CN1163456C - Ethylene oligomerizing catalyst coated with solid hydrocarbon compound and its preparation method - Google Patents

Ethylene oligomerizing catalyst coated with solid hydrocarbon compound and its preparation method Download PDF

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CN1163456C
CN1163456C CNB001358995A CN00135899A CN1163456C CN 1163456 C CN1163456 C CN 1163456C CN B001358995 A CNB001358995 A CN B001358995A CN 00135899 A CN00135899 A CN 00135899A CN 1163456 C CN1163456 C CN 1163456C
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ethylene
hydrocarbon compound
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CN1361093A (en
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方义群
刘元霞
胡友良
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中国科学院化学研究所
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Abstract

本发明提供了一种乙烯齐聚催化剂,该催化剂由乙烯齐聚催化剂和包裹在该催化剂上的固态的烃类化合物组成,这种固态烃类化合物的熔点范围在30-300℃。 The present invention provides an ethylene oligomerization catalyst which is wrapped by the oligomerization of ethylene and the catalyst solid hydrocarbons on the catalyst composition, melting point range such solid hydrocarbon compounds in 30-300 ℃. 本发明还提供了这种催化剂的制备方法。 The present invention further provides a method for preparing such a catalyst. 本发明的催化剂在空气中比较稳定,不易受水和氧的影响。 The catalyst of the present invention is relatively stable in air, easily affected by water and oxygen. 也不会因含有三乙基铝而起火燃烧。 It is not due to the presence of triethyl aluminum and burst into flames.

Description

一种固态烃类化合物包裹的乙烯齐聚催化剂及其制备方法 A solid hydrocarbons wrapped ethylene oligomerization catalyst and preparation method

技术领域 FIELD

本发明涉及一种固态烃类化合物包裹的乙烯齐聚催化剂及其制备方法。 The present invention relates to a solid hydrocarbons wrapped ethylene oligomerization catalyst and preparation method.

背景技术 Background technique

目前有关铬系催化剂催化乙烯齐聚的反应及其工艺研究已经有许多报道,US 5,331,104的齐聚催化剂体系中过渡金属化合物是吡啶铬,而JP 08,239,328是二乙基己酸铬(Cr(EH)3),他们是将2,5-二甲基吡咯(2,5-DMP)、四氯化锗(GeCl4),三乙基铝(TEA)和Cr(EH)3,未预混合直接加入齐聚反应器中,US 5,523,507是将上述各组分先进行预混合,然后再加入到齐聚反应器中进行乙烯齐聚反应。 At present the process of Reaction and chromium-catalyzed oligomerization of ethylene have been many reports, oligomerization catalyst system of US 5,331,104 in pyridine transition metal compound is chromium, and JP 08,239,328 chromium di-ethylhexanoate (Cr (EH) 3), they are the 2,5-dimethylpyrrole (2,5-DMP), germanium tetrachloride (of GeCl4), triethyl aluminum (TEA) and Cr (EH) 3, not directly into the pre-mixed together polymerization reactor, US 5,523,507 above components are first premixed and then added to the reactor for oligomerization of ethylene oligomerization. 但是这些反应体系在常温下均为液相,极易受空气中的水和氧的影响而失效,而且在空气中会因有三乙基铝(TEA)而起火燃烧。 However, these systems are the reaction liquid at room temperature, and failure easily affected by oxygen and moisture in the air, and in the air due triethyl aluminum (TEA) and burst into flames.

发明内容 SUMMARY

本发明的目的是克服背景技术中的催化体系易受空气中水和氧的影响的缺点,通过采用一种惰性物质包裹催化体系的方法,使得催化剂在空气中较稳定,受水和氧的影响较小,也不会因含有三乙基铝而起火燃烧。 Object of the present invention is to overcome the disadvantages of the background art catalyst system is susceptible to water and oxygen in the air by using a method of inert material wrapped catalyst system, such that the catalyst is stable in air, is affected by water and oxygen is small, it will not contain triethyl aluminum and burst into flames.

本发明中所涉及的情性包裹物是固态的烃类化合物,熔点范围在30-300℃,烷烃可以是单一的烃类,也可为混合烃,常用的是熔点在50-150℃的烃类化合物,最常用的是50-80℃的石蜡。 The present invention relates in case of wrap hydrocarbon compounds are solid, the melting point range at 30-300 deg.] C, may be a single alkane hydrocarbons, may also be a mixed hydrocarbon, the hydrocarbon is used at a melting point of 50-150 deg.] C compounds, the most commonly used are paraffin of 50-80 ℃.

本发明中所涉及的惰性包裹物的包埋方法可以适用于任何一种烯烃齐聚或聚合的催化剂,乙烯聚合或齐聚,丙烯聚合或齐聚,常用于乙烯齐聚。 Embedding method of the present invention relates to an inert wrap may be applicable to any olefin oligomerization or polymerization catalyst, the polymerization or oligomerization of ethylene, propylene polymerization or oligomerization, commonly used in ethylene oligomerization. 这些催化剂的制备是现有技术中已知的,如下所述。 The preparation of these catalysts are known in the prior art, as described below.

金属铬的化合物根据US 5,523,507中报道,可以是有机或无机铬的化合物。 The metallic chromium compounds reported in US 5,523,507, may be an organic or inorganic chromium compounds. 铬的氧化态是0-6,通常的形式是CrXn,X可以相同,也可以不同,n是1-6的整数,每个有机基团的碳原子数是1-20,可以从烷基、烷氧基、酯基、酮基、或者是氨基,有机的基团可以是直链,也可以是支链,可以是芳香基、脂肪基、或者环基,也可以是混合基团。 Oxidation state of chromium is 0-6, usually in the form CrXn, X may be the same or different, n being an integer of 1 to 6 carbon atoms per organic group of 1 to 20, from alkyl, an alkoxy group, an ester group, a ketone group or an amino group, an organic group may be linear, may be branched, may be an aromatic group, aliphatic group, or cyclic group, it may be a mixed group. 常用铬的二价和三价化合物,更常用的是三价铬化合物,二氯乙基己酸铬,二氧乙基己酸铬,月桂酸铬,β-二酮铬,吡啶铬,二乙基己酸铬,最常用二乙基己酸铬(Cr(EH)3)。 Common chromium divalent and trivalent compounds, more usually trivalent chromium compound, dichloro-ethylhexanoate, chromium, chromium-dioxo-ethylhexanoate, laurate, chromium, chromium-dione [beta], chromium pyridine, diethyl chromium-yl hexanoic acid, most commonly two chromium ethylhexanoate (Cr (EH) 3).

铝的化合物的通式有AlR3,AlR2X,AlRX2,AlR2OR,AlRXOR,Al2R3X3,R是烷基基团,X是卤素原子。 Aluminum compound has the general formula AlR3, AlR2X, AlRX2, AlR2OR, AlRXOR, Al2R3X3, R is an alkyl group, X is a halogen atom. 通常用三乙基铝、三异丁基铝、二乙基氯化铝、乙基乙氧基氯化铝,齐聚中常用三烷基铝、最常用三乙基铝。 Usually triethylaluminum, triisobutylaluminum, diethyl aluminum chloride, ethyl aluminum ethoxy chloride, commonly used oligomerization trialkylaluminum, most commonly aluminum triethyl.

含氮化合物有吡咯及其衍生物、吡啶及其衍生物,常用吡咯化合物,二乙基吡咯,四氢吡咯,2,5-二甲基吡咯,2,4-二甲基-3-乙基吡咯,最常用2,5-二甲基吡咯。 Pyrrole nitrogen-containing compounds and derivatives thereof, pyridine and its derivatives, pyrrole compound used, diethyl pyrrole, pyrrolidine, 2,5-dimethylpyrrole, 2,4-dimethyl-3-ethyl pyrrole, 2,5-dimethylpyrrole most commonly used.

卤素化合物可以增加催化体系的活性和选择性,也可以增加产物的选择性。 Halogen compounds can increase the activity and selectivity of the catalytic system, it may also increase product selectivity. 卤素有氟、氯、溴、碘。 A halogen are fluorine, chlorine, bromine, iodine. 通常是氯,卤素化合物的形式是RmXn,R可以是有机或无机基,X为卤素。 Usually chlorine, in the form of a halogen compound is RmXn, R may be an organic or inorganic group, X is a halogen. m+n大于0。 m + n is greater than 0. R为无机基团时,常为铝、硅、锗、锡、铅等,最常用四氯化锗。 When R is an inorganic group, usually of aluminum, silicon, germanium, tin, lead, germanium tetrachloride is most commonly used.

该催化体系易于在不饱和碳氢化合物中进行,可以用芳香烃或脂肪烃,可以为气相、液相、固相,常用甲苯、苯、苯乙烯等芳香烃或乙烯、1-己烯、1,3-丁二烯等烯烃,最常用甲苯。 The catalytic system is susceptible to unsaturated hydrocarbons, aromatic or aliphatic hydrocarbon can be used, and may be gas, liquid, solid phase, commonly toluene, benzene, an aromatic hydrocarbon such as styrene or ethylene, 1-hexene, 1 1,3-butadiene and other olefins, the most common of toluene.

本发明提供了一种乙烯齐聚催化剂,该催化剂由乙烯齐聚催化剂和包裹在该催化剂上的固态的烃类化合物组成,这种固态烃类化合物的熔点范围在30-300℃。 The present invention provides an ethylene oligomerization catalyst which is wrapped by the oligomerization of ethylene and the catalyst solid hydrocarbons on the catalyst composition, melting point range such solid hydrocarbon compounds in 30-300 ℃.

在本发明的催化剂中,所述的固态烃类化合物最好是石蜡。 In the catalyst of the present invention, the solid paraffin is preferably a hydrocarbon compound.

本发明中所涉及的催化剂包裹温度能够在40-300℃,通常在50-150℃,最好是50-80℃。 The temperature of the catalyst package of the present invention can be involved at 40-300 ℃, usually at 50-150 ℃, preferably 50-80 ℃.

本发明的催化剂制备方法顺序如下:1.制备乙烯齐聚催化剂;2.将制备出的乙烯齐聚催化剂与固态烃类化合物进行包埋处理,其中固态烃类化合物与乙烯齐聚催化剂的重量比为100∶1-1∶200,优选75∶-1∶20。 The method of preparing the catalyst of the present invention the order as follows: 1. Preparation of catalyst for ethylene oligomerization; 2 ethylene oligomerization catalyst is prepared with a solid embedding processing a hydrocarbon compound wherein the hydrocarbon compound and solid catalyst weight ratio of ethylene oligomerization. is 100:1-1:200, preferably-75:25 1:20. 反应温度为60-150℃,最好是75-100℃,反应时间为15分钟-2小时,最好是30分钟-1小时。 The reaction temperature is 60-150 deg.] C, preferably 75-100 deg.] C, the reaction time is 15 minutes to 2 hours, preferably 30 minutes to 1 hour.

上述的固态烃类化合物最好先进行脱水处理,可以用抽真空、加热、化学方法或其他方法。 The above solid hydrocarbon compounds preferably subjected to dehydration treatment, can be evacuated, heating, chemical methods, or other methods. 常用加热抽真空的方法,温度50-150℃,最好是70-100℃。 Common vacuum heating method, the temperature of 50-150 deg.] C, preferably 70-100 ℃. 处理时间可以有很大的变化范围,通常为4-48小时,最好为20-30小时。 Treatment time range can vary widely, typically 4-48 hours, preferably 20-30 hours.

在本发明的方法中,所述的固态烃类化合物最好是石蜡。 In the method of the present invention, the solid paraffin is preferably a hydrocarbon compound.

本发明所制备的催化剂有如下的特点:1、本发明用固态烃类化合物包裹的催化剂可以在空气中进行操作使用,不易受水的影响,而且可以放置在空气中保存;2、本发明催化剂活性较高,选择性好,1-己烯选择性高达97.9%;3、本发明催化剂的1-己烯产率可达到94.41%;4、本发明所采用的助催化剂是相对价格低廉的烷基铝。 The catalyst prepared in the present invention has the following characteristics: 1, the present invention is a solid hydrocarbon compounds encapsulated catalyst may be operated in the air, not by the influence of water, but also may be placed in the air storage; 2, the present invention is a catalyst higher activity, selectivity, hexene-1 selectivity 97.9%; 3, 1-hexene yield can reach the catalyst of the present invention 94.41%; 4, cocatalyst employed in the present invention is relatively inexpensive alkoxy aluminum group.

按本发明的方法制备催化剂及将所制催化剂用于乙烯齐聚所得结果列于表一。 A catalyst was prepared according to the method of the present invention and the prepared catalyst is used for ethylene oligomerization results are shown in Table I.

表一:催化剂制备和齐聚催化结果 Table I: Preparation of Catalyst and Catalytic oligomerization results

注:催化剂体系是Cr(EH)3+TEA+2,5-DMP+GeCl4摩尔比是:1/3/15/2实施例实施例一:载体处理:石蜡在80℃抽真空24小时在干燥氮气下备用。 NOTE: The catalyst system was Cr (EH) 3 + TEA + 2,5-DMP + GeCl4 molar ratio: Example a Example 1/3/15/2: vehicle treated: Paraffin drawn at 80 deg.] C vacuum drying for 24 hours under nitrogen for standby.

催化剂制备:取上述石蜡载体40克放入100ml圆底两口烧瓶中,抽真空置换干燥N2保护。 Preparation of Catalyst: Paraffin take the above carrier 40 grams into a 100ml round bottom two-necked flask, vacuum dried replaced N2 protection. 取0.22g Cr(EH)3(溶解在甲苯溶液中)和0.13ml的2,5-DMP,加入0.1ml的GeCl4,1.9M的TEA(溶解在甲苯溶液中)3.4ml,产物抽真空除去甲苯溶剂。 Take 0.22g Cr (EH) 3 (dissolved in toluene) and 0.13ml of 2,5-DMP, added 0.1ml of GeCl4,1.9M of TEA (dissolved in a toluene solution) 3.4ml, the toluene was removed in vacuo the product solvent. 将所制得的催化剂在60℃加入石蜡中,搅拌冷却至室温,称重42.234g。 The prepared catalyst was added paraffin at 60 ℃, cooled to room temperature with stirring, weighed 42.234g. Cr(g)/石蜡(g)为2.2×10-4g/g。 Cr (g) / paraffin (g) of 2.2 × 10-4g / g.

乙烯齐聚:取上述载体催化剂10g加入0.2升反应釜中,抽真空5小时,在常温常压下将40ml壬烷溶剂加入反应釜,升温至80℃,注入乙烯进行聚合反应。 Ethylene oligomerization: Take 10g of the supported catalyst described above was added 0.2 l autoclave evacuated for 5 hours at normal temperature and pressure to 40ml nonane solvent into a reactor, heated to 80 ℃, injecting ethylene polymerization. 乙烯压力为2.68MPa,反应30min后降温。 Ethylene pressure was 2.68MPa, the reaction cooled after 30min. 共得液相产物14.896g,固相产物0.034g。 To give a total liquid product 14.896g, solid product was 0.034g.

实施例二:乙烯齐聚:取实施例一中的载体催化剂10g放置24小时后加入0.2升反应釜中,抽真空5小时,在常温常压下将40ml壬烷溶剂加入反应釜,升温至80℃,注入乙烯进行聚合反应。 Example II: Ethylene oligomerization: after taking 10g embodiment a supported catalyst for 24 hours in 0.2 liter reaction kettle was evacuated for 5 hours at normal temperature and pressure to 40ml nonane solvent into a reactor, heated to 80 ℃, injecting ethylene polymerization. 乙烯压力为2.68MPa,反应30min后降温。 Ethylene pressure was 2.68MPa, the reaction cooled after 30min. 共得液相产物9.57g,固相产物0.17g。 To give a total liquid product 9.57g, solid product was 0.17g.

实施例三:催化剂制备:取上述石蜡载体100克放入100ml圆底两口烧瓶中,抽真空置换干燥N2保护。 Example Three: Preparation of Catalyst: Paraffin take the above carrier 100 grams into a 100ml round bottom two-necked flask, vacuum dried replaced N2 protection. 如实施例一中的加料次序加入石蜡中,称重102.234g。 The order of addition of the first embodiment added paraffin, weighed 102.234g. Cr(g)/石蜡(g)为8.8×10-5g/g。 Cr (g) / paraffin (g) of 8.8 × 10-5g / g.

乙烯齐聚:取上述载体催化剂20g加入0.2升反应釜中,抽真空5小时,在常温常压下将40ml壬烷溶剂加入反应釜,升温至80℃,注入乙烯进行聚合反应。 Ethylene oligomerization: Take 20g of the supported catalyst described above was added 0.2 l autoclave evacuated for 5 hours at normal temperature and pressure to 40ml nonane solvent into a reactor, heated to 80 ℃, injecting ethylene polymerization. 乙烯压力为2.68MPa,反应30min后降温。 Ethylene pressure was 2.68MPa, the reaction cooled after 30min. 共得液相产物9.56g,固相产物0.06g。 To give a total liquid product 9.56g, solid product was 0.06g.

实施例四:乙烯齐聚:取实施例三中的载体催化剂20g放置24小时后加入0.2升反应釜中,抽真空5小时,在常温常压下将20ml壬烷溶剂加入反应釜,升温至80℃,注入乙烯进行聚合反应。 Embodiment Example 4: Ethylene oligomerization: the carrier according to a third embodiment taken 0.2 liter reaction kettle was evacuated for 24 hours after 5 hours the catalyst 20g, at normal temperature and pressure to 20ml nonane solvent into a reactor, heated to 80 ℃, injecting ethylene polymerization. 乙烯压力为2.68MPa,反应80min后降温,共得液相产物24.65g,固相产物0.11g。 Ethylene pressure was 2.68MPa, after 80min the reaction cooled, to give a total liquid product was 24.65g, a solid product was 0.11g.

实施例五:催化剂制备:取上述石蜡载体100克放入100ml圆底两口烧瓶中,抽真空置换干燥N2保护。 Example V: Preparation of Catalyst: Paraffin take the above carrier 100 grams into a 100ml round bottom two-necked flask, vacuum dried replaced N2 protection. 如实施例一中的加料次序将所制得的催化剂取0.11g在60℃加入石蜡中,搅拌冷却至室温,称重101.167g。 The order of addition of embodiment example 1 The catalyst prepared was added 0.11g paraffin taken at 60 ℃, cooled to room temperature with stirring, weighed 101.167g. Cr(g)/石蜡(g)为4.4×10-5g/g。 Cr (g) / paraffin (g) of 4.4 × 10-5g / g.

乙烯齐聚:取上述载体催化剂50g加入0.2升反应釜中,抽真空5小时,升温至80℃,注入乙烯进行聚合反应。 Ethylene oligomerization: Take 50g of the supported catalyst described above was added 0.2 l autoclave evacuated for 5 hours and allowed to warm to 80 ℃, injecting ethylene polymerization. 乙烯压力为2.68MPa,反应30min后降温。 Ethylene pressure was 2.68MPa, the reaction cooled after 30min. 共得液相产物6.77g,固相产物0.13g。 To give a total liquid product 6.77g, solid product was 0.13g.

实施例六:催化剂制备:取上述石蜡载体20克放入100ml圆底两口烧瓶中,抽真空置换干燥N2保护。 Example VI: Preparation of Catalyst: Paraffin take the above carrier 20 grams into a 100ml round bottom two-necked flask, vacuum dried replaced N2 protection. 如实施例一中的加料次序所制得的催化剂在60℃加入石蜡中,搅拌冷却至室温,称重22.34g。 The order of addition of the first embodiment of the prepared catalyst was added at 60 deg.] C paraffin, cooled to room temperature with stirring, weighed 22.34g. Cr(g)/石蜡(g)为4.4×10-4g/g。 Cr (g) / paraffin (g) of 4.4 × 10-4g / g.

乙烯齐聚:取上述载体催化剂5g加入0.2升反应釜中,抽真空5小时,在常温常压下将40ml壬烷溶剂加入反应釜,升温至80℃,注入乙烯进行聚合反应。 Ethylene oligomerization: Take 5g supported catalyst described above was added 0.2 l autoclave evacuated for 5 hours at normal temperature and pressure to 40ml nonane solvent into a reactor, heated to 80 ℃, injecting ethylene polymerization. 乙烯压力为2.68MPa,反应30min后降温。 Ethylene pressure was 2.68MPa, the reaction cooled after 30min. 共得液相产物6.79g,固相产物0/36g。 To give a total liquid product was 6.79g, the solid phase product 0 / 36g.

实施例七:乙烯齐聚:取实施例六中的载体催化剂5g放置24小时后加入0.2升反应釜中,抽真空5小时,在常温常压下将40ml壬烷溶剂加入反应釜,升温至80℃,注入乙烯进行聚合反应。 Example Seven: Ethylene oligomerization: was added to the supported catalyst in Example 5g Sixth embodiment taken 24 hours after the 0.2 l autoclave evacuated for 5 hours at normal temperature and pressure to 40ml nonane solvent into a reactor, heated to 80 ℃, injecting ethylene polymerization. 乙烯压力为2.68MPa,反应30min后降温。 Ethylene pressure was 2.68MPa, the reaction cooled after 30min. 共得液相产物5.43g,固相产物0.33g。 To give a total liquid product 5.43g, solid product was 0.33g.

比较例一:催化剂制备:取0.22gCr(EH)3(溶解在甲苯溶液中)和0.13ml的2,5-DMP,加入0.1ml的GeCl4,1.9M的TEA(溶解在甲苯溶液中)3.4ml,出现褐色、黄褐色溶液及固体,真空移走溶剂,15ml壬烷提取,过滤。 Comparative Example a: Preparation of Catalyst: Take 0.22gCr (EH) 3 (dissolved in toluene) and 0.13ml of 2,5-DMP, added GeCl4,1.9M 0.1ml of TEA (dissolved in toluene) 3.4 ml of appears brown, brown solution and a solid, the solvent was removed in vacuo, 15ml nonane extraction, filtration. 用壬烷稀释至25ml。 Was diluted to 25ml with nonane.

烯烃聚合:将0.2升反应釜在40℃加热抽真空4小时,在常温常压下依次加入40ml壬烷、3ml上述催化剂,升温至80℃,注入乙烯进行聚合反应。 Olefin polymerization: A 0.2 l autoclave was heated for 4 hours evacuated 40 ℃, at normal temperature and pressure were added 40ml nonane, 3ml of the catalyst, was heated to 80 ℃, injecting ethylene polymerization. 乙烯压力为2.68Mpa,反应30min后降温。 Ethylene pressure is 2.68Mpa, the reaction cooled after 30min. 共得液相产物18.65g,固相产物0.04g。 To give a total liquid product was 18.65g, a solid product was 0.04g.

比较例二:催化剂制备如比较实例一。 Comparative Example Two: Preparation of the catalyst as a comparative example.

烯烃聚合:将0.2升反应釜在40℃加热抽真空4小时,在常温常压下依次加入40ml壬烷、3ml实施例一中放置24h的催化剂,升温至80℃,注入乙烯进行聚合反应。 Olefin polymerization: A 0.2 l autoclave was heated for 4 hours evacuated 40 ℃, at normal temperature and pressure were added 40ml nonane, for example, a catalyst is placed in 3ml embodiments 24h, warmed to 80 ℃, injecting ethylene polymerization. 乙烯压力为2.68Mpa,反应60min后降温。 Ethylene pressure is 2.68Mpa, the reaction was cooled 60min. 共得液相产物32.644g,固相产物0.04g。 To give a total liquid product 32.644g, solid product was 0.04g.

比较例三:催化剂制备如比较实例一。 Comparative Example Three: Catalyst prepared as a comparative example.

烯烃聚合:将0.2升反应釜在40℃加热抽真空4小时,在常温常压下依次加入40ml壬烷、6ml催化剂,升温至80℃,注入乙烯进行聚合反应。 Olefin polymerization: A 0.2 l autoclave was heated for 4 hours evacuated 40 ℃, at normal temperature and pressure were added 40ml nonane, 6 ml of the catalyst was heated to 80 ℃, injecting ethylene polymerization. 乙烯压力为2.68MPa,反应30min后降温。 Ethylene pressure was 2.68MPa, the reaction cooled after 30min. 共得液相产物6.48g,固相产物0.04g。 To give a total liquid product 6.48g, solid product was 0.04g.

Claims (8)

1.一种固态烃类化合物包裹的乙烯齐聚催化剂,该催化剂由乙烯齐聚催化剂和包裹在该催化剂上的固态的烃类化合物组成,这种固态烃类化合物的熔点范围在30-300℃。 A solid hydrocarbon compound wrapped ethylene oligomerization catalyst which is wrapped by the oligomerization of ethylene and the catalyst solid hydrocarbons on the catalyst composition, the melting point range of the hydrocarbon compound solid at 30-300 ℃ .
2.按照权利要求1所述的催化剂,其中,所述的固态烃类化合物是石蜡。 2. The catalyst according to claim 1, wherein the solid compound is a hydrocarbon paraffin wax.
3.一种制备权利要求1所述的固态烃类化合物包裹的乙烯齐聚催化剂的方法,包括以下步骤:(1)制备乙烯齐聚催化剂;(2)将制备出的乙烯齐聚催化剂与固态烃类化合物进行包埋处理,其中固态烃类化合物与乙烯齐聚催化剂的重量比为100∶1-1∶200,反应温度为60-150℃,反应时间为15分钟-2小时; Ethylene oligomerization catalyst solid hydrocarbon compound according to claim 1 or 2 for preparing a package, comprising the steps of: (1) preparing an ethylene oligomerization catalyst; (2) the ethylene oligomerization catalyst is prepared by solid-state hydrocarbon compound embedding process, wherein the solid weight of the hydrocarbon compound with ethylene oligomerization catalyst 100:1-1:200 ratio, the reaction temperature is 60-150 deg.] C, the reaction time is 15 minutes to 2 hours;
4.按照权利要求3所述的方法,其中,固态烃类化合物与乙烯齐聚催化剂的重量比为75∶1-1∶20。 4. The method according to claim 3, wherein the hydrocarbon compound and solid catalyst weight ratio of ethylene oligomerization is 75:1-1:20.
5.按照权利要求3所述的方法,其中,包埋时的反应温度是75-100℃,反应时间为30分钟-1小时。 5. The method according to claim 3, wherein the reaction temperature is 75-100 deg.] C embedding, the reaction time from 30 minutes to 1 hour.
6.按照权利要求3所述的方法,其中,在进行包埋处理前,先将固态烃类化合物进行脱水处理。 6. The method according to claim 3, wherein, before performing embedding processing, first solid hydrocarbons dehydrated.
7.按照权利要求6所述的方法,其中,所述的脱水处理是在50-150℃下抽真空进行的,时间为4-48小时。 7. The method according to claim 6, wherein said vacuum dehydration treatment is carried out at 50-150 deg.] C, time is 4-48 hours.
8.按照权利要求7所述的方法,其中,所述的脱水处理是在70-100℃下抽真空进行的,时间为20-30小时。 8. The method according to claim 7, wherein the dehydration treatment is carried out evacuation at 70-100 deg.] C, time is 20-30 hours.
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US20050187098A1 (en) 2004-02-20 2005-08-25 Knudsen Ronald D. Methods of preparation of an olefin oligomerization catalyst
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US20070043181A1 (en) 2005-08-19 2007-02-22 Knudsen Ronald D Methods of preparation of an olefin oligomerization catalyst
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