2/g，孔体积为0.5-1.6mL/g，孔径呈双峰分布，且双峰分别对应的最可几孔径为2-4nm和10-40nm，双孔硅胶载体能够具有较高的催化剂活性组分的负载率，制备得到的负载型聚乙烯催化剂能够具有较高的催化活性。Chinese patent CN201510623065.6 discloses a dual-porous silica gel carrier and a supported polyethylene catalyst, its preparation method and application, and a method of ethylene polymerization. The average particle diameter of the dual-porous silica gel carrier is 20-50μm, the specific surface area is 150-600m2 /g, the pore volume is 0.5-1.6mL/g, and the pore diameter is bimodal, and the most probable pore diameter corresponding to the bimodal is 2-4nm and 10-40nm, the dual-hole silica gel carrier can have a higher loading rate of the catalyst active component, and the prepared supported polyethylene catalyst can have a higher catalytic activity.
中国专利CN1624011A公开了一种聚乙烯催化剂及其制备方法，该催化剂具有聚合效率高、在低氢含量和高氢含量时活性相差不大、聚合反应平稳、催化剂颗粒形态好、聚合产品细粉含量少的特点。Chinese patent CN1624011A discloses a polyethylene catalyst and its preparation method. The catalyst has the advantages of high polymerization efficiency, little difference in activity between low hydrogen content and high hydrogen content, stable polymerization reaction, good catalyst particle shape, and fine powder content of polymerization products. few features.
纵观聚烯烃催化剂相关的专利可以看出，聚烯烃催化剂的制备过程繁琐，在涉及到载体的方面，一些特种载体需要特别制备，在催化剂工业化生产过程中，会造成不小的困难；在催化剂应用方面，相关专利涉及的催化剂，对于石化企业不同的聚乙烯工艺，适应性均存在较大的局限，有些催化剂无法成功实现工业化应用。Looking at the patents related to polyolefin catalysts, it can be seen that the preparation process of polyolefin catalysts is cumbersome. In terms of carriers, some special carriers need to be specially prepared, which will cause considerable difficulties in the industrial production of catalysts; In terms of application, the catalysts involved in the relevant patents have relatively limited adaptability to the different polyethylene processes of petrochemical enterprises, and some catalysts cannot be successfully applied industrially.
发明内容Contents of the invention
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种可以适应不同类型的聚乙烯生产工艺、生产流程简单的烯烃聚合催化剂及其制备方法和应用。The object of the present invention is to provide an olefin polymerization catalyst capable of adapting to different types of polyethylene production processes with simple production process and its preparation method and application in order to overcome the above-mentioned defects in the prior art.
本发明的目的可以通过以下技术方案来实现：一种烯烃聚合催化剂，其特征在于，该催化剂是由催化剂主体组份和助催化剂组成，其中催化剂的主体组分为金属元素或/和含有金属元素的化合物、含有孤对电子的有机化合物、分散剂通过特定的化学方式反应制得，助催化剂为有机铝化合物。The object of the present invention can be achieved through the following technical scheme: a kind of olefin polymerization catalyst, it is characterized in that, this catalyst is made up of catalyst body component and cocatalyst, wherein the body component of catalyst is metal element or/and contains metal element Compounds, organic compounds containing lone pairs of electrons, and dispersants are prepared through specific chemical reactions, and the co-catalyst is an organoaluminum compound.
所述的金属元素为镁金属和铝金属，所述的含有金属元素的化合物为钛化合物和/或卤化镁化合物。The metal element is magnesium metal and aluminum metal, and the compound containing metal element is titanium compound and/or magnesium halide compound.
催化剂主体组份由以下方法制得：Catalyst main component is made by following method:
(1)将镁、铝金属按照摩尔比为1：0-2，且不为0，配置成合金；(1) The magnesium and aluminum metals are configured into an alloy according to the molar ratio of 1:0-2, and not 0;
(2)将合金粉碎成粉状，颗粒尺寸<40目；(2) Pulverize the alloy into powder, particle size <40 mesh;
(3)将合金粉分散在含有孤对电子的有机溶剂中，在10-100℃搅拌加热的条件下缓慢加入钛化合物，加入完毕后，在保持反应温度为10-100℃的情况下，继续搅拌30分钟-40小时使反应完全；(3) Disperse the alloy powder in an organic solvent containing a lone pair of electrons, slowly add the titanium compound under the condition of stirring and heating at 10-100°C, after the addition is completed, keep the reaction temperature at 10-100°C, continue Stir for 30 minutes to 40 hours to complete the reaction;
(4)向反应完全的体系中加入和/或在反应完全的体系中原位产生卤化镁化合物，搅拌使卤化镁化合物充分分散；然后向反应体系中加入分散剂，搅拌使分散剂充分分散；(4) adding and/or generating magnesium halide compounds in situ in the fully reacted system, stirring to fully disperse the magnesium halide compounds; then adding a dispersant to the reaction system, stirring to fully disperse the dispersant;
(5)干燥，部分除去溶剂，然后用矿物油将得到的固体粉末分散，得到催化剂主体组分。(5) drying to partially remove the solvent, and then dispersing the obtained solid powder with mineral oil to obtain a catalyst main body component.
加入原料的量以1摩尔镁粉计，含钛化合物为2-8摩尔，优选2-4摩尔，卤化镁化合物为5-80摩尔，优选6-40摩尔，分散剂为6-250摩尔，优选15-50摩尔。The amount of raw materials added is based on 1 mole of magnesium powder, the titanium-containing compound is 2-8 moles, preferably 2-4 moles, the magnesium halide compound is 5-80 moles, preferably 6-40 moles, and the dispersant is 6-250 moles, preferably 15-50 moles.
步骤(3)所述的含有孤对电子的有机溶剂为含有氧、硫、氮、硅、磷的液态溶剂。包括二乙醚、四氢呋喃、乙酸乙酯、苯甲酸乙酯、磷酸三丁酯、异丁醇、异辛醇、正硅酸乙酯、钛酸丁酯等中的一种或几种混合。The organic solvent containing a lone pair of electrons described in step (3) is a liquid solvent containing oxygen, sulfur, nitrogen, silicon, and phosphorus. Including diethyl ether, tetrahydrofuran, ethyl acetate, ethyl benzoate, tributyl phosphate, isobutanol, isooctyl alcohol, ethyl orthosilicate, butyl titanate, etc. or a combination of several.
步骤(3)所述的钛化合物的结构通式为Ti(OR1)mX4-m，式中R1是具有2-20个碳原子的烷基中的一种或多种组合，其中m＝0-3，包括市售的和/或原位生成的四氯化钛、三氯钛酸乙酯、二氯钛酸乙酯、一氯钛酸乙酯、三氯钛酸丙酯、二氯钛酸丙酯、一氯钛酸丙酯、三氯钛酸丁酯、二氯钛酸丁酯、一氯钛酸丁酯及其同分异构体，优选四氯化钛。The general structural formula of the titanium compound described in step (3) is Ti(OR1 )m X4-m , wherein R1 is one or more combinations of alkyl groups with 2-20 carbon atoms, wherein m=0-3, including commercially available and/or in situ generated titanium tetrachloride, ethyl trichlorotitanate, ethyl dichlorotitanate, ethyl monochlorotitanate, propyl trichlorotitanate, Propyl dichlorotitanate, propyl monochlorotitanate, butyl trichlorotitanate, butyl dichlorotitanate, butyl monochlorotitanate and their isomers, preferably titanium tetrachloride.
所述的卤化镁化合物的结构式为MgR2nCl2-n，式中R2是具有2-20个碳原子的烷基中的一种或多种组合，其中n＝0-2，包括市售的和/或原位生成的氯化镁、乙基氯化镁、二乙基镁、丙基氯化镁、二丙基氯镁、氯丁基镁、二丁基镁、丁基辛基镁、戊基氯化镁、二戊基镁及其同分异构体，优选二氯化镁。The structural formula of the magnesium halide compound is MgR2n Cl2-n , where R2 is one or more combinations of alkyl groups with 2-20 carbon atoms, where n=0-2, including Magnesium Chloride, Ethyl Magnesium Chloride, Diethyl Magnesium Chloride, Propyl Magnesium Chloride, Dipropyl Magnesium Chloride, Butyl Magnesium Chloride, Dibutyl Magnesium, Butyl Octyl Magnesium, Amyl Magnesium Chloride, Dipentylmagnesium and its isomers, preferably magnesium dichloride.
所述的分散剂为平均粒径范围是5-40um的无机载体，包括二氧化硅、氧化铝、二氧化钛、二氧化硅-氧化铝、硅藻土、蒙脱土、高岭土中的一种或多种组合，优选二氧化硅；The dispersant is an inorganic carrier with an average particle size range of 5-40um, including one or more of silica, alumina, titania, silica-alumina, diatomite, montmorillonite, and kaolin A combination, preferably silicon dioxide;
所述的矿物油为具有长碳链结构的高沸点液态石油烃；Described mineral oil is the high boiling point liquid petroleum hydrocarbon with long carbon chain structure;
所述的干燥，部分除去溶剂是指干燥去除含有孤对电子的有机溶剂，使具有孤对电子的有机溶剂残留量为10-40wt％，优选18-30wt％，得到流动性好的固体，干燥方法包括常压干燥、减压干燥、喷雾干燥或旋转干燥。The described drying and partial removal of the solvent refer to drying and removal of the organic solvent containing the lone pair of electrons, so that the residual amount of the organic solvent with the lone pair of electrons is 10-40wt%, preferably 18-30wt%, to obtain a solid with good fluidity, dry Methods include atmospheric drying, reduced pressure drying, spray drying or spin drying.
所述的助催化剂为至少一种通式为AlR3xCl3-x的有机铝化合物，其中R3为含有1-18个碳原子的烷基的一种或多种组合，x＝0-3，包括但不局限于三甲基铝、一氯二甲基铝、二氯甲基铝、三乙基铝、一氯二乙基铝、二氯乙基铝、三丙基铝及其氯代衍生物、三丁基铝及其氯代衍生物，优选三乙基铝、一氯二乙基铝。The cocatalyst is at least one organoaluminum compound with the general formula AlR3x Cl3-x , wherein R3 is one or more combinations of alkyl groups containing 1-18 carbon atoms, x=0- 3. Including but not limited to trimethylaluminum, dimethylaluminum monochloride, methylaluminum dichloride, triethylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, tripropylaluminum and its chlorine Derivatives, tributylaluminum and its chlorinated derivatives, preferably triethylaluminum, diethylaluminum monochloride.
助催化剂的使用量为铝含量与催化剂主体组份的摩尔比为(50-300)：1。The usage amount of the co-catalyst is (50-300):1 molar ratio of the aluminum content to the main component of the catalyst.
所述的催化剂在应用之前，采用烷基铝进行还原，或者在催化剂进入反应器过程中进行在线还原。Before the catalyst is used, it is reduced by alkylaluminum, or it is reduced on-line when the catalyst enters the reactor.
上述烯烃聚合催化剂的应用，其特征在于，所述的催化剂可以用于石油化工、煤化工、天然气化工中聚烯烃的工业化生产。The application of the above-mentioned olefin polymerization catalyst is characterized in that the catalyst can be used for the industrialized production of polyolefins in petrochemical, coal chemical and natural gas chemical industries.
上述烯烃聚合催化剂的应用，其特征在于，所述的催化剂可以用于烯烃的气-液、气-固、气-液-固态聚合。The application of the above olefin polymerization catalyst is characterized in that the catalyst can be used for gas-liquid, gas-solid, gas-liquid-solid polymerization of olefins.
上述烯烃聚合催化剂的应用，其特征在于，所述的催化剂可以用于乙烯均聚和/或乙烯与α-烯烃共聚聚合。The application of the above olefin polymerization catalyst is characterized in that the catalyst can be used for the homopolymerization of ethylene and/or the copolymerization of ethylene and α-olefin.
催化剂在应用之前，可以包括还原过程，还原根据生产装置的实际情况及生产产品的具体要求，用一种或多种烷基铝化合物进行。Before the catalyst is applied, it may include a reduction process, and the reduction is carried out with one or more alkylaluminum compounds according to the actual situation of the production device and the specific requirements of the produced product.
与现有技术相比，本发明具有以下有益效果：本发明所述的催化剂生产流程简单、应用范围广泛。该催化剂可以但不局限于用于石油化工、煤化工、天然气化工等石化企业中聚烯烃的工业化生产；该催化剂可以但不局限适用于烯烃的气-液、气-固、气-液-固态聚合；该催化剂可以但不局限用于乙烯均聚和/或乙烯与α-烯烃共聚。该催化剂较易在上述场景实现工业化应用，且催化效率高。Compared with the prior art, the invention has the following beneficial effects: the catalyst production process of the invention is simple and has a wide range of applications. The catalyst can be used but not limited to the industrial production of polyolefins in petrochemical enterprises such as petrochemical, coal chemical and natural gas chemical industries; the catalyst can be used but not limited to gas-liquid, gas-solid, gas-liquid-solid Polymerization; the catalyst can be used for, but not limited to, homopolymerization of ethylene and/or copolymerization of ethylene and α-olefin. The catalyst is easier to realize industrial application in the above scenarios, and has high catalytic efficiency.
具体实施方式Detailed ways
下面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具体的操作过程，但本发明的保护范围不限于下述的实施例。The embodiments of the present invention are described in detail below. This embodiment is implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operating procedures are provided, but the protection scope of the present invention is not limited to the following implementation example.
实施例1Example 1
在无水无氧氮气保护下，向250ml的四口烧瓶中加入100ml四氢呋喃，在保持搅拌状态下，加入0.15克镁铝合金粉，(其中铝与镁的摩尔比为0.2)，加热到30℃，在搅拌状态下，加入1.24g四氯化钛和1.85g Tipt，反应4小时，然后加入7克无水氯化镁，维持温度继续搅拌4小时，再加入10克D(50)为40um的二氧化硅，搅拌2小时，然后升温蒸馏，蒸去部分四氢呋喃。Under the protection of anhydrous and oxygen-free nitrogen, add 100ml of tetrahydrofuran to a 250ml four-necked flask, and keep stirring, add 0.15g of magnesium-aluminum alloy powder (the molar ratio of aluminum to magnesium is 0.2), and heat to 30°C , under stirring, add 1.24g titanium tetrachloride and 1.85g Tipt, react for 4 hours, then add 7 grams of anhydrous magnesium chloride, keep the temperature and continue stirring for 4 hours, then add 10 grams of D (50) is 40um of carbon dioxide Silicon, stirred for 2 hours, then heated up and distilled to evaporate part of tetrahydrofuran.
得到的固体粉末中，含有四氢呋喃的质量百分数为25％，按照固含量为20％的比例将粉末分散至矿物油中，加入三正己基铝和一氯二乙基铝，得到催化剂，将催化剂主体组分还原。In the obtained solid powder, the mass percentage containing tetrahydrofuran is 25%, and the powder is dispersed in mineral oil according to the ratio of solid content of 20%, and tri-n-hexylaluminum and diethylaluminum chloride are added to obtain the catalyst, and the catalyst body is Component reduction.
聚合评价Aggregate evaluation
在2升的反应釜中加入己烷1200ml，三乙基铝1.5ml，然后加入一定量的催化剂，聚合条件为乙烯总压1.0MPa，80℃下聚合2小时。Add 1200ml of hexane and 1.5ml of triethylaluminum into a 2-liter reactor, and then add a certain amount of catalyst. The polymerization conditions are ethylene total pressure 1.0MPa, polymerization at 80°C for 2 hours.
实际加入催化剂0.0148g，得到聚乙烯319g，催化效率为14554g PE/g Cat，聚合物的堆积密度为0.341g/cm3。0.0148g of catalyst was actually added to obtain 319g of polyethylene, the catalytic efficiency was 14554g PE/g Cat, and the bulk density of the polymer was 0.341g/cm3 .
实施例2Example 2
将实施例1中的“1.24g四氯化钛和1.85g TiPT”换成“2.47g四氯化钛”，“7克无水氯化镁”换成“3.5g无水氯化镁和含5g二丁基镁的已烷溶液”，其它同实施例1。Replace "1.24g titanium tetrachloride and 1.85g TiPT" in Example 1 with "2.47g titanium tetrachloride", "7 grams of anhydrous magnesium chloride" with "3.5g anhydrous magnesium chloride and 5g dibutyl The hexane solution of magnesium ", other are with embodiment 1.
聚合评价条件同实施例1。Polymerization evaluation conditions are the same as in Example 1.
实际加入催化剂0.0208g，得到聚乙烯269g，催化效率为12933g PE/g Cat，聚合物的堆积密度为0.336g/cm3。0.0208g of catalyst was actually added to obtain 269g of polyethylene, the catalytic efficiency was 12933g PE/g Cat, and the bulk density of the polymer was 0.336g/cm3 .
实施例3Example 3
催化剂的制备Catalyst preparation
在无水无氧氮气保护下，向250ml的四口烧瓶中加入100ml四氢呋喃，在保持搅拌状态下，加入0.1克铝镁合金粉(其中铝与镁的摩尔比为1)，加热到50℃，在搅拌状态下，加入1.6克四氯化钛，反应8小时，然后加入含有5.8g 1-戊基氯化镁的四氢呋喃溶液，维持温度继续搅拌4小时，再加入6.1克D(50)为15um的二氧化硅，搅拌2小时，然后升温蒸馏，蒸去部分四氢呋喃。Under the protection of anhydrous and oxygen-free nitrogen, add 100ml tetrahydrofuran to a 250ml four-necked flask, and keep stirring, add 0.1 gram of aluminum-magnesium alloy powder (wherein the molar ratio of aluminum to magnesium is 1), and heat to 50°C. Under stirring state, add 1.6 gram of titanium tetrachlorides, react 8 hours, then add the tetrahydrofuran solution that contains 5.8g 1-pentylmagnesium chlorides, maintain temperature and continue to stir for 4 hours, then add 6.1 grams of D (50) is 15um di Silicon oxide, stirred for 2 hours, then heated up and distilled to remove part of tetrahydrofuran.
得到的固体粉末中，含有四氢呋喃的质量百分数为28％，按照固含量为20％的比例将粉末分散至矿物油中，加入三正己基铝和一氯二乙基铝，将催化剂主体组分还原。In the obtained solid powder, the mass percentage containing tetrahydrofuran is 28%, and the powder is dispersed in mineral oil according to the ratio of solid content of 20%, and tri-n-hexyl aluminum and diethyl aluminum chloride are added to reduce the catalyst main component .
聚合评价条件同实施例1。Polymerization evaluation conditions are the same as in Example 1.
实际加入催化剂0.0197g，得到聚乙烯371g，催化效率为18832g PE/g Cat，聚合产物的堆积密度为0.354g/cm3。0.0197g of catalyst was actually added to obtain 371g of polyethylene, the catalytic efficiency was 18832g PE/g Cat, and the bulk density of the polymerization product was 0.354g/cm3 .
实施例4Example 4
将实施例3中的“1.6克四氯化钛”换成“1g四氯化钛和1g钛酸丁酯”，其它同实施例1。Replace "1.6 grams of titanium tetrachloride" in Example 3 with "1 g of titanium tetrachloride and 1 g of butyl titanate", and the others are the same as in Example 1.
聚合评价条件同实施例1。Polymerization evaluation conditions are the same as in Example 1.
实际加入催化剂0.0137g，得到聚乙烯198g，催化效率为14452g PE/g Cat，聚合物的堆积密度为0.345g/cm3。0.0137g of catalyst was actually added to obtain 198g of polyethylene, the catalytic efficiency was 14452g PE/g Cat, and the bulk density of the polymer was 0.345g/cm3 .
实施例5Example 5
在无水无氧氮气保护下，向250ml的四口烧瓶中加入100ml四氢呋喃，在保持搅拌状态下，加入0.1克镁铝合金粉，(其中铝与镁的摩尔比为2)，加热到60℃，在搅拌状态下，加入1.824克四氯化钛，反应4小时，然后加入5.36克无水氯化镁，维持温度继续搅拌8小时，再加入7克D(15)为20um的高岭土，搅拌半小时，然后升温蒸馏，蒸去部分四氢呋喃。Under the protection of anhydrous and oxygen-free nitrogen, add 100ml of tetrahydrofuran into a 250ml four-necked flask, and keep stirring, add 0.1g of magnesium-aluminum alloy powder (where the molar ratio of aluminum to magnesium is 2), and heat to 60°C , under stirring, add 1.824 grams of titanium tetrachloride, react for 4 hours, then add 5.36 grams of anhydrous magnesium chloride, keep the temperature and continue stirring for 8 hours, then add 7 grams of kaolin whose D(15) is 20um, stir for half an hour, Then heat up and distill to evaporate part of tetrahydrofuran.
得到的固体粉末中，含有四氢呋喃的质量百分数为34％，按照固含量为20％的比例将粉末分散至有机硅油中，加入三正己基铝和一氯二乙基铝，将催化剂主体组分还原。In the obtained solid powder, the mass percentage containing tetrahydrofuran is 34%, and the powder is dispersed in the silicone oil according to the ratio of solid content of 20%, and tri-n-hexylaluminum and diethylaluminum chloride are added to reduce the main component of the catalyst .
聚合评价条件同实施例1。Polymerization evaluation conditions are the same as in Example 1.
实际加入催化剂0.0168g，得到聚乙烯289g，催化效率为17202g PE/g Cat，聚合物的堆积密度为0.351g/cm3。0.0168g of catalyst was actually added to obtain 289g of polyethylene, the catalytic efficiency was 17202g PE/g Cat, and the bulk density of the polymer was 0.351g/cm3 .
实施例6Example 6
在无水无氧氮气保护下，向250ml的四口烧瓶中加入100ml四氢呋喃，在保持搅拌状态下，加入0.1克镁铝合金粉，(其中铝与镁的摩尔比为0.5)，加热到50℃，在搅拌状态下，加入1.5克四氯化钛和0.6g Tipt，反应半小时，然后加入5克无水氯化镁，维持温度继续搅拌2小时，再加入10克D(50)为20um的硅藻土，搅拌1小时，然后升温蒸馏，蒸去部分四氢呋喃。Under the protection of anhydrous and oxygen-free nitrogen, add 100ml of tetrahydrofuran into a 250ml four-necked flask, and keep stirring, add 0.1g of magnesium-aluminum alloy powder (the molar ratio of aluminum to magnesium is 0.5), and heat to 50°C , under stirring, add 1.5 grams of titanium tetrachloride and 0.6 g Tipt, react for half an hour, then add 5 grams of anhydrous magnesium chloride, maintain the temperature and continue stirring for 2 hours, then add 10 grams of diatoms with a D(50) of 20um Soil, stirred for 1 hour, then heated up and distilled to remove part of THF.
得到的固体粉末中，含有四氢呋喃的质量百分数为18％，按照固含量为20％的比例将粉末分散至矿物油中，加入三正己基铝，和一氯二乙基铝，将催化剂主体组分还原。In the obtained solid powder, the mass percentage containing tetrahydrofuran is 18%, and the powder is dispersed in mineral oil according to the ratio of solid content of 20%, and tri-n-hexylaluminum and diethylaluminum monochloride are added, and the main catalyst component is reduction.
聚合评价条件为在实施例1的基础上，向体系中加入20mL己烯。Polymerization evaluation conditions were based on Example 1, adding 20 mL of hexene to the system.
实际加入催化剂0.0156g，得到聚乙烯347g，催化效率为16244g PE/g Cat，聚合物的堆密度为0.363g/cm3。0.0156 g of catalyst was actually added to obtain 347 g of polyethylene, the catalytic efficiency was 16244 g PE/g Cat, and the bulk density of the polymer was 0.363 g/cm3 .
实施例7Example 7
一种烯烃聚合催化剂，通过以下方法制得：A kind of olefin polymerization catalyst is made by following method:
(1)将镁、铝金属按照摩尔比为1：0.1，配置成镁铝合金；(1) Magnesium and aluminum are configured into magnesium-aluminum alloy according to the molar ratio of 1:0.1;
(2)将镁铝合金粉碎成粉状，颗粒尺寸<40目；(2) Grinding the magnesium-aluminum alloy into powder, particle size<40 mesh;
(3)将合金粉分散在含有孤对电子的有机溶剂中，在10℃搅拌加热的条件下缓慢加入钛化合物，加入完毕后，在保持反应温度为10℃的情况下，继续搅拌40小时使反应完全；(3) Disperse the alloy powder in an organic solvent containing a lone pair of electrons, slowly add the titanium compound under the condition of stirring and heating at 10°C, and after the addition is completed, keep stirring for 40 hours while keeping the reaction temperature at 10°C Complete response;
(4)在反应完全的体系中原位产生卤化镁化合物，搅拌使卤化镁化合物充分分散；然后向反应体系中加入载体分散剂，搅拌使分散剂充分分散；(4) In-situ generation of magnesium halide compound in the fully reacted system, stirring to fully disperse the magnesium halide compound; then adding carrier dispersant to the reaction system, stirring to fully disperse the dispersant;
加入原料的量以1摩尔镁粉计，含钛化合物为2摩尔，卤化镁化合物为5摩尔，载体分散剂为6摩尔。The amount of raw materials added is based on 1 mole of magnesium powder, 2 moles of the titanium-containing compound, 5 moles of the magnesium halide compound, and 6 moles of the carrier dispersant.
(5)干燥，部分除去含有孤对电子的有机溶剂，使具有孤对电子的有机溶剂残留量为10wt％，得到流动性好的固体，干燥方法包括常压干燥、减压干燥、喷雾干燥或旋转干燥，然后用矿物油将得到的固体粉末分散，得到催化剂主体组分。(5) dry, partially remove the organic solvent containing the lone pair of electrons, make the residual amount of the organic solvent with the lone pair of electrons be 10wt%, obtain a solid with good fluidity, and the drying method includes normal pressure drying, decompression drying, spray drying or Spin dry, and then disperse the obtained solid powder with mineral oil to obtain the main catalyst component.
其中，所述的含有孤对电子的有机溶剂为二乙醚。所述的钛化合物为三氯钛酸乙酯。所述的卤化镁化合物为乙基氯化镁。所述的分散剂为平均粒径范围是5-40um的二氧化硅；所述的矿物油为具有长碳链结构的高沸点液态石油烃。Wherein, the organic solvent containing lone pair electrons is diethyl ether. The titanium compound is ethyl trichlorotitanate. The magnesium halide compound is ethylmagnesium chloride. The dispersant is silicon dioxide with an average particle size range of 5-40um; the mineral oil is a high-boiling liquid petroleum hydrocarbon with a long carbon chain structure.
使用时，采用烷基铝将催化剂进行还原，然后加入助催化剂，其中助催化剂为三甲基铝，使用量为铝含量与催化剂主体组份的摩尔比为50：1。用于石油化工中聚烯烃的工业化生产。When in use, the catalyst is reduced with alkylaluminum, and then a co-catalyst is added, wherein the co-catalyst is trimethylaluminum, and the molar ratio of the aluminum content to the main component of the catalyst is 50:1. It is used in the industrial production of polyolefin in petrochemical industry.
实施例8Example 8
一种烯烃聚合催化剂，通过以下方法制得：A kind of olefin polymerization catalyst is made by following method:
(1)将镁、铝金属按照摩尔比为1：2，配置成镁铝合金；(1) Magnesium and aluminum are configured into magnesium-aluminum alloy according to the molar ratio of 1:2;
(2)将镁铝合金粉碎成粉状，颗粒尺寸<40目；(2) Grinding the magnesium-aluminum alloy into powder, particle size<40 mesh;
(3)将合金粉分散在含有孤对电子的有机溶剂中，在100℃搅拌加热的条件下缓慢加入钛化合物，加入完毕后，在保持反应温度为100℃的情况下，继续搅拌30分钟使反应完全；(3) Disperse the alloy powder in an organic solvent containing a lone pair of electrons, and slowly add the titanium compound under the condition of stirring and heating at 100°C. Complete response;
(4)在反应完全的体系中原位产生卤化镁化合物，搅拌使卤化镁化合物充分分散；然后向反应体系中加入分散剂，搅拌使分散剂充分分散；(4) In-situ generation of magnesium halide compound in the fully reacted system, stirring to fully disperse the magnesium halide compound; then adding a dispersant to the reaction system, stirring to fully disperse the dispersant;
加入原料的量以1摩尔镁粉计，含钛化合物为8摩尔，卤化镁化合物为80摩尔，分散剂为250摩尔。The amount of added raw materials is based on 1 mole of magnesium powder, 8 moles of the titanium-containing compound, 80 moles of the magnesium halide compound, and 250 moles of the dispersant.
(5)干燥，部分除去含有孤对电子的有机溶剂，使具有孤对电子的有机溶剂残留量为40wt％，得到流动性好的固体，干燥方法包括常压干燥、减压干燥、喷雾干燥或旋转干燥，然后用矿物油将得到的固体粉末分散，得到催化剂主体组分。(5) dry, partially remove the organic solvent containing the lone pair of electrons, make the residual amount of the organic solvent with the lone pair of electrons be 40wt%, obtain a solid with good fluidity, and the drying method includes normal pressure drying, decompression drying, spray drying or Spin dry, and then disperse the obtained solid powder with mineral oil to obtain the main catalyst component.
其中，所述的含有孤对电子的有机溶剂为乙酸乙酯。所述的钛化合物为二氯钛酸乙酯。所述的卤化镁化合物的为丙基氯化镁。Wherein, the organic solvent containing a lone pair of electrons is ethyl acetate. The titanium compound is ethyl dichlorotitanate. The magnesium halide compound is propylmagnesium chloride.
所述的分散剂为平均粒径范围是5-40um的无机载体硅藻土；所述的矿物油为具有长碳链结构的高沸点液态石油烃。The dispersant is an inorganic carrier diatomite with an average particle size range of 5-40um; the mineral oil is a high-boiling liquid petroleum hydrocarbon with a long carbon chain structure.
使用时，将催化剂采用烷基铝进行还原，然后加入助催化剂，其中助催化剂为二氯甲基铝，使用量为铝含量与催化剂主体组份的摩尔比为300：1。用于煤化工中烯烃的气-液态下的乙烯均聚聚合反应。When in use, the catalyst is reduced with alkylaluminum, and then a co-catalyst is added, wherein the co-catalyst is dichloromethylaluminum, and the molar ratio of the aluminum content to the main component of the catalyst is 300:1. It is used in the gas-liquid ethylene homopolymerization reaction of olefins in coal chemical industry.
实施例9Example 9
一种烯烃聚合催化剂，通过以下方法制得：A kind of olefin polymerization catalyst is made by following method:
(1)将镁、铝金属按照摩尔比为1：1，配置成镁铝合金；(1) The magnesium and aluminum metals are configured into magnesium and aluminum alloys according to the molar ratio of 1:1;
(2)将镁铝合金粉碎成粉状，颗粒尺寸<40目；(2) Grinding the magnesium-aluminum alloy into powder, particle size<40 mesh;
(3)将合金粉分散在含有孤对电子的有机溶剂中，在30℃搅拌加热的条件下缓慢加入钛化合物，加入完毕后，在保持反应温度为30℃的情况下，继续搅拌2小时使反应完全；(3) Disperse the alloy powder in an organic solvent containing a lone pair of electrons, slowly add the titanium compound under the condition of stirring and heating at 30°C, and after the addition is completed, keep stirring for 2 hours while keeping the reaction temperature at 30°C Complete response;
(4)在反应完全的体系中原位产生卤化镁化合物，搅拌使卤化镁化合物充分分散；然后向反应体系中加入分散剂，搅拌使分散剂充分分散；(4) In-situ generation of magnesium halide compound in the fully reacted system, stirring to fully disperse the magnesium halide compound; then adding a dispersant to the reaction system, stirring to fully disperse the dispersant;
加入原料的量以1摩尔镁粉计，含钛化合物为4摩尔，卤化镁化合物为6摩尔，载体分散剂为15摩尔。The amount of added raw materials is based on 1 mole of magnesium powder, 4 moles of the titanium-containing compound, 6 moles of the magnesium halide compound, and 15 moles of the carrier dispersant.
(5)干燥，部分除去含有孤对电子的有机溶剂，使具有孤对电子的有机溶剂残留量为18wt％，得到流动性好的固体，干燥方法包括常压干燥、减压干燥、喷雾干燥或旋转干燥，然后用矿物油将得到的固体粉末分散，得到催化剂主体组分。(5) dry, partially remove the organic solvent containing the lone pair of electrons, make the residual amount of the organic solvent with the lone pair of electrons be 18wt%, obtain a solid with good fluidity, and the drying method includes normal pressure drying, decompression drying, spray drying or Spin dry, and then disperse the obtained solid powder with mineral oil to obtain the main catalyst component.
其中，所述的含有孤对电子的有机溶剂为磷酸三丁酯。所述的钛化合物为二氯钛酸丙酯。所述的卤化镁化合物为二丙基氯镁。Wherein, the organic solvent containing a lone pair of electrons is tributyl phosphate. The titanium compound is propyl dichlorotitanate. The magnesium halide compound is dipropylmagnesium chloride.
所述的分散剂为平均粒径范围是5-40um的无机载体蒙脱土；所述的矿物油为具有长碳链结构的高沸点液态石油烃。The dispersant is an inorganic carrier montmorillonite with an average particle size range of 5-40um; the mineral oil is a high-boiling liquid petroleum hydrocarbon with a long carbon chain structure.
使用时，将催化剂采用烷基铝进行还原，然后加入助催化剂，其中助催化剂为三甲基铝、一氯二乙基铝，使用量为铝含量与催化剂主体组份的摩尔比为100：1。用于石油化工中聚烯烃的工业化生产。When in use, the catalyst is reduced with alkylaluminum, and then a cocatalyst is added, wherein the cocatalyst is trimethylaluminum and diethylaluminum chloride, and the molar ratio of the aluminum content to the main component of the catalyst is 100:1 . It is used in the industrial production of polyolefin in petrochemical industry.
实施例10Example 10
一种烯烃聚合催化剂，通过以下方法制得：A kind of olefin polymerization catalyst is made by following method:
(1)将镁、铝金属按照摩尔比为1：0.05，配置成镁铝合金；(1) Magnesium and aluminum are configured into magnesium-aluminum alloy according to the molar ratio of 1:0.05;
(2)将镁铝合金粉碎成粉状，颗粒尺寸<40目；(2) Grinding the magnesium-aluminum alloy into powder, particle size<40 mesh;
(3)将合金粉分散在含有孤对电子的有机溶剂中，在80℃搅拌加热的条件下缓慢加入钛化合物，加入完毕后，在保持反应温度为80℃的情况下，继续搅拌15小时使反应完全；(3) Disperse the alloy powder in an organic solvent containing a lone pair of electrons, slowly add the titanium compound under the condition of stirring and heating at 80°C, after the addition is completed, keep stirring for 15 hours while keeping the reaction temperature at 80°C Complete response;
(4)向反应完全的体系中加入卤化镁化合物，搅拌使卤化镁化合物充分分散；然后向反应体系中加入分散剂，搅拌使分散剂充分分散；(4) adding a magnesium halide compound to the fully reacted system, stirring to fully disperse the magnesium halide compound; then adding a dispersant to the reaction system, stirring to fully disperse the dispersant;
加入原料的量以1摩尔镁粉计，含钛化合物为3摩尔，卤化镁化合物为40摩尔，分散剂为50摩尔。The amount of raw materials added is based on 1 mole of magnesium powder, 3 moles of the titanium-containing compound, 40 moles of the magnesium halide compound, and 50 moles of the dispersant.
(5)干燥，部分除去含有孤对电子的有机溶剂，使具有孤对电子的有机溶剂残留量为30wt％，得到流动性好的固体，干燥方法包括常压干燥、减压干燥、喷雾干燥或旋转干燥，然后用矿物油将得到的固体粉末分散，得到催化剂主体组分。(5) dry, partially remove the organic solvent containing the lone pair of electrons, make the residual amount of the organic solvent with the lone pair of electrons be 30wt%, obtain a solid with good fluidity, and the drying method includes normal pressure drying, decompression drying, spray drying or Spin dry, and then disperse the obtained solid powder with mineral oil to obtain the main catalyst component.
其中，所述的含有孤对电子的有机溶剂为异丁醇。所述的钛化合物的为一氯钛酸丁酯。所述的卤化镁化合物的为二戊基镁。所述的分散剂为高岭土；所述的矿物油为具有长碳链结构的高沸点液态石油烃。Wherein, the organic solvent containing a lone pair of electrons is isobutanol. The titanium compound is butyl monochlorotitanate. The magnesium halide compound is dipentyl magnesium. The dispersant is kaolin; the mineral oil is a high-boiling liquid petroleum hydrocarbon with a long carbon chain structure.
使用时，将催化剂采用烷基铝进行还原，然后加入助催化剂，其中助催化剂为三丁基铝，使用量为铝含量与催化剂主体组份的摩尔比为200：1。用于石油化工中聚烯烃的工业化生产。When in use, the catalyst is reduced with alkylaluminum, and then a cocatalyst is added, wherein the cocatalyst is tributylaluminum, and the molar ratio of the aluminum content to the catalyst main component is 200:1. It is used in the industrial production of polyolefin in petrochemical industry.
实施例11Example 11
一种烯烃聚合催化剂，通过以下方法制得：A kind of olefin polymerization catalyst is made by following method:
(1)将镁、铝金属按照摩尔比为1：1.2，配置成镁铝合金；(1) Magnesium and aluminum are configured into magnesium-aluminum alloy according to the molar ratio of 1:1.2;
(2)将镁铝合金粉碎成粉状，颗粒尺寸<40目；(2) Grinding the magnesium-aluminum alloy into powder, particle size<40 mesh;
(3)将合金粉分散在含有孤对电子的有机溶剂中，在50℃搅拌加热的条件下缓慢加入钛化合物，加入完毕后，在保持反应温度为50℃的情况下，继续搅拌20小时使反应完全；(3) Disperse the alloy powder in an organic solvent containing a lone pair of electrons, slowly add the titanium compound under the condition of stirring and heating at 50°C, and after the addition is completed, keep stirring for 20 hours while keeping the reaction temperature at 50°C Complete response;
(4)在反应完全的体系中原位产生卤化镁化合物，搅拌使卤化镁化合物充分分散；然后向反应体系中加入分散剂，搅拌使分散剂充分分散；(4) In-situ generation of magnesium halide compound in the fully reacted system, stirring to fully disperse the magnesium halide compound; then adding a dispersant to the reaction system, stirring to fully disperse the dispersant;
加入原料的量以1摩尔镁粉计，含钛化合物为5摩尔，卤化镁化合物为10摩尔，分散剂为30摩尔。The amount of added raw materials is based on 1 mole of magnesium powder, 5 moles of the titanium-containing compound, 10 moles of the magnesium halide compound, and 30 moles of the dispersant.
(5)干燥，部分除去含有孤对电子的有机溶剂，使具有孤对电子的有机溶剂残留量为20wt％，得到流动性好的固体，干燥方法包括常压干燥、减压干燥、喷雾干燥或旋转干燥，然后用矿物油将得到的固体粉末分散，得到催化剂主体组分。(5) dry, partially remove the organic solvent containing the lone pair of electrons, make the residual amount of the organic solvent with the lone pair of electrons be 20wt%, obtain a solid with good fluidity, and the drying method includes normal pressure drying, decompression drying, spray drying or Spin dry, and then disperse the obtained solid powder with mineral oil to obtain the main catalyst component.
其中，所述的含有孤对电子的有机溶剂为乙酸乙酯。所述的钛化合物为一氯钛酸乙酯。所述的卤化镁化合物为氯丁基镁。Wherein, the organic solvent containing a lone pair of electrons is ethyl acetate. The titanium compound is ethyl monochlorotitanate. The magnesium halide compound is chlorobutylmagnesium.
所述的分散剂为平均粒径范围是5-40um的无机载体蒙脱土；所述的矿物油为具有长碳链结构的高沸点液态石油烃。The dispersant is an inorganic carrier montmorillonite with an average particle size range of 5-40um; the mineral oil is a high-boiling liquid petroleum hydrocarbon with a long carbon chain structure.
使用时，将催化剂采用烷基铝进行还原，然后加入助催化剂，其中助催化剂为三甲基铝、一氯二乙基铝，使用量为铝含量与催化剂主体组份的摩尔比为150：1。用于石油化工中聚烯烃的工业化生产。When in use, the catalyst is reduced with alkylaluminum, and then a cocatalyst is added, wherein the cocatalyst is trimethylaluminum and diethylaluminum chloride, and the molar ratio of the aluminum content to the main component of the catalyst is 150:1 . It is used in the industrial production of polyolefin in petrochemical industry.
实施例12Example 12
一种烯烃聚合催化剂，通过以下方法制得：A kind of olefin polymerization catalyst is made by following method:
(1)将镁、铝金属按照摩尔比为1：0.8，配置成镁铝合金；(1) Magnesium and aluminum are configured into magnesium-aluminum alloy according to the molar ratio of 1:0.8;
(2)将镁铝合金粉碎成粉状，颗粒尺寸<40目；(2) Grinding the magnesium-aluminum alloy into powder, particle size<40 mesh;
(3)将合金粉分散在含有孤对电子的有机溶剂中，在60℃搅拌加热的条件下缓慢加入钛化合物，加入完毕后，在保持反应温度为60℃的情况下，继续搅拌30小时使反应完全；(3) Disperse the alloy powder in an organic solvent containing a lone pair of electrons, and slowly add the titanium compound under the condition of stirring and heating at 60°C. Complete response;
(4)向反应完全的体系中加入卤化镁化合物，搅拌使卤化镁化合物充分分散；然后向反应体系中加入分散剂，搅拌使分散剂充分分散；(4) adding a magnesium halide compound to the fully reacted system, stirring to fully disperse the magnesium halide compound; then adding a dispersant to the reaction system, stirring to fully disperse the dispersant;
加入原料的量以1摩尔镁粉计，含钛化合物为6摩尔，卤化镁化合物为60摩尔，分散剂为150摩尔。The amount of raw materials added is based on 1 mole of magnesium powder, 6 moles of the titanium-containing compound, 60 moles of the magnesium halide compound, and 150 moles of the dispersant.
(5)干燥，部分除去含有孤对电子的有机溶剂，使具有孤对电子的有机溶剂残留量为35wt％，得到流动性好的固体，干燥方法包括常压干燥、减压干燥、喷雾干燥或旋转干燥，然后用矿物油将得到的固体粉末分散，得到催化剂主体组分。(5) dry, partially remove the organic solvent containing the lone pair of electrons, make the residual amount of the organic solvent with the lone pair of electrons be 35wt%, obtain a solid with good fluidity, and the drying method includes normal pressure drying, decompression drying, spray drying or Spin dry, and then disperse the obtained solid powder with mineral oil to obtain the main catalyst component.
其中，所述的含有孤对电子的有机溶剂为异丁醇。所述的钛化合物的为一氯钛酸丁酯。所述的卤化镁化合物的为二戊基镁。所述的分散剂为高岭土；所述的矿物油为具有长碳链结构的高沸点液态石油烃。Wherein, the organic solvent containing a lone pair of electrons is isobutanol. The titanium compound is butyl monochlorotitanate. The magnesium halide compound is dipentyl magnesium. The dispersant is kaolin; the mineral oil is a high-boiling liquid petroleum hydrocarbon with a long carbon chain structure.
使用时，将催化剂采用烷基铝进行还原，然后加入助催化剂，其中助催化剂为三丁基铝，使用量为铝含量与催化剂主体组份的摩尔比为250：1。用于石油化工中聚烯烃的工业化生产。When in use, the catalyst is reduced with alkylaluminum, and then a cocatalyst is added, wherein the cocatalyst is tributylaluminum, and the molar ratio of the aluminum content to the main component of the catalyst is 250:1. It is used in the industrial production of polyolefin in petrochemical industry.
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| CN201810096135.0ACN108299577A (en) | 2018-01-31 | 2018-01-31 | A kind of olefin polymerization catalysis and its preparation method and application |
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| CN201810096135.0ACN108299577A (en) | 2018-01-31 | 2018-01-31 | A kind of olefin polymerization catalysis and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB976097A (en)* | 1960-11-25 | 1964-11-25 | Eastman Kodak Co | Process for producing a reduced transition metal halide,polymerization catalysts containing it and process for the polymerization of ª-olefins with such catalysts |
| JPS5291797A (en)* | 1976-01-30 | 1977-08-02 | Mitsubishi Chem Ind Ltd | Preparation of alpha-olefin polymerization catalyst |
| US5290745A (en)* | 1992-08-10 | 1994-03-01 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing ethylene polymers having reduced hexane extractable content |
| CN1223267A (en)* | 1998-01-14 | 1999-07-21 | 中国石油化工集团公司 | Gas-phase method total density polyvinyl high-efficiency catalyst |
| CN1451669A (en)* | 2002-04-19 | 2003-10-29 | 天津天大天海科技发展有限公司 | Ethylene polymerization and copolymerization catalyst preparing process |
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