Búsqueda Imágenes Maps Play YouTube Noticias Gmail Drive Más »
Iniciar sesión
Usuarios de lectores de pantalla: deben hacer clic en este enlace para utilizar el modo de accesibilidad. Este modo tiene las mismas funciones esenciales pero funciona mejor con el lector.

Patentes

  1. Búsqueda avanzada de patentes
Número de publicaciónCN103769100 B
Tipo de publicaciónConcesión
Número de solicitudCN 201210408285
Fecha de publicación12 Ago 2015
Fecha de presentación24 Oct 2012
Fecha de prioridad24 Oct 2012
También publicado comoCN103769100A
Número de publicación201210408285.3, CN 103769100 B, CN 103769100B, CN 201210408285, CN-B-103769100, CN103769100 B, CN103769100B, CN201210408285, CN201210408285.3
Inventores李 杰, 张舒冬, 张喜文, 倪向前, 宋喜军
Solicitante中国石油化工股份有限公司, 中国石油化工股份有限公司抚顺石油化工研究院
Exportar citaBiBTeX, EndNote, RefMan
Enlaces externos:  SIPO, Espacenet
一种费托合成催化剂及其制备方法和应用 One kind of Fischer-Tropsch synthesis catalyst and preparation method and application traducido del chino
CN 103769100 B
Resumen  traducido del chino
本发明公开一种钴基费托合成催化剂及其制备方法和应用。 The present invention discloses a cobalt-based Fischer - Tropsch synthesis catalyst preparation method and applications. 钴基费托合成催化剂以硅胶为载体,按催化剂的重量含量计,含有0.5%-6%的金属助剂,5%-35%的活性组分钴,所述的金属助剂为Re、Zr、Hf、Ce和Th等中的一种或几种,所述的硅胶载体为热氢气处理过的硅胶载体,热氢气的温度为350-650℃,处理时间1-30h,热氢气的空速为1000h-1-2000h-1。 Cobalt-based Fischer - Tropsch synthesis catalyst with silica gel as a carrier, according to the weight content of the catalyst, containing 0.5% to 6% of metal additives, 5% -35% of the active ingredient cobalt, said metal additive is Re, Zr , Hf, Ce and Th and the like of one or several, of the silica carrier is hot hydrogen-treated silica gel support, the temperature of hot hydrogen 350-650 ℃, the processing time is 1-30h, hot hydrogen space velocity to 1000h-1-2000h-1. 该方法制备过程简单,催化剂在长周期及高空速的运转条件下显示出优良的活性稳定性,适合于工业应用。 The preparation process is simple, the catalyst exhibits excellent activity stability under operating conditions and high altitude long cycle speed, suitable for industrial applications.
Reclamaciones(10)  traducido del chino
1. 一种钴基费托合成催化剂,以硅胶为载体,按催化剂的重量含量计,含有0. 5%-6%的金属助剂,5%-35%的活性组分钴,所述的金属助剂为Re、Zr、Hf、Ce和Th中的一种或几种, 其特征在于:所述的硅胶载体为热氢气处理过的硅胶载体,热氢气的温度为350_650°C,处理时间l-30h,热氢气的空速为1000 1^-2000 h' A cobalt-based Fischer - Tropsch synthesis catalyst and silica gel as a carrier, according to the weight content of the catalyst, containing 0.5% -6% of metal additives, 5% -35% of the active ingredient cobalt, said metal promoter is Re, Zr, Hf, Ce and Th in one or several, characterized in that: said silica carrier is hot hydrogen-treated silica gel support, the temperature of hot hydrogen 350_650 ° C, the processing time l-30h, hot hydrogen space velocity 1000 1 ^ -2000 h '
2. 根据权利要求1所述的催化剂,其特征在于:所述的钴基费托合成催化剂中按催化剂的重量含量计含有1%_3%的金属助剂,所述的助剂为锆。 2. The catalyst according to claim 1, characterized in that: a cobalt based Fischer - Tropsch synthesis catalyst in the catalyst by weight content _3% containing 1% of metal additives, said additive is zirconium.
3. 根据权利要求1所述的催化剂,其特征在于:所述的钴基费托合成催化剂中硅胶载体热氢气处理过程中压力控制为0. 5-2. 5 MPa。 The catalyst according to claim 1, characterized in that: said cobalt based Fischer - Tropsch synthesis catalyst treated silica gel support during hot hydrogen pressure was controlled to 0. 5-2 5 MPa..
4. 权利要求1所述的钴基费托合成催化剂的制备方法,包括如下过程:以硅胶为载体, 首先对硅胶载体进行预处理,然后采用浸渍法负载金属助剂和活性组分Co ;其特征在于: 其中硅胶载体的预处理方法为向硅胶载体中通入温度为350-650°C的热氢气,处理时间l_30h,热氢气的空速为10001^-200(¾' The method for preparing a cobalt based Fischer - Tropsch synthesis catalyst according to claim, the process comprising the following: silica gel as a carrier, first pretreated silica carrier, and then by impregnation loading of metal additives and active ingredients Co; thereof characterized by: wherein silica support pretreatment method to pass into the silica support is 350-650 ° C temperature of hot hydrogen, treatment time l_30h, hot hydrogen space velocity 10001 ^ -200 (¾ '
5. 根据权利要求4所述的方法,其特征在于:所述的硅胶载体的预处理方法为向硅胶载体中通入温度为400-600°C的热氢气,处理时间不少于10h,热氢气的空速为12001^-180(¾' 5. The method according to claim 4, wherein: said silica carrier pretreatment method is to pass into the silica support to a temperature of 400-600 ° C hot hydrogen, treatment time of not less than 10h, heat hydrogen space velocity of 12001 ^ -180 (¾ '
6. 根据权利要求4所述的方法,其特征在于:热氢气处理过程中压力控制为0. 5-2. 5 MPa0 6. The method according to claim 4, characterized in that: the heat treatment process hydrogen pressure was controlled to 0. 5-2 5 MPa0.
7. 根据权利要求4所述的方法,其特征在于:热氢气预处理过程在固定床反应器中进行,通入热氢气之前需要进行气体置换,保证固定床内氧气的体积浓度小于99. 9%,热氢气来自于氢气加热炉。 7. The method according to claim 4, characterized in that: hot hydrogen pretreatment process in a fixed bed reactor, the gas replacement is required before introducing hot hydrogen, to ensure the volume concentration of oxygen in a fixed bed is less than 99.9 %, hot hydrogen from the hydrogen furnace.
8. 按照权利要求4所述的方法,其特征在于:所述的金属助剂为Re、Zr、Hf、Ce和Th中的一种或几种,金属助剂的重量百分含量为〇. 5%-6% ;所述活性组分钴的重量百分含量为5%-35%〇 8. The method according to claim 4, wherein, wherein: said metal additive is Re, Zr, Hf, Ce and Th in one or more of the metal weight percentage of aid for the square. 5% -6%; the weight percentage of the active component cobalt is 5% -35% billion
9. 按照权利要求4所述的方法,其特征在于:金属助剂和活性组分Co采用先浸渍金属助剂,然后浸渍活性组分Co的分步浸渍法。 9. A method according to claim 4 or claim, characterized in that: the metal additives and the active ingredient Co impregnation using the first metal additives, and then impregnated with the active ingredient Co stepwise impregnation method.
10. 权利要求1至3任一权利要求所述的催化剂在费托合成反应中的应用。 10. The process according to any one of 1-3 Claim wherein the reaction catalyst used in the Fischer-Tropsch synthesis.
Descripción  traducido del chino
一种费托合成催化剂及其制备方法和应用 One kind of Fischer-Tropsch synthesis catalyst and preparation method and application

技术领域 TECHNICAL FIELD

[0001] 本发明涉及一种钴基费托合成催化剂及其制备方法和应用,具体地说涉及一种以改性硅胶为载体,添加金属助剂修饰的高活性稳定性的钴基费托合成催化剂的制备方法。 [0001] The present invention relates to a cobalt-based Fischer - Tropsch synthesis catalyst preparation method and application, and more particularly relates to a modified silica gel as a carrier, adding a metal additive modified high activity cobalt-based Fischer - Tropsch synthesis stability method of catalyst preparation.

背景技术 Background technique

[0002] 随着石油资源的日益枯竭,以费托合成反应制备液体燃料更加受到了世界各国的重视。 [0002] With the increasing depletion of oil resources to the preparation of Fischer-Tropsch synthesis reaction of the liquid fuel more by the world's attention. 催化剂是费托合成反应的关键技术之一。 The catalyst is a key technology for Fischer-Tropsch synthesis reaction. 在近八十年的费托催化剂的研宄中,人们已发现Fe、Co和Ru等是费托催化剂有效的活性组分,Zr、K和Cu等各种助剂元素对费托催化剂的活性、稳定性起着重要的作用,而催化剂的载体以无定型的Si02、1102和Al 203为主。 In nearly 80 years of study based Fischer-Tropsch catalyst, people have been found Fe, Co, and Ru, Fischer-Tropsch catalyst is effective active ingredients, Zr, K and Cu and other elements on the Fischer-Tropsch catalyst additives activity stability plays an important role, and the catalyst carrier with amorphous Si02,1102 and Al 203-based. 如何对活性组分、金属助剂和载体进行有效合理的搭配,制备出具有高活性、高选择性和高稳定性的费托合成催化剂是研宄的热点。 How many of the active ingredient, metal additives and carrier effective and reasonable collocation, prepared with high activity, high selectivity and high stability of Fischer-Tropsch synthesis catalyst is a study based on focus. 使用钴基催化剂不仅能最大限度地生成重质径,而且钴基催化剂积炭倾向低、活性高,因此,以钴基催化剂为基础的研宄具有重要意义。 Using a cobalt-based catalyst not only to maximize the generation of heavy diameter, and low cobalt-based catalyst coke tendency, high activity, so the cobalt-based catalyst based study based on great significance.

[0003] CN1454714A公开了一种钴基费托合成催化剂的制备方法,该方法采用1%-25%的氨水溶液对SiO2载体室温老化6-150小时,100-150°C下烘8-24小时进行表面改性,提高了钴基费托合成催化剂的活性,在220°C,2MPa下,CO转化率为90. 1%,C5+选择性为85. 7%。 [0003] CN1454714A discloses a method for preparing a cobalt-based Fischer - Tropsch synthesis catalyst, which uses 1% -25% ammonia solution at room temperature for SiO2 carrier aging 6-150 hours, bake at 100-150 ° C for 8-24 hours surface modified to improve the activity of cobalt-based Fischer - Tropsch synthesis catalyst, at 220 ° C, under 2MPa, CO conversion was 90. 1%, C5 + selectivity of 85.7%. 碱金属和氨的氢氧化物会对催化剂载体的表面具有一定的破坏作用,某些改性剂还可能引入一些金属离子杂质。 The surface of the catalyst carrier alkali metal hydroxides and ammonia will have some destructive effect, certain modifiers may also introduce some metal ion impurities.

[0004] CN200510130076. 7公开了一种钴基费托合成催化剂的制备方法,先将含钴化合物、含铝化合物和有机助溶剂与水混合成溶液,将该溶液在含氧气氛下加热至燃烧,烧除有机助溶剂,得到一种粉体产物,最后在空气存在下,将所述粉体产物在100-1000 °c中焙烧0. 5-36小时的方法制备。 [0004] CN200510130076. 7 discloses a method for preparing a cobalt based Fischer - Tropsch synthesis catalyst, the first containing cobalt compound, aluminum compound and an organic co-solvent and water are mixed into a solution, the solution was heated to combustion in an oxygen-containing atmosphere, burning organic cosolvent, to obtain a powder product, and finally in the presence of air, the powder was calcined at 100-1000 ° c 0.5 5-36 hours in the preparation of addition. 其中使用的有机助溶剂为有机胺、有机酸、有机肼中的一种或几种。 Wherein the organic cosolvent used is an organic amine, organic acids, organic hydrazine in one or several. 该方法制备过程复杂。 The preparation process is complicated.

[0005] CN200910011990. 8、CN200910011989. 5、CN200910011988. 0 公开的钴基费托合成催化剂的制备方法中,以硅胶为载体,首先对硅胶载体进行表面改性,然后采用浸渍法负载金属助剂和活性组分Co ;其中硅胶载体的表面改性方法分别采用含铵盐的缓冲溶液、含氮有机化合物溶液及糖的酸性溶液进行浸渍处理。 [0005] CN200910011990. 8, CN200910011989. 5, CN200910011988. Preparation 0 cobalt based Fischer - Tropsch synthesis catalysts disclosed in the silica gel as a carrier, the first carrier of the silica surface modification, then by impregnation load metal additives and the active ingredient Co; wherein the surface modification method of the silica support were used a buffer solution containing ammonium salt, an acidic solution of a nitrogen-containing organic compound is a sugar solution and an immersion treatment. 上述方法在降低费托合成反应温度、避免载体改性过程中强酸或强碱性溶液对其表面的腐蚀和对载体孔结构的损坏,提高催化剂寿命及活性等方面取得了显著的进步。 The above methods have made significant progress in reducing the Fischer-Tropsch synthesis reaction temperature to avoid carrier modified during strong acid or alkaline solution to their corrosion and damage the surface of the pore structure of the carrier, to improve catalyst life and activity and so on. 但是随着研宄的深入进行,发现上述制备方法得到的催化剂在长周期及高空速的运转条件下,催化剂的活性稳定性仍有待进一步的提高。 But with the study based on the depth and found that the above-prepared catalyst obtained under operating conditions of a long cycle and high space velocity, catalyst activity and stability still need to be further improved.

发明内容 SUMMARY OF THE INVENTION

[0006] 针对现有技术的不足,特别是针对在长周期及高空速的运转条件下,钴基费托合成催化剂存在着活性稳定性不理想的问题,本发明公开一种钴基费托合成催化剂及其制备方法和应用,该方法制备过程简单,催化剂在长周期及高空速的运转条件下显示出优良的活性稳定性,适合于工业应用。 [0006] for the deficiencies of the prior art, especially in the operating conditions for a long period and a high space velocity, cobalt based Fischer - Tropsch synthesis catalyst there is the problem of undesirable activity stability, discloses a cobalt based Fischer - Tropsch synthesis of the present invention The catalyst preparation method and application, the preparation process is simple and the catalyst exhibits excellent activity stability under operating conditions and high altitude long cycle speed, suitable for industrial applications.

[0007] -种钴基费托合成催化剂,以硅胶为载体,按催化剂的重量含量计,含有0. 5%_6% 的金属助剂,5%-35%的活性组分钴,所述的金属助剂为Re、Zr、Hf、Ce和Th等中的一种或几种,所述的硅胶载体为热氢气处理过的硅胶载体,热氢气的温度为350-650°C,处理时间l_30h,热氢气的空速为1000 1^-2000 h' [0007] - kind of cobalt based Fischer - Tropsch synthesis catalyst, the silica gel as a carrier, by weight content of the catalyst, containing 0.5% of metal additives _6%, 5% to 35% of the active ingredient cobalt, wherein metal promoter is Re, Zr, Hf, Ce and Th and the like of one or several, of the silica carrier is hot hydrogen-treated silica gel support, the temperature of the hydrogen heat 350-650 ° C, the processing time l_30h hot hydrogen space velocity 1000 1 ^ -2000 h '

[0008] 本发明所述的钴基费托合成催化剂中按催化剂的重量含量计含有1%_3%的金属助剂,所述的助剂为锆。 [0008] Cobalt based Fischer - Tropsch synthesis catalyst in the present invention by a catalyst containing 1% weight content _3% metal additive, wherein the additive is zirconium.

[0009] 本发明所述的钴基费托合成催化剂中硅胶载体为热氢气处理过的硅胶载体,处理过程中压力控制为〇· 5-2. 5 MPa。 [0009] cobalt-based Fischer - Tropsch synthesis catalyst of the present invention, the carrier is silica gel in hot hydrogen-treated silica gel support, the pressure control process is square · 5-2. 5 MPa.

[0010] 一种钴基费托合成催化剂的制备方法,包括如下过程:以硅胶为载体,首先对硅胶载体进行预处理,然后采用浸渍法负载金属助剂和活性组分Co ;其中硅胶载体的预处理方法为向硅胶载体中通入温度为350-650°C的热氢气,处理时间l_30h,热氢气的空速为1000 h_1-2000 h_1〇 [0010] A method for preparing a cobalt based Fischer - Tropsch synthesis catalyst, comprising the following processes: silica gel as a carrier, first pretreated silica carrier, and then by impregnation loading of metal additives and the active ingredient Co; wherein the silica support pretreatment of the silica support was introduced into a temperature of 350-650 ° C hot hydrogen, treatment time l_30h, hot hydrogen space velocity of 1000 h_1-2000 h_1〇

[0011] 本发明方法中所述的硅胶载体的预处理方法为向硅胶载体中通入温度为400-600°C的热氢气,处理时间不少于10h,热氢气的空速为1200 1^-1800 h' [0011] The pretreated silica carrier in the method of the present invention is to pass into the silica support to a temperature of 400-600 ° C hot hydrogen, treatment time of not less than 10h, hot hydrogen space velocity of 12,001 ^ -1800 h '

[0012] 本发明方法中,处理过程中压力控制为0· 5-2. 5 MPa,优选1. 0-2. 0 MPa。 [0012] The method of the present invention, the process pressure is controlled to 0 · 5-2. 5 MPa, preferably 1. 0-2. 0 MPa.

[0013] 本发明方法中,热氢气预处理过程可以在固定床反应器中进行,通入热氢气之前需要进行气体置换,保证固定床内氧气的体积浓度小于99. 9%。 [0013] The method of the present invention, the hot hydrogen pretreatment process can be carried out in a fixed bed reactor, the gas replacement is required before introducing hot hydrogen, to ensure that the volume concentration of oxygen in a fixed bed is less than 99.9%. 热氢气来自于氢气加热炉。 Hot hydrogen from the hydrogen furnace.

[0014] 本发明钴基费托合成催化剂的制备方法中,硅胶载体可以采用现有硅胶产品,如大孔或细孔的干燥微球,硅胶可以按需要采用商品,也可以按现有方法制备。 [0014] The method for preparing a cobalt based Fischer - Tropsch synthesis catalyst of the present invention, the silica gel support can be employed conventional silicone products, such as dried microspheres or macroporous pores, silica gel may be adopted as needed commodity, can also be prepared by a conventional method .

[0015] 本发明钴基费托合成催化剂的制备方法中,金属助剂可以是Re、Zr、Hf、Ce和Th等中的一种或几种,优选Zr。 [0015] preparation of cobalt based Fischer - Tropsch synthesis catalyst of the present invention, the metal additive can be Re, Zr, Hf, Ce and Th in one or several, preferably Zr. 金属助剂和活性组分Co的负载方法优选先浸渍金属助剂,然后浸渍活性组分Co的分步浸渍法。 Load method metal additives and active ingredient Co is preferably first impregnated metal additives, then dipping the active ingredient Co stepwise impregnation method. 金属助剂和活性组分Co的浸渍过程可以采用本领域技术人员熟知的方法。 Metal impregnation process aids and Co of the active ingredient well known to those skilled in methods may be employed. 如采用如下过程:先采用含助剂元素盐的溶液浸渍改性硅胶载体,然后采用含活性金属组分Co盐的溶液浸渍,每步浸渍后可以包括干燥步骤和焙烧步骤。 Process as follows: first impregnation solution containing modified silica support element salt adjuvants, and containing the active metal component by impregnation of a solution of Co salt, after each impregnation step may comprise a drying step and calcining step. 干燥步骤在50-150°C下干燥8-24小时,焙烧步骤在280-600°C下焙烧2-10小时。 Drying step of drying at 50-150 ° C for 8-24 hours, the baking step calcination at 280-600 ° C for 2-10 hours. 制备的催化剂中金属助剂锆的重量百分含量为〇. 5%-6%,优选1%-3%,钴的重量百分含量为5%-35%。 Catalyst prepared in the weight percentage of zirconium is square metal promoters. 5% -6%, preferably 1% to 3%, the weight percentage of cobalt is 5% to 35%.

[0016] 上述钴基费托合成催化剂在费托合成反应中的应用。 [0016] Such cobalt based Fischer - Tropsch synthesis catalyst used in the Fischer-Tropsch synthesis reaction.

[0017] 经过研宄发现,硅胶载体的表面富含丰富的有机基团,这些有机基团中某些可能属于氧化性的有机基团;此外,硅胶在制备过程中会引入某些阴离子,特别是现有技术中工业生产硅胶通常使用硫酸,这时不可避免的在硅胶载体表面残留有大量的硫酸根离子。 [0017] After a Subsidiary found that the surface of the silica gel support rich-rich organic groups, these organic groups may belong to some oxidizing organic group; in addition, silica in the preparation process will introduce some anion, especially Industrial production of the prior art is generally used sulfuric acid silica gel, then inevitably the silica gel support a large number of surface residual sulfate ion. 以上所述的氧化有机基团和阴离子与金属活性组分的作用较强,因此,这些氧化性有机基团和阴离子有可能在浸渍过程中或者长时间运转时同活性组分发生作用,影响金属活性组分在硅胶载体上的分散度、还原度及活性稳定性。 Above the oxidation of organic anion radicals and the role of the active ingredient of strong metal, so these oxidizing organic group and an anionic or effect might occur during the operation time during impregnation with the active ingredient, the impact of metal dispersion of the active ingredient, to restore stability and activity of the silica carrier.

[0018] 与现有技术相比,本发明首先采用高温的氢气对硅胶载体进行预处理,然后再负载金属助剂和活性组分钴的制备方法具有如下优点: [0018] Compared with the prior art, the invention of the first high-temperature hydrogen pretreated silica support, and then load the metal additives and preparation of the active ingredient of cobalt has the following advantages:

[0019] 1、本发明方法能够有效的还原硅胶表面的氧化性基团及制备硅胶载体时引入的阴离子特别是硫酸根离子,降低硅胶表面氧化性基团及阴离子的种类和数量,减少了硅胶表面氧化性基团及阴离子在负载活性组分钴及长时间反应过程中对活性组分的强相互作用,提高了催化剂的分散度、还原性及活性稳定性; Anion [0019] 1, the method of the present invention can effectively redox group and preparing the introduction of the silica surface silica support, particularly sulfate ions, reducing the types and quantities of silica surface oxide anion radicals and reduce the silica Surface oxide group and an anionic load the active ingredient in a long time during the reaction of cobalt and the strong interaction of the active ingredient to improve the dispersion of the catalyst, reducing the stability and activity;

[0020] 2、本发明方法对硅胶载体的结构破坏性小,基本保留了硅胶载体的原有物理性能,制备简单,工艺技术成熟,有利于催化剂的工业生产; [0020] 2. The method of the present invention, the structure of the silica support destructive small, basically to retain the original physical properties of the silica support, preparation is simple, mature technology, industrial production in favor of a catalyst;

[0021] 3、本发明方法制备的催化剂在高空速及长周期的运转条件下,显示出优良的活性稳定性,试验结果表明,在合成气空速为2000 1Γ1,装置运转500小时,CO的转化率仍高达50%以上,比现有技术提高了10%以上。 [0021] 3, the catalyst prepared by the method of the present invention at high altitude speed and operating conditions of a long period, showed excellent activity and stability, test results showed that the synthesis gas space velocity of 2000 1Γ1, means 500 hours of operation, CO of Conversion rate is still as high as 50 percent, an increase of more than 10 percent over the prior art.

具体实施方式 DETAILED DESCRIPTION

[0022] 下面结合实施例进一步说明本发明方法的过程和效果。 [0022] The following examples further illustrate the combined effect of the invention process and methods.

[0023] 实例1 [0023] Example 1

[0024] 称取市售硅胶(孔容为I. 06ml/g,比表面积为386. 81m2/g,此硅胶每10克滴加蒸馏水至初润时消耗水的体积为16ml,以下实施例均使用该硅胶)30g,装入固定床反应器中, 经气体置换以保证固定床内氧气的体积浓度小于99. 9%后通入热氢气,来自于氢气加热炉的热氢气温度为500°C,体积空速为1500 1Γ1,处理时间为15h,体系压力为1.5MPa。 [0024] Weigh commercially available silica gel (pore volume is I. 06ml / g, a specific surface area of 386. 81m2 / g, this silicone dropping water consumption volume of distilled water to First Run when 16ml per 10 grams, the following examples are The use of silica gel) 30g, charged in a fixed bed reactor, through the gas replacement to ensure that after a fixed bed of the oxygen concentration by volume is less than 99.9% of hydrogen introduced into heat, the heat from the hydrogen furnace temperature of 500 ° C hydrogen , volume space velocity of 1500 1Γ1, the processing time is 15h, the system pressure is 1.5MPa. 按最终催化剂锆含量3wt%计,称取硝酸锆溶解于48ml,加入上述改性后的载体硅胶中浸渍,老化3 小时,80°C干燥8小时,在350°C中焙烧4小时。 Press 3wt% zirconium content of the final catalyst meter, said take zirconium nitrate were dissolved in 48ml, was added after the modified silica carrier was immersed, aged 3 hours, 80 ° C and dried for 8 hours and calcined at 350 ° C for 4 hours. 按最终催化剂钴含量20wt%计,称取硝酸钴溶解于48ml,加入上述浸渍锆后的样品中,老化3小时,80°C干燥8小时,在350°C中焙烧4 小时。 The catalyst according to the final count 20wt% cobalt content, said take cobalt nitrate were dissolved in 48ml, was added to the sample after the impregnation of zirconium, aged 3 hours, 80 ° C and dried for 8 hours and calcined at 350 ° C for 4 hours. 所得催化剂记为C-1。 The resultant catalyst is denoted as C-1.

[0025] 催化剂评价试验在高压连续搅拌釜式反应器中,以石蜡作为溶剂,以纯氢350°C下还原12小时,压力为l.OMPa。 [0025] Catalyst evaluation test in a high pressure continuous stirred tank reactors, paraffin as a solvent, to 350 ° C under pure hydrogen reduction of 12 hours, a pressure of l.OMPa. 降温后切换合成气进行反应。 After switching cooling syngas reaction. 反应流出物分别由热阱、冷阱收集。 The reaction effluent from the heat sink are cold trap collection. 反应条件为220°〇,20001^,2. 0MPa,H2/C0=2 (摩尔比)。 The reaction conditions were 220 ° square, 20001 ^, 2. 0MPa, H2 / C0 = 2 (molar ratio). 运转时间为500h时CI催化剂费托合成反应结果如表1所示。 Running time for the CI catalysts for Fischer-Tropsch synthesis reaction results are shown in Table 1 500h time.

[0026] 实例2 [0026] Example 2

[0027] 称取市售硅胶30g,装入固定床反应器中,经气体置换以保证固定床内氧气的体积浓度小于99. 9%后通入热氢气,来自于氢气加热炉的热氢气温度为350°C,体积空速为1200 1Γ1,处理时间为10h,体系压力为1.0 MPa。 [0027] Weigh commercially available silica gel 30g, charged a fixed bed reactor, the gas replacement in order to guarantee a fixed bed after the volume concentration of oxygen is less than 99.9 percent through into the hot hydrogen from the hydrogen furnace hot hydrogen temperature to 350 ° C, volume space velocity of 1200 1Γ1, the processing time is 10h, the system pressure of 1.0 MPa. 按最终催化剂锆含量lwt%计,称取硝酸锆溶解于48ml,加入上述改性后的载体硅胶中浸渍,老化3小时,80°C干燥8小时,在350°C中焙烧4 小时。 The catalyst according to the final count zirconium content lwt%, said zirconium nitrate dissolved in taking 48ml, was added after the modified silica carrier was immersed, aged 3 hours, 80 ° C and dried for 8 hours and calcined at 350 ° C for 4 hours. 按最终催化剂钴含量l〇wt%计,称取硝酸钴溶解于48ml,加入上述浸渍锆后的样品中,老化3小时,80°C干燥8小时,在350°C中焙烧4小时。 The cobalt content of the final catalyst by l〇wt percent, said cobalt nitrate was dissolved in taking 48ml, was added to the sample after the impregnation of zirconium, aged 3 hours, 80 ° C and dried 8 hours, calcined at 350 ° C for 4 hours. 所得催化剂记为C-2。 The resultant catalyst is denoted as C-2. 催化剂活性评价实验条件同实施例1。 The catalyst activity evaluation test conditions are the same as in Example 1. C-2催化剂费托合成反应结果如表1所示。 C-2 catalyst for Fischer-Tropsch synthesis reaction results are shown in Table 1.

[0028] 实例3 [0028] Example 3

[0029] 称取市售硅胶30g,装入固定床反应器中,经气体置换以保证固定床内氧气的体积浓度小于99. 9%后通入热氢气,来自于氢气加热炉的热氢气温度为400°C,体积空速为1600 1Γ1,处理时间为20h,体系压力为I. 5MPa。 [0029] Weigh commercially available silica gel 30g, charged a fixed bed reactor, the gas replacement in order to guarantee a fixed bed after the volume concentration of oxygen is less than 99.9 percent through into the hot hydrogen from the hydrogen furnace hot hydrogen temperature to 400 ° C, volume space velocity of 1600 1Γ1, the processing time is 20h, the system pressure is I. 5MPa. 按最终催化剂锆含量6wt%计,称取硝酸锆溶解于48ml,加入上述改性后的载体硅胶中浸渍,老化3小时,80°C干燥8小时,在350°C中焙烧4 小时。 Press 6wt% zirconium content of the final catalyst meter, said take zirconium nitrate were dissolved in 48ml, was added after the modified silica carrier was immersed, aged 3 hours, 80 ° C and dried for 8 hours and calcined at 350 ° C for 4 hours. 按最终催化剂钴含量5wt%计,称取硝酸钴溶解于48ml,加入上述浸渍锆后的样品中, 老化3小时,80°C干燥8小时,在350°C中焙烧4小时。 The catalyst according to the final count 5wt% cobalt content, said take cobalt nitrate were dissolved in 48ml, was added to the sample after the impregnation of zirconium, aged 3 hours, 80 ° C and dried for 8 hours and calcined at 350 ° C for 4 hours. 所得催化剂记为C-3。 The resultant catalyst is denoted as C-3. 催化剂活性评价实验条件同实施例1。 The catalyst activity evaluation test conditions are the same as in Example 1. C-3催化剂费托合成反应结果如表1所示。 C-3 Catalyst for Fischer-Tropsch synthesis reaction results are shown in Table 1.

[0030] 实例4 [0030] Example 4

[0031] 称取市售硅胶30g,装入固定床反应器中,经气体置换以保证固定床内氧气的体积浓度小于99. 9%后通入热氢气,来自于氢气加热炉的热氢气温度为450°C,体积空速为1800 tr1,处理时间为25h,体系压力为2MPa。 [0031] Weigh commercially available silica gel 30g, charged a fixed bed reactor, the gas replacement in order to guarantee a fixed bed after the volume concentration of oxygen is less than 99.9 percent through into the hot hydrogen from the hydrogen furnace hot hydrogen temperature to 450 ° C, volume space velocity of 1800 tr1, the processing time is 25h, the system pressure of 2MPa. 按最终催化剂锆含量4wt%计,称取硝酸锆溶解于48ml,加入上述改性后的载体硅胶中浸渍,老化3小时,80°C干燥8小时,在350°C中焙烧4 小时。 Press 4wt% zirconium content of the final catalyst meter, said take zirconium nitrate were dissolved in 48ml, was added after the modified silica carrier was immersed, aged 3 hours, 80 ° C and dried for 8 hours and calcined at 350 ° C for 4 hours. 按最终催化剂钴含量15wt%计,称取硝酸钴溶解于48ml,加入上述浸渍锆后的样品中,老化3小时,80°C干燥8小时,在350°C中焙烧4小时。 The catalyst according to the final count 15wt% cobalt content, said take cobalt nitrate were dissolved in 48ml, was added to the sample after the impregnation of zirconium, aged 3 hours, 80 ° C and dried for 8 hours and calcined at 350 ° C for 4 hours. 所得催化剂记为C-4。 The resultant catalyst is denoted as C-4. 催化剂活性评价实验条件同实施例1。 The catalyst activity evaluation test conditions are the same as in Example 1. C-4催化剂费托合成反应结果如表1所示。 C-4 Catalyst for Fischer-Tropsch synthesis reaction results are shown in Table 1.

[0032] 实例5 [0032] Example 5

[0033] 称取市售硅胶30g,装入固定床反应器中,经气体置换以保证固定床内氧气的体积浓度小于99. 9%后通入热氢气,来自于氢气加热炉的热氢气温度为550°C,体积空速为2000 1Γ1,处理时间为30h,体系压力为2. 5MPa。 [0033] Weigh commercially available silica gel 30g, charged a fixed bed reactor, the gas replacement in order to guarantee a fixed bed after the volume concentration of oxygen is less than 99.9 percent through into the hot hydrogen from the hydrogen furnace hot hydrogen temperature to 550 ° C, volume space velocity of 2000 1Γ1, the processing time is 30h, the system pressure was 2. 5MPa. 按最终催化剂锆含量5wt%计,称取硝酸锆溶解于48ml,加入上述改性后的载体硅胶中浸渍,老化3小时,80°C干燥8小时,在350°C中焙烧4 小时。 Press 5wt% zirconium content of the final catalyst meter, said take zirconium nitrate were dissolved in 48ml, was added after the modified silica carrier was immersed, aged 3 hours, 80 ° C and dried for 8 hours and calcined at 350 ° C for 4 hours. 按最终催化剂钴含量25wt%计,称取硝酸钴溶解于48ml,加入上述浸渍锆后的样品中,老化3小时,80°C干燥8小时,在350°C中焙烧4小时。 The catalyst according to the final count 25wt% cobalt content, said take cobalt nitrate were dissolved in 48ml, was added to the sample after the impregnation of zirconium, aged 3 hours, 80 ° C and dried for 8 hours and calcined at 350 ° C for 4 hours. 所得催化剂记为C-5。 The resultant catalyst is denoted as C-5. 催化剂活性评价实验条件同实施例1。 The catalyst activity evaluation test conditions are the same as in Example 1. C-5催化剂费托合成反应结果如表1所示。 C-5 catalysts for Fischer-Tropsch synthesis reaction results are shown in Table 1.

[0034] 实例6 [0034] Example 6

[0035] 称取市售硅胶30g,装入固定床反应器中,经气体置换以保证固定床内氧气的体积浓度小于99. 9%后通入热氢气,来自于氢气加热炉的热氢气温度为600°C,体积空速为1500 1Γ1,处理时间为20h,体系压力为I. 5MPa。 [0035] Weigh commercially available silica gel 30g, charged a fixed bed reactor, the gas replacement in order to guarantee a fixed bed after the volume concentration of oxygen is less than 99.9 percent through into the hot hydrogen from the hydrogen furnace hot hydrogen temperature to 600 ° C, volume space velocity of 1500 1Γ1, the processing time is 20h, the system pressure is I. 5MPa. 按最终催化剂锆含量2wt%计,称取硝酸锆溶解于48ml,加入上述改性后的载体硅胶中浸渍,老化3小时,80°C干燥8小时,在350°C中焙烧4 小时。 The catalyst according to the final count zirconium content 2wt%, said zirconium nitrate dissolved in taking 48ml, was added after the modified silica carrier was immersed, aged 3 hours, 80 ° C and dried for 8 hours and calcined at 350 ° C for 4 hours. 按最终催化剂钴含量30wt%计,称取硝酸钴溶解于48ml,加入上述浸渍锆后的样品中,老化3小时,80°C干燥8小时,在350°C中焙烧4小时。 The catalyst according to the final count 30wt% cobalt content, said take cobalt nitrate were dissolved in 48ml, was added to the sample after the impregnation of zirconium, aged 3 hours, 80 ° C and dried for 8 hours and calcined at 350 ° C for 4 hours. 所得催化剂记为C-6。 The resultant catalyst is denoted as C-6. 催化剂活性评价实验条件同实施例1。 The catalyst activity evaluation test conditions are the same as in Example 1. C-6催化剂费托合成反应结果如表1所示。 C-6 catalyst for Fischer-Tropsch synthesis reaction results are shown in Table 1.

[0036] 实例7 [0036] Example 7

[0037] 称取市售硅胶30g,装入固定床反应器中,经气体置换以保证固定床内氧气的体积浓度小于99. 9%后通入热氢气,来自于氢气加热炉的热氢气温度为450°C,体积空速为1000 1Γ1,处理时间为15h,体系压力为2MPa。 [0037] Weigh commercially available silica gel 30g, charged a fixed bed reactor, the gas replacement in order to guarantee a fixed bed after the volume concentration of oxygen is less than 99.9 percent through into the hot hydrogen from the hydrogen furnace hot hydrogen temperature to 450 ° C, volume space velocity of 1000 1Γ1, the processing time is 15h, the system pressure of 2MPa. 按最终催化剂锆含量I. 5wt%计,称取硝酸锆溶解于48ml,加入上述改性后的载体硅胶中浸渍,老化2小时,50°C干燥24小时,在280°C中焙烧10小时。 Press final catalyst I. 5wt% zirconium content meter, said take zirconium nitrate were dissolved in 48ml, was added after the modified silica carrier was immersed, aged 2 hours, 50 ° C dry for 24 hours, calcined at 280 ° C for 10 hours. 按最终催化剂钴含量35wt%计,称取硝酸钴溶解于48ml,加入上述浸渍锆后的样品中,老化3小时,80°C干燥8小时,在350°C中焙烧4小时。 The catalyst according to the final count 35wt% cobalt content, said take cobalt nitrate were dissolved in 48ml, was added to the sample after the impregnation of zirconium, aged 3 hours, 80 ° C and dried for 8 hours and calcined at 350 ° C for 4 hours. 所得催化剂记为C-7。 The resultant catalyst is denoted as C-7. 催化剂活性评价实验条件同实施例1。 The catalyst activity evaluation test conditions are the same as in Example 1. C-7催化剂费托合成反应结果如表1所示。 C-7 catalyst for Fischer-Tropsch synthesis reaction results are shown in Table 1.

[0038] 比较例1 [0038] Comparative Example 1

[0039] 按照CN200910011988. 0的催化剂制备方法,得到催化剂记为C-B1,该催化剂的组成同实例1,催化剂活性评价实验条件同实施例1。 [0039] The catalyst preparation method CN200910011988. 0 to obtain a catalyst referred to as C-B1, the same composition of the catalyst of Example 1, the catalyst activity evaluation test conditions are the same as in Example 1. 评价结果见表1。 The evaluation results are shown in Table 1.

[0040] 比实例2 [0040] than in Example 2

[0041] 按照CN200910011989. 5的催化剂制备方法,得到催化剂记为C-B2,该催化剂的组成同实例1,催化剂活性评价实验条件同实施例1。 [0041] The catalyst preparation method CN200910011989. 5 to obtain a catalyst referred to as C-B2, the same composition of the catalyst of Example 1, the catalyst activity evaluation test conditions are the same as in Example 1. 评价结果见表1。 The evaluation results are shown in Table 1.

[0042] 表1 [0042] Table 1

[0043] [0043]

Figure CN103769100BD00061

Figure CN103769100BD00071
Citas de patentes
Patente citada Fecha de presentación Fecha de publicación Solicitante Título
CN101920200A *9 Jun 200922 Dic 2010中国石油化工股份有限公司;中国石油化工股份有限公司抚顺石油化工研究院Method for preparing long-life cobalt-based catalyst for Fischer-Tropsch synthesis
EP1031375A2 *15 Feb 200030 Ago 2000CPC Cellular Process Chemistry GmbHMicroreactor
US6765025 *17 Ene 200220 Jul 2004Dalian Institute Of Chemical Physics, Chinese Academy Of ScienceProcess for direct synthesis of diesel distillates with high quality from synthesis gas through Fischer-Tropsch synthesis
*US2009282975 Título no disponible
WO2008147014A3 *30 Ene 200819 Mar 2009Jong-Wook BaeSynthetic methods for liquid hydrocarbons from syngas over alumina-silica based catalysts and preparation methods thereof
Clasificaciones
Clasificación internacionalB01J23/75, C10G2/00
Eventos legales
FechaCódigoEventoDescripción
7 May 2014C06Publication
11 Jun 2014C10Request of examination as to substance
12 Ago 2015C14Granted