CN116041130A - Ethylene oligomerization catalysis process - Google Patents
Ethylene oligomerization catalysis processDownload PDFInfo
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Abstract
Description
Translated fromChinese技术领域technical field
本发明涉及乙烯齐聚工艺技术领域，具体涉及一种乙烯齐聚催化工艺。The invention relates to the technical field of ethylene oligomerization process, in particular to an ethylene oligomerization catalytic process.
背景技术Background technique
线性α-烯烃通常是指C4以上的高碳直链端烯烃，广泛应用于合成润滑油基础油、共聚单体、表面活性剂、增塑剂、杀菌剂、乳化剂等化工产品。例如1-丁烯、1-己烯和1-辛烯主要用作聚乙烯共聚单体；1-癸烯是合成高级润滑油基础油的原料；C10-C14的α-烯烃可用于生产降凝剂，C14-C18的α-烯烃可用来生产α-烯烃磺酸盐AOS，AOS是重垢低磷洗衣粉的主要成分；C18以上的α-烯烃可直接用作润滑油添加剂及钻井液。近年来，高功能PE、润滑剂和先进洗涤剂的迅猛发展，导致对α-烯烃的需求量剧增。Linear α-olefins usually refer to high-carbon linear terminal olefins aboveC4 , which are widely used in chemical products such as synthetic lubricant base oils, comonomers, surfactants, plasticizers, fungicides, and emulsifiers. For example, 1-butene, 1-hexene and 1-octene are mainly used as polyethylene comonomers; 1-decene is the raw material for synthesizing high-grade lubricant base oil; C10 -C14 α-olefins can be used to produce Pour point depressant, C14 -C18 α-olefins can be used to produce α-olefin sulfonate AOS, AOS is the main component of heavy-duty low-phosphorus washing powder; C18 and above α-olefins can be directly used as lubricating oil additives and drilling fluid. In recent years, the rapid development of high-functional PE, lubricants and advanced detergents has led to a sharp increase in the demand for α-olefins.
线性α-烯烃最初采用石蜡裂解法生产，但石蜡裂解法得到的是含有奇偶碳数的α-烯烃混合物，其中还含有内烯烃、二烯烃、支链烯烃及芳烃等杂质，组成复杂，产品纯度差，难以满足共聚单体、合成表面活性剂等产品的需要。为了制取满足市场需要的高质量α-烯烃产品，欧美等国家逐步开发并发展了乙烯齐聚法，该法是在催化剂存在下，由乙烯单体进行碳链增长反应，得到含有偶数碳原子的α-烯烃产品。随着乙烯齐聚法的发展，石蜡裂解法逐渐被淘汰，到二十世纪，国外石蜡裂解生产装置已全部停产，代之以乙烯齐聚法来制取高质量的α-烯烃产品。Linear α-olefins are initially produced by paraffin cracking, but the paraffin cracking method produces a mixture of α-olefins with odd and even carbon numbers, which also contains impurities such as internal olefins, dienes, branched olefins, and aromatics. The composition is complex and the product purity is low. Poor, it is difficult to meet the needs of products such as comonomers and synthetic surfactants. In order to produce high-quality α-olefin products that meet the needs of the market, countries such as Europe and the United States have gradually developed and developed the ethylene oligomerization method. α-olefin products. With the development of the ethylene oligomerization method, the paraffin cracking method was gradually eliminated. By the 20th century, all foreign paraffin cracking production facilities had been shut down and replaced by the ethylene oligomerization method to produce high-quality α-olefin products.
德国专利DE1443927公开了Gulf公司的一步法工艺，美国专利US3906053公开了Ethyl公司的两步法工艺，但均没有解决齐聚中生成聚乙烯蜡对反应设备的堵塞等问题。美国专利US3676523、US3686351和US3726938公开了Shell公司的高级α-烯烃生产工艺(ShellHigherOlefinProcess)，即SHOP工艺。这是目前世界上公认的最成功的乙烯齐聚工艺，该工艺采用镍系催化剂，产物分布宽，存在大量C20及以上的固体低聚物，严重影响设备操作。该工艺对这部分产物进行异构化并通过与低碳烯烃的交互置换来转换消化，致使工艺路线长能耗高，只有大规模生产时才具有经济效益。欧洲专利EP177999和日本JP6259225公开了日本出光公司采用茂金属催化剂进行乙烯齐聚制备线性α-烯烃的工艺，该工艺反应压力较高，且生成高聚物，同样容易造成管路堵塞。German patent DE1443927 discloses the one-step process of Gulf Company, and U.S. Patent US3906053 discloses the two-step process of Ethyl Company, but neither solves the problems such as the clogging of reaction equipment by polyethylene wax generated during oligomerization. US Patents US3676523, US3686351 and US3726938 disclose Shell Higher Olefin Production Process (Shell Higher Olefin Process), namely SHOP process. This is currently the most successful ethylene oligomerization process recognized in the world. This process uses nickel-based catalysts, and the product distribution is wide. There are a large number of solid oligomers with C20 and above, which seriously affects the operation of the equipment. This process isomerizes this part of the product and converts and digests it by alternating replacement with low-carbon olefins, resulting in a long process route and high energy consumption. Only in large-scale production can it be economically beneficial. European patent EP177999 and Japanese JP6259225 disclose the process of Japan Idemitsu Company using metallocene catalysts to carry out ethylene oligomerization to prepare linear α-olefins. This process has high reaction pressure and generates high polymers, which is also easy to cause pipeline blockage.
专利US610394、US5955555、CN01105268.6、CN01109134.7和CN101649012A中公开采用了2,6-吡啶羧酸(双亚胺)或者2,6-二酰基吡啶(双亚胺)的配位体与铁的络合物作为乙烯齐聚生产线性α-烯烃的催化剂，具有优异的催化性能。美国专利US2002/0016521中公开了使用该类催化剂制造α-烯烃的方法，其中使用了全液体连续搅拌釜反应器，也可以在全液体连续搅拌釜反应器上任意接续一个反应器，作为最后的反应器，该最后的反应器可以是平推流管式反应器；该方法的反应温度较低，在35℃-80℃之间，但反应压力需要在乙烯的泡点以上，才能确保全部成分(包括乙烯)保持在液相中，以使反应器中只存在单一的液相，并且所得α-烯烃的产品分布范围较窄，K值在0.65-0.8(K＝链增长速率/(链增长速率+链转移速率)＝Cn+2的摩尔数/Cn的摩尔数，n为正整数)。美国专利US2004/0111002和公告号CN1330612C的中国专利中均公开了使用这类铁系催化剂在改进的平推流反应器中沿着反应器长度方向的α-烯烃的平均浓度比连续搅拌反应器低很多，形成的非线性α-烯烃的杂质含量较少，有利于生产出较纯的α-烯烃；与未改进的活塞流反应器相比，该方法可以使用较低的乙烯压力，从而降低投资费用，但该方法中反应的压力也需要保持在乙烯的泡点以上，才能确保全部成分(包括乙烯)保持在液相中，以使反应器中只有单一的液相，并且所得α-烯烃的产品分布范围较窄。Patents US610394, US5955555, CN01105268.6, CN01109134.7 and CN101649012A disclose the use of ligands of 2,6-pyridinecarboxylic acid (bisimine) or 2,6-diacylpyridine (bisimine) and iron The complex has excellent catalytic performance as a catalyst for ethylene oligomerization to produce linear α-olefins. U.S. Patent US2002/0016521 discloses the method of using this type of catalyst to produce α-olefins, wherein a full liquid continuous stirred tank reactor is used, and a reactor can also be arbitrarily connected to the full liquid continuous stirred tank reactor as the last Reactor, the last reactor can be a plug-flow tube reactor; the reaction temperature of this method is relatively low, between 35°C and 80°C, but the reaction pressure needs to be above the bubble point of ethylene to ensure all components (including ethylene) remain in the liquid phase, so that there is only a single liquid phase in the reactor, and the product distribution range of the resulting α-olefin is narrow, and the K value is at 0.65-0.8 (K=chain growth rate/(chain growth rate rate+chain transfer rate)=the number of moles of Cn+2 /the number of moles of Cn , n is a positive integer). U.S. Patent US2004/0111002 and Chinese Patent No. CN1330612C all disclose that the average concentration of α-olefins along the length of the reactor in the improved plug flow reactor is lower than that of the continuous stirring reactor by using this type of iron-based catalyst Many, non-linear α-olefins formed with fewer impurities favor the production of purer α-olefins; compared to unmodified plug flow reactors, the process allows the use of lower ethylene pressures, thereby reducing capital investment cost, but the pressure of the reaction in this method also needs to be kept above the bubble point of ethylene to ensure that all components (including ethylene) remain in the liquid phase, so that there is only a single liquid phase in the reactor, and the resulting α-olefin Product distribution is narrow.
可见，现有的线性α-烯烃的制备工艺仍然存在着相当多的问题，大多反应条件苛刻，操作流程复杂，且反应产物中存在高分子量聚乙烯蜡以及非线性α-烯烃等杂质，催化剂的活性和催化效率也是线性α-烯烃的工业生产需要关注的问题。因而，有必要对乙烯齐聚制备线性α-烯烃工艺进行进一步的研究。It can be seen that there are still quite a lot of problems in the existing preparation process of linear α-olefins. Most of the reaction conditions are harsh, the operation process is complicated, and there are impurities such as high molecular weight polyethylene wax and nonlinear α-olefins in the reaction products. Activity and catalytic efficiency are also concerns for the industrial production of linear α-olefins. Therefore, it is necessary to conduct further research on the preparation of linear α-olefins by ethylene oligomerization.
发明内容Contents of the invention
鉴于上述现有技术中存在的问题，本发明的目的在于提供一种乙烯齐聚催化工艺，其通过使用特定的催化剂，能够使得齐聚反应在较高的温度下进行，齐聚反应引发迅速、运行平稳、重复性好；并且随着反应的升高，催化剂的活性依然保持在很高的水平，同时随着反应温度的逐渐升高，到60-70℃的较高温时，产物分布系数依然能够达到0.7左右而不明显下降，而且反应温度为60-70℃，反应撤热介质可以采用冷凝水，与冷冻水相比降低了能耗，工业应用价值明显提升。上述实验结果克服了本领域技术人员的技术偏见，取得了预料不到的技术效果。In view of the problems existing in the above-mentioned prior art, the object of the present invention is to provide a kind of ethylene oligomerization catalytic process, it can make oligomerization to carry out at higher temperature by using specific catalyst, and oligomerization initiates rapidly, The operation is stable and repeatable; and as the reaction increases, the activity of the catalyst remains at a high level. At the same time, with the gradual increase of the reaction temperature, the product distribution coefficient remains the same at a higher temperature of 60-70°C. It can reach about 0.7 without significant drop, and the reaction temperature is 60-70°C, and the reaction heat removal medium can be condensed water, which reduces energy consumption compared with chilled water and significantly improves industrial application value. The above experimental results overcome the technical bias of those skilled in the art and achieve unexpected technical effects.
为实现上述目的，本发明采取的技术方案如下：In order to achieve the above object, the technical scheme that the present invention takes is as follows:
一种乙烯齐聚催化工艺，包括：使乙烯与催化剂在反应器内接触，其中，所述接触的条件包括：温度为40℃～90℃，优选为40℃～80℃，进一步优选为50℃～70℃，以及A catalytic process for ethylene oligomerization, comprising: contacting ethylene with a catalyst in a reactor, wherein the contact conditions include: a temperature of 40°C to 90°C, preferably 40°C to 80°C, more preferably 50°C ~70°C, and
所述催化剂包括主催化剂、含铝助催化剂、有机溶剂和水，所述主催化剂选自式(1)所示的化合物中的一种或多种，The catalyst includes a main catalyst, an aluminum-containing cocatalyst, an organic solvent and water, and the main catalyst is selected from one or more of the compounds shown in formula (1),
式(1)中，R1-R11相同或不同，各自独立地选自氢、C1-C6烷基、卤素、C1-C6烷氧基和硝基；R12选自氢、C1-C6烷基、C6-C18烷芳基和C6-C18芳烷基；M为Fe(II)、Co(II)或Ni(II)。In formula (1), R1 -R11 are the same or different, each independently selected from hydrogen, C1 -C6 alkyl, halogen, C1 -C6 alkoxy and nitro; R12 is selected from hydrogen, C1 -C6 alkyl, C6 -C18 alkaryl and C6 -C18 aralkyl; M is Fe(II), Co(II) or Ni(II).
在本发明的一些优选的实施方式中，所述接触的温度优选为45℃～65℃。In some preferred embodiments of the present invention, the contacting temperature is preferably 45°C-65°C.
在本发明的一些优选的实施方式中，所述接触的条件还包括：采用冷凝水作为所述反应器的撤热介质，优选地，所述冷凝水的温度为10℃～35℃，优选为20℃～35℃，更优选为25℃～35℃。In some preferred embodiments of the present invention, the contact conditions also include: using condensed water as the heat removal medium of the reactor, preferably, the temperature of the condensed water is 10°C to 35°C, preferably 20°C to 35°C, more preferably 25°C to 35°C.
在本发明的一些优选的实施方式中，所述接触的条件还包括：控制乙烯在所述反应器内的压力为0.1MPa～30MPa，优选为0.5MPa～10MPa，更优选为0.5MPa～3MPa。In some preferred embodiments of the present invention, the contacting conditions further include: controlling the pressure of ethylene in the reactor to be 0.1MPa-30MPa, preferably 0.5MPa-10MPa, more preferably 0.5MPa-3MPa.
在本发明的一些优选的实施方式中，所述接触的条件还包括：控制所述接触的时间为10min～100min，优选为10min～50min，更优选为20min～40min。In some preferred embodiments of the present invention, the contact conditions further include: controlling the contact time to be 10 min to 100 min, preferably 10 min to 50 min, more preferably 20 min to 40 min.
在本发明的一些优选的实施方式中，式(1)中，R1-R11相同或不同，各自独立地选自氢、C1-C4直链烷基、C3-C6支链烷基、C3-C6环烷基、卤素、C1-C4烷氧基和硝基；R12选自氢、C1-C4直链烷基、C3-C6支链烷基、C3-C6环烷基、C6-C12烷芳基和C6-C12芳烷基；M为Fe(II)。In some preferred embodiments of the present invention, in formula (1), R1 -R11 are the same or different, each independently selected from hydrogen, C1 -C4 straight chain alkyl, C3 -C6 branched chain Alkyl, C3 -C6 cycloalkyl, halogen, C1 -C4 alkoxy and nitro; R12 is selected from hydrogen, C1 -C4 straight chain alkyl, C3 -C6 branched chain alkane group, C3 -C6 cycloalkyl group, C6 -C12 alkaryl group and C6 -C12 aralkyl group; M is Fe(II).
在本发明的一些优选的实施方式中，R1-R11相同或不同，各自独立地选自氢、甲基、乙基、正丙基、异丙基、氟、氯、溴、甲氧基、乙氧基和硝基；R12选自氢、C1-C4烷基、甲基苯基、1,2-二甲基苯基、1,3-二甲基苯基、1,4-二甲基苯基、苯甲基和苯乙基。In some preferred embodiments of the present invention, R1 -R11 are the same or different, each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, methoxy , ethoxy and nitro; R12 is selected from hydrogen, C1 -C4 alkyl, methylphenyl, 1,2-dimethylphenyl, 1,3-dimethylphenyl, 1,4 -Dimethylphenyl, benzyl and phenethyl.
在本发明的一些优选的实施方式中，R1-R6为氢，R7和R11为甲基，R8-R10为氢。In some preferred embodiments of the present invention, R1 -R6 are hydrogen, R7 and R11 are methyl, R8 -R10 are hydrogen.
在本发明的一些优选的实施方式中，所述含铝助催化剂选自选自烷基铝、三烯基铝、二烷基铝卤化物、烷基铝倍半卤化物、二烷基铝氢化物、部分氢化烷基铝、铝氧烷和二烷基铝醇盐中的一种或多种，In some preferred embodiments of the present invention, the aluminum-containing cocatalyst is selected from the group consisting of alkylaluminum, trienylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, dialkylaluminum hydride One or more of compounds, partially alkylaluminum hydrides, aluminoxanes and dialkylaluminum alkoxides,
其中，所述烷基铝的通式如式(2)所示，Wherein, the general formula of the alkylaluminum is shown in formula (2),
AlRnXm 式(2)AlRn Xm formula (2)
式(2)中，R各自独立地为直链或支链C1-C8烷基；X为卤素，优选氯或溴；n为1～3的整数，m为0～2的整数，并且m+n等于3；优选地，所述烷基铝选自三甲基铝、三乙基铝、三丙基铝、三异丁基铝、三正己基铝、三正辛基铝、氯化二乙基铝和二氯化乙基铝中的至少一种；更优选三乙基铝；In formula (2), R is each independently straight chain or branched C1 -C8 alkyl; X is halogen, preferably chlorine or bromine; n is an integer of 1 to 3, m is an integer of 0 to 2, and m+n is equal to 3; preferably, the alkylaluminum is selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, chloride At least one of diethylaluminum and ethylaluminum dichloride; more preferably triethylaluminum;
所述三烯基铝为三异戊二烯基铝；The trienyl aluminum is triisoprenyl aluminum;
所述烷基铝卤化物选自二乙基铝氯化物、二丁基铝氯化物、二异丁基铝氯化物和二乙基铝溴化物；The alkylaluminum halide is selected from diethylaluminum chloride, dibutylaluminum chloride, diisobutylaluminum chloride and diethylaluminum bromide;
所述烷基铝倍半卤化物选自乙基铝倍半氯化物、丁基铝倍半氯化物和乙基铝倍半溴化物；The alkyl aluminum sesquihalide is selected from ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide;
所述二烷基铝氢化物选自二乙基铝氢化物和二丁基铝氢化物；The dialkylaluminum hydride is selected from diethylaluminum hydride and dibutylaluminum hydride;
所述部分氢化烷基铝选自乙基铝二氢化物和丙基铝二氢化物；The partially alkylaluminum hydride is selected from ethylaluminum dihydride and propylaluminum dihydride;
所述氧烷选自甲基铝氧烷、异丁基铝氧烷、四乙基铝氧烷和四异丁基铝氧烷；The oxane is selected from methylalumoxane, isobutylalumoxane, tetraethylalumoxane and tetraisobutylalumoxane;
所述二烷基铝醇盐为二乙基铝乙醇盐。The dialkylaluminum alkoxide is diethylaluminum ethoxide.
在本发明的一些优选的实施方式中，所述有机溶剂选自惰性有机溶剂，优选为选自未经取代或经卤素取代的芳族烃溶剂、脂族烷烃、脂环族烃化合物和卤代烷烃中的一种或多种，优选自甲苯、苯、二甲苯、氯苯、二氯苯、氯甲苯、烷、己烷、庚烷、辛烷、壬烷、癸烷、环己烷、十氢化萘、二氯乙烷和二氯丁烷中的一种或多种，更优选为环己烷。In some preferred embodiments of the present invention, the organic solvent is selected from inert organic solvents, preferably from unsubstituted or halogen-substituted aromatic hydrocarbon solvents, aliphatic alkanes, alicyclic hydrocarbon compounds and halogenated alkanes One or more of, preferably selected from toluene, benzene, xylene, chlorobenzene, dichlorobenzene, chlorotoluene, alkane, hexane, heptane, octane, nonane, decane, cyclohexane, decahydro One or more of naphthalene, dichloroethane and dichlorobutane, more preferably cyclohexane.
在本发明的一些优选的实施方式中，所述催化剂中，以所述有机溶剂的总重量为计算基准，所述水的重量含量为100ppm～550ppm，优选为210ppm～240ppm，更优选为210ppm～230ppm，进一步优选为220ppm～230ppm。In some preferred embodiments of the present invention, in the catalyst, based on the total weight of the organic solvent, the weight content of the water is 100 ppm to 550 ppm, preferably 210 ppm to 240 ppm, more preferably 210 ppm to 230ppm, more preferably 220ppm-230ppm.
在本发明的一些优选的实施方式中，所述催化剂中，所述含铝助催化剂中的铝元素与所述主催化剂中的M元素的摩尔比为30:1～小于900:1，优选为100:1～700:1，更优选为148:1～196:1。In some preferred embodiments of the present invention, in the catalyst, the molar ratio of the aluminum element in the aluminum-containing cocatalyst to the M element in the main catalyst is 30:1 to less than 900:1, preferably 100:1-700:1, more preferably 148:1-196:1.
在本发明的一些优选的实施方式中，所述催化剂中，以所述催化剂的总体积为计算基准，所述主催化剂的含量为1μmol/L～500μmol/L，优选为10μmol/L～300μmol/L，更优选为10μmol/L～100μmol/L。In some preferred embodiments of the present invention, in the catalyst, based on the total volume of the catalyst, the content of the main catalyst is 1 μmol/L to 500 μmol/L, preferably 10 μmol/L to 300 μmol/L L is more preferably 10 μmol/L to 100 μmol/L.
根据本发明，本发明所提供的催化工艺可以适用于单釜工艺也可以采用多釜串联工艺。本领域技术人员可以根据生产需求进行选择。According to the present invention, the catalytic process provided by the present invention can be applied to a single-pot process or a multi-pot process in series. Those skilled in the art can make a selection according to production requirements.
本发明的有益效果至少在于以下几个方面：The beneficial effects of the present invention lie at least in the following aspects:
其一，本发明所提供的催化工艺能够在较高的温度范围内(例如40℃～90℃)进行，反应撤热介质可以采用冷凝水，与冷冻水相比降低了能耗。从而克服了本领域技术人员的技术偏见，取得了预料不到的技术效果。First, the catalytic process provided by the present invention can be carried out in a relatively high temperature range (for example, 40°C to 90°C), and the heat removal medium for the reaction can be condensed water, which reduces energy consumption compared with chilled water. Thereby, the technical bias of those skilled in the art is overcome, and unexpected technical effects are achieved.
其二，本发明所提供的催化工艺能够具有较高的催化活性，且α-烯烃的选择性可以达到96％以上。Second, the catalytic process provided by the present invention can have high catalytic activity, and the selectivity of α-olefins can reach more than 96%.
其三，本发明所提供的催化工艺可以以廉价易得的环己烷作为溶剂，并且，除了能够降低生产成本，采用环己烷作为溶剂还能够使得齐聚产品中不含有杂质。Third, the catalytic process provided by the present invention can use cheap and easy-to-obtain cyclohexane as a solvent, and, in addition to reducing production costs, using cyclohexane as a solvent can also make the oligomerization product free of impurities.
具体实施方式Detailed ways
以下通过实施例对本发明进行详细说明，但本发明的保护范围并不限于下述说明。The present invention will be described in detail through examples below, but the protection scope of the present invention is not limited to the following description.
实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购途径获得的常规产品。Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be obtained through commercial channels.
在本发明中，产物分布系数(k)＝乙烯齐聚链增长速率/(链增长速率+链转移速率)＝C2n+2/C2n。In the present invention, product distribution coefficient (k)=ethylene oligomerization chain growth rate/(chain growth rate+chain transfer rate)=C2n+2 /C2n .
在本发明中，Al/Fe均是指铝元素与铁元素的摩尔比。In the present invention, Al/Fe both refer to the molar ratio of aluminum element to iron element.
下述实施方式中，所用环己烷溶剂均为无水环己烷。In the following embodiments, the cyclohexane solvent used is anhydrous cyclohexane.
实施例1Example 1
(1)通过高温烘干、真空置换等操作对反应釜进行置换，确保反应釜中无水无氧；(1) Replace the reactor by high-temperature drying, vacuum replacement and other operations to ensure that there is no water and oxygen in the reactor;
(2)使用乙烯对反应釜进行置换，使反应体系处于乙烯环境；(2) Use ethylene to replace the reactor so that the reaction system is in an ethylene environment;
(3)在反应釜中加入水和环己烷溶剂，加入1.37mL三乙基铝环己烷溶液(三乙基铝的浓度为715μmol/mL)，加入2mL氯化-2-甲酰基-1,10-菲咯啉缩-2,6-二甲基苯胺合铁(II)配合物的环己烷溶液(氯化-2-甲酰基-1,10-菲咯啉缩-2,6-二甲基苯胺合铁(II)配合物的浓度为2.5μmol/mL)后，使组合物总量为100mL，其中，以环己烷的重量为计算基准，水的重量含量为225ppm，Al/Fe(摩尔比)＝196，充分搅拌后，通入乙烯开始齐聚反应；(3) Add water and cyclohexane solvent into the reaction kettle, add 1.37mL triethylaluminum cyclohexane solution (the concentration of triethylaluminum is 715μmol/mL), add 2mL chloride-2-formyl-1 , 10-phenanthroline-2,6-dimethylanilinium iron (II) complex cyclohexane solution (chloro-2-formyl-1,10-phenanthroline-2,6- After the concentration of dimethylaniline iron (II) complex is 2.5 μ mol/mL), make the composition total amount be 100mL, wherein, take the weight of cyclohexane as calculation basis, the weight content of water is 225ppm, Al/ Fe (molar ratio)=196, after fully stirring, feed ethylene and start oligomerization reaction;
(4)保持乙烯压力为1MPa且反应温度为60℃下反应30分钟；(4) Keeping the ethylene pressure at 1 MPa and the reaction temperature at 60° C. for 30 minutes;
(5)停止反应，取出少量反应产物用气相色谱进行(GC)分析，具体分析结果见表1。(5) Stop the reaction, take out a small amount of reaction product and carry out (GC) analysis with gas chromatography, the specific analysis results are shown in Table 1.
实施例2Example 2
(1)通过高温烘干、真空置换等操作对反应体系进行置换，确保反应釜中无水无氧；(1) Replace the reaction system through high temperature drying, vacuum replacement and other operations to ensure that there is no water and no oxygen in the reaction kettle;
(2)使用乙烯对反应体系进行置换，使反应体系处于乙烯环境；(2) Use ethylene to replace the reaction system so that the reaction system is in an ethylene environment;
(3)在反应釜中加入水和无水环己烷溶剂，加入1.37mL三乙基铝环己烷溶液(三乙基铝的浓度为715μmol/mL)，加入2mL氯化-2-苯甲酰基-1,10-菲咯啉缩-2,6-二甲基苯胺合铁(II)配合物的环己烷溶液(氯化-2-苯甲酰基-1,10-菲咯啉缩-2,6-二甲基苯胺合铁(II)配合物的浓度为2.5μmol/mL)后，使环己烷溶液总量为100mL，其中，以环己烷的重量为计算基准，水的重量含量为225ppm，Al/Fe＝196，充分搅拌后，通入乙烯开始齐聚反应；(3) Add water and anhydrous cyclohexane solvent into the reaction kettle, add 1.37mL triethylaluminum cyclohexane solution (the concentration of triethylaluminum is 715μmol/mL), add 2mL chloride-2-benzene Cyclohexane solution of acyl-1,10-phenanthroline-2,6-dimethylanilinate iron (II) complex (chloro-2-benzoyl-1,10-phenanthroline- After the concentration of 2,6-dimethylaniline iron (II) complex is 2.5 μ mol/mL), make the cyclohexane solution total amount be 100mL, wherein, take the weight of cyclohexane as calculation basis, the weight of water The content is 225ppm, Al/Fe=196, after fully stirring, feed ethylene to start the oligomerization reaction;
(4)保持乙烯压力为1MPa且反应温度为50℃下反应30分钟；(4) Keeping the ethylene pressure at 1 MPa and the reaction temperature at 50° C. for 30 minutes;
(5)停止反应，取出少量反应产物用气相色谱进行(GC)分析：齐聚活性为2.59×107g·mol(Fe)-1·h-1，C4含量为17.82％，其中含线性α-烯烃98.60％。剩余的混合物用5％的盐酸酸化的乙醇溶液中和，没有得到聚合物。K值为0.63。(5) Stop the reaction, take out a small amount of reaction product and analyze it by gas chromatography (GC): the oligomerization activity is 2.59×107 g·mol(Fe)-1 ·h-1 , the C4 content is 17.82%, which contains linear α-olefin 98.60%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained. The K value is 0.63.
具体分析结果见表1。The specific analysis results are shown in Table 1.
实施例3Example 3
(1)通过高温烘干、真空置换等操作对反应体系进行置换，确保反应釜中无水无氧；(1) Replace the reaction system through high temperature drying, vacuum replacement and other operations to ensure that there is no water and no oxygen in the reaction kettle;
(2)使用乙烯对反应体系进行置换，使反应体系处于乙烯环境；(2) Use ethylene to replace the reaction system so that the reaction system is in an ethylene environment;
(3)在反应釜中加入水和环己烷溶剂，加入1.37mL三乙基铝环己烷溶液(三乙基铝的浓度为715μmol/mL)，加入2mL氯化-2-丙酰基-1,10-菲咯啉缩-2,6-二甲基苯胺合铁(II)配合物的环己烷溶液(氯化-2-丙酰基-1,10-菲咯啉缩-2,6-二甲基苯胺合铁(II)配合物的浓度为2.5μmol/mL)后，使组合物总量为100mL，其中，以环己烷的重量为计算基准，水的重量含量为225ppm，Al/Fe＝196，充分搅拌后，通入乙烯开始齐聚反应；(3) Add water and cyclohexane solvent into the reaction kettle, add 1.37mL triethylaluminum cyclohexane solution (the concentration of triethylaluminum is 715μmol/mL), add 2mL chloride-2-propionyl-1 , 10-phenanthroline-2,6-dimethylanilinium iron (II) complex in cyclohexane (chlorinated-2-propionyl-1,10-phenanthroline-2,6- After the concentration of dimethylaniline iron (II) complex is 2.5 μ mol/mL), make the composition total amount be 100mL, wherein, take the weight of cyclohexane as calculation basis, the weight content of water is 225ppm, Al/ Fe=196, after fully stirring, feed ethylene to start oligomerization;
(4)保持乙烯压力为1MPa且反应温度为50℃下反应30分钟；(4) Keeping the ethylene pressure at 1 MPa and the reaction temperature at 50° C. for 30 minutes;
(5)停止反应，取出少量反应产物用气相色谱进行(GC)分析：齐聚活性为3.06×107g·mol(Fe)-1·h-1，C4含量为14.24％，其中含线性α-烯烃98.7％。剩余的混合物用5％的盐酸酸化的乙醇溶液中和，没有得到聚合物。K值为0.66。(5) Stop the reaction, take out a small amount of reaction product and analyze it by gas chromatography (GC): the oligomerization activity is 3.06×107 g·mol(Fe)-1 ·h-1 , the C4 content is 14.24%, which contains linear α-olefin 98.7%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained. The K value is 0.66.
具体分析结果见表1。The specific analysis results are shown in Table 1.
实施例4Example 4
(1)通过高温烘干、真空置换等操作对反应体系进行置换，确保反应釜中无水无氧；(1) Replace the reaction system through high temperature drying, vacuum replacement and other operations to ensure that there is no water and no oxygen in the reaction kettle;
(2)使用乙烯对反应体系进行置换，使反应釜处于乙烯环境；(2) Use ethylene to replace the reaction system so that the reactor is in an ethylene environment;
(3)在反应釜中加入水和无水环己烷溶剂，加入1.37mL三乙基铝环己烷溶液(三乙基铝的浓度为715μmol/mL)，加入2mL氯化-2-丁酰基-1,10-菲咯啉缩-2,6-二甲基苯胺合铁(II)配合物的环己烷溶液(氯化-2-丁酰基-1,10-菲咯啉缩-2,6-二甲基苯胺合铁(II)配合物的浓度为2.5μmol/mL)后，使组合物总量为100mL，其中，以环己烷的重量为计算基准，水的重量含量为225ppm，Al/Fe＝196，充分搅拌后，通入乙烯开始齐聚反应；(3) Add water and anhydrous cyclohexane solvent into the reaction kettle, add 1.37mL triethylaluminum cyclohexane solution (the concentration of triethylaluminum is 715μmol/mL), add 2mL chloride-2-butyryl Cyclohexane solution of -1,10-phenanthroline-2,6-dimethylanilinium iron (II) complex (chloro-2-butyryl-1,10-phenanthroline-2, After the concentration of 6-dimethylaniline iron (II) complex is 2.5 μ mol/mL), make the composition total amount be 100mL, wherein, take the weight of cyclohexane as calculation basis, the weight content of water is 225ppm, Al/Fe=196, after fully stirring, feed ethylene to start oligomerization;
(4)保持乙烯压力为1MPa且反应温度为50℃下反应30分钟；(4) Keeping the ethylene pressure at 1 MPa and the reaction temperature at 50° C. for 30 minutes;
(5)停止反应，取出少量反应产物用气相色谱进行(GC)分析：齐聚活性为3.12×107g·mol(Fe)-1·h-1，C4含量为13.40％，其中含线性α-烯烃98.6％。剩余的混合物用5％的盐酸酸化的乙醇溶液中和，没有得到聚合物。K值为0.67。(5) Stop the reaction, take out a small amount of reaction product and analyze it by gas chromatography (GC): the oligomerization activity is 3.12×107 g·mol(Fe)-1 ·h-1 , the C4 content is 13.40%, which contains linear α-olefin 98.6%. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was obtained. The K value is 0.67.
具体分析结果见表1。The specific analysis results are shown in Table 1.
实施例5Example 5
(1)通过高温烘干、真空置换等操作对反应釜进行置换，确保反应釜中无水无氧；(1) Replace the reactor by high-temperature drying, vacuum replacement and other operations to ensure that there is no water and oxygen in the reactor;
(2)使用乙烯对反应釜进行置换，使反应体系处于乙烯环境；(2) Use ethylene to replace the reactor so that the reaction system is in an ethylene environment;
(3)在反应釜中加入水和环己烷溶剂，加入1.37mL三乙基铝环己烷溶液(三乙基铝的浓度为715μmol/mL)，加入2mL氯化-2-异丁酰基-1,10-菲咯啉缩-2,6-二甲基苯胺合铁(II)配合物的环己烷溶液(氯化-2-异丁酰基-1,10-菲咯啉缩-2,6-二甲基苯胺合铁(II)配合物的浓度为2.5μmol/mL)后，使组合物总量为100mL，其中，以环己烷的重量为计算基准，水的重量含量为225ppm，Al/Fe＝196，充分搅拌后，通入乙烯开始齐聚反应；(3) Add water and cyclohexane solvent into the reaction kettle, add 1.37mL triethylaluminum cyclohexane solution (the concentration of triethylaluminum is 715μmol/mL), add 2mL chloride-2-isobutyryl- Cyclohexane solution of 1,10-phenanthroline-2,6-dimethylanilinium iron (II) complex (chloro-2-isobutyryl-1,10-phenanthroline-2, After the concentration of 6-dimethylaniline iron (II) complex is 2.5 μ mol/mL), make the composition total amount be 100mL, wherein, take the weight of cyclohexane as calculation basis, the weight content of water is 225ppm, Al/Fe=196, after fully stirring, feed ethylene to start oligomerization;
(4)保持乙烯压力为1MPa且反应温度为50℃下反应30分钟；(4) Keeping the ethylene pressure at 1 MPa and the reaction temperature at 50° C. for 30 minutes;
(5)停止反应，取出少量反应产物用气相色谱进行(GC)分析，具体分析结果见表1。(5) Stop the reaction, take out a small amount of reaction product and carry out (GC) analysis with gas chromatography, the specific analysis results are shown in Table 1.
实施例6Example 6
采用“氯化-2-甲酰基-1,10-菲咯啉缩-2,6-二乙基苯胺合铁(II)配合物”替换实施例1中的“氯化-2-甲酰基-1,10-菲咯啉缩-2,6-二甲基苯胺合铁(II)配合物”。Replace the "chlorinated-2-formyl- 1,10-phenanthroline-2,6-dimethylanilinate iron (II) complex".
在反应停止后，取出少量反应产物用气相色谱进行(GC)分析，具体分析结果见表1。After the reaction stopped, a small amount of reaction product was taken out and analyzed by gas chromatography (GC). The specific analysis results are shown in Table 1.
实施例7Example 7
采用“甲苯”替换实施例1中的“环己烷”。"Cyclohexane" in Example 1 is replaced with "toluene".
在反应停止后，取出少量反应产物用气相色谱进行(GC)分析，具体分析结果见表1。After the reaction stopped, a small amount of reaction product was taken out and analyzed by gas chromatography (GC). The specific analysis results are shown in Table 1.
实施例8Example 8
采用“甲基铝氧烷”替换实施例1中的“三乙基铝”。"Triethylaluminum" in Example 1 was replaced with "methylaluminoxane".
在反应停止后，取出少量反应产物用气相色谱进行(GC)分析，具体分析结果见表1。After the reaction stopped, a small amount of reaction product was taken out and analyzed by gas chromatography (GC). The specific analysis results are shown in Table 1.
对比例1Comparative example 1
与实施例1的不同之处仅在于“反应温度为10℃”。The only difference from Example 1 is "the reaction temperature is 10°C".
在反应停止后，取出少量反应产物用气相色谱进行(GC)分析，具体分析结果见表1。After the reaction stopped, a small amount of reaction product was taken out and analyzed by gas chromatography (GC). The specific analysis results are shown in Table 1.
对比例2Comparative example 2
与实施例1的不同之处仅在于“反应温度为30℃”。The only difference from Example 1 is "the reaction temperature is 30°C".
在反应停止后，取出少量反应产物用气相色谱进行(GC)分析，具体分析结果见表1。After the reaction stopped, a small amount of reaction product was taken out and analyzed by gas chromatography (GC). The specific analysis results are shown in Table 1.
表1Table 1
注：上表中，k指产物分布系数。Note: In the above table, k refers to the product distribution coefficient.
根据上表中的数据可以看出，采用本发明所提供的乙烯齐聚工艺能够降低不期望的C4烯烃和C20～C28烯烃的含量，提高期望的C6～C18，尤其是C6～C18线性α-烯烃的含量。并且，本发明的乙烯齐聚工艺能够在较高的温度下进行，这使得工业应用中，均可以采用冷凝水作为撤热介质而不必采用冷却水。According to the data in the above table, it can be seen that the ethylene oligomerization process provided by the present invention can reduce the content of undesired C4 olefins and C20 -C28 olefins, and increase the desired C6 -C18 , especially C6 ~C18 linear α-olefin content. Moreover, the ethylene oligomerization process of the present invention can be carried out at a relatively high temperature, which makes it possible to use condensed water as a heat removal medium instead of cooling water in industrial applications.
应当注意的是，以上所述的实施例仅用于解释本发明，并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述，但应当理解为其中所用的词语为描述性和解释性词汇，而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改，以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可扩展至其他所有具有相同功能的方法和应用。It should be noted that the above-mentioned embodiments are only used to explain the present invention, and do not constitute any limitation to the present invention. The invention has been described with reference to typical embodiments, but the words which have been used therein are words of description and explanation rather than words of limitation. The present invention can be modified within the scope of the claims of the present invention as prescribed, and the present invention can be revised without departing from the scope and spirit of the present invention. Although the invention described therein refers to specific methods, materials and examples, it is not intended that the invention be limited to the specific examples disclosed therein, but rather, the invention extends to all other methods and applications having the same function.
Claims (10)
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