New! View global litigation for patent families

CN103769100B - A Fischer-Tropsch synthesis catalyst and its preparation method and application - Google Patents

A Fischer-Tropsch synthesis catalyst and its preparation method and application Download PDF

Info

Publication number
CN103769100B
CN103769100B CN 201210408285 CN201210408285A CN103769100B CN 103769100 B CN103769100 B CN 103769100B CN 201210408285 CN201210408285 CN 201210408285 CN 201210408285 A CN201210408285 A CN 201210408285A CN 103769100 B CN103769100 B CN 103769100B
Authority
CN
Grant status
Grant
Patent type
Application number
CN 201210408285
Other languages
Chinese (zh)
Other versions
CN103769100A (en )
Inventor
李�杰
张舒冬
张喜文
倪向前
宋喜军
Original Assignee
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Abstract

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 and a preparation method and application. 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 in a silica gel support, by weight content of the catalyst, containing 0.5% to 6% metal promoter, 5% to 35% of active ingredient cobalt, said metal promoter is Re, Zr , one or more of Hf, Ce and Th and the like, the silica support is treated silica support hot hydrogen, a temperature of hot hydrogen 350-650 ℃, 1-30h, the processing time of hot hydrogen airspeed 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 the operating conditions of long cycle and high speed, suitable for industrial application.

Description

一种费托合成催化剂及其制备方法和应用 A Fischer-Tropsch synthesis catalyst and its preparation method and application

技术领域 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 and its preparation and use, particularly to a kind of a high activity and stability modified silica gel as a carrier, adding cobalt metal promoter modified Fischer-Tropsch synthesis preparation of the catalyst.

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, in order to prepare Fischer-Tropsch synthesis reaction liquid fuel has been more attention around the world. 催化剂是费托合成反应的关键技术之一。 Catalyst is one of the key 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 the nearly 80 years of study based Fischer-Tropsch catalyst in it has been found that Fe, Co and Ru Fischer-Tropsch catalysts and the like are effective active ingredients, the active Zr, K, and Cu, and other additives to the Fischer-Tropsch catalyst elements stability plays an important role, in the catalyst carrier and amorphous Al 203 Si02,1102 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 effective reasonable match to the active ingredient, and a carrier metal promoter, prepared with a high activity, high selectivity and high stability Fischer-Tropsch synthesis catalyst is a Subsidiary hot. 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 can not only generate the maximum diameter heavy, and low tendency to coke cobalt-based catalysts, high activity, and therefore, cobalt-based catalyst based on a Subsidiary important.

[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, the method uses 1% to 25% aqueous ammonia solution was aged at room temperature for 6-150 hours SiO2 support, drying at 100-150 ° C for 8-24 hours the surface modification improves the active 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。 Surface of the catalyst support of alkali metal hydroxides and ammonia will have some destructive effect, certain modifiers may 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 first cobalt-containing compound, an organic aluminum compound and a co-solvent and water mixed into a solution, the solution was heated to combustion in oxygen-containing atmosphere , Sintering processes other organic cosolvent, to obtain a powder product, and finally in the presence of air, the powder was calcined at 100-1000 ° c in 0. 5-36 hours. 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 co-solvent used is an organic amine, an organic acid, one or more organic hydrazine. 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. The method of preparing a cobalt based Fischer-Tropsch synthesis catalyst disclosed 0 in the silica gel as a carrier, the carrier first surface modification of silica gel, and then the supported metal impregnation method auxiliaries and the active component of Co; wherein the surface modification method of the silica support were used a buffer solution containing an ammonium salt, an acidic solution of a nitrogen-containing organic compound and glucose solution 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 method described above has made significant progress in reducing the Fischer-Tropsch synthesis reaction temperature, the support modifier avoid corrosion during acidic or basic solution and damage to the pore structure of the support surface thereof, to improve catalyst life and activity and the like. 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。 However, as will be further study based, we found that the above prepared catalyst obtained by the method under the operating conditions of long cycle and high space velocities, the activity stability of the catalyst still needs to be further improved.

发明内容 SUMMARY

[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 under the operating conditions for a long period and high speed, there is a cobalt based Fischer-Tropsch synthesis catalyst activity is not ideal stability problems, the present invention discloses a cobalt based Fischer-Tropsch synthesis catalyst and its preparation method and application, the preparation process is simple, the catalyst exhibits excellent activity stability under the operating conditions of long cycle and high speed, suitable for industrial application.

[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] - cobalt-based Fischer-Tropsch synthesis catalyst species, silica gel support, the content by weight of the catalyst containing 0.5% of metal additives _6%, 5% to 35% of the active cobalt component, said metal promoter is Re, Zr, Hf, Ce and Th and the like of one or several of the silica gel support is treated silica support hot hydrogen, the temperature of hot hydrogen is 350-650 ° C, the treatment time l_30h , hot hydrogen space velocity is 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] The cobalt-based Fischer-Tropsch synthesis catalyst of the present invention, the content by weight of the catalyst containing 1% _3% of metal additives, said additives 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 silica support is treated silica support hot hydrogen, the pressure control process is a 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, the process comprising the following: silica gel support, firstly pretreated silica support, and the supported metal impregnation method auxiliaries and active components of Co; wherein the silica support pretreatment is passed through a silica gel carrier to 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] Pretreatment of the silica gel support The method of the present invention in the method according to the silica gel support is passed through hot hydrogen temperature is 400-600 ° C, the processing time is less than 10H, the 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 was 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 may be performed in a fixed bed reactor, the gas needs to be replaced before introducing hot hydrogen, guarantee a fixed bed volume concentration of oxygen 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 preparation of cobalt based Fischer-Tropsch synthesis catalyst of the present invention, the silica support may be employed conventional silicone products, such as large pores or pores dry microspheres, silica gel may be employed as desired product, may also be prepared by the 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] The preparation of cobalt based Fischer-Tropsch synthesis catalyst of the present invention, the metal promoter may be Re, Zr, Hf, Ce and Th, and 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。 Auxiliaries and Co metal active component loading method preferably first immersed metal promoter, then stepwise impregnation method of impregnating the active ingredient Co. 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 promoter and the active ingredient Co impregnation methods well known to those skilled in the art 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。 The procedure is as follows: first, using a modified silica support impregnated with a solution containing the element salt adjuvants, and then impregnation solution containing the active metal components of Co salt, after each impregnation step may include the step of drying and calcination steps. 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 8-24 hours, calcined at a calcining step 280-600 ° C 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%。 The catalyst prepared in weight percent zirconium metal promoter is square. 5% -6%, preferably 1% to 3%, by weight percent cobalt content of 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。 Applications [0016] The cobalt-based Fischer-Tropsch synthesis catalyst in 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-rich support rich organic group, the organic groups which may belong to some of the oxidizing organic group; furthermore, silica in the manufacturing process introduces certain anionic, especially the prior art is generally used sulfuric acid silica gel in industrial production, a lot of time inevitably sulfate ions remaining on the surface of silica support. 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。 The above-described effect oxidation of the organic anion groups and strong metal active component, therefore, the oxidizing organic group and an anionic likely occur with prolonged effect of the active ingredient during the operation or during the impregnation process, the influence of metal dispersion of the active ingredient, and degree of reduction in activity stability on a silica gel support.

[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 present invention first high-temperature hydrogen gas to the pretreated silica support, metal promoters and methods of preparation of the active ingredient and then the cobalt load 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; Introduced when [0019] 1, the method of the present invention can effectively redox group and silica gel preparative silica gel supporting surface anion particular sulfate ions, reducing the kind and amount of the silica surface-oxidizable group and the anion, reduced silica surface oxidation anionic group and the active component cobalt, and the load during the reaction time of the strong interaction of the active ingredient, 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 is less disruptive a silica gel support structure, substantially retains its original physical properties of a silica gel support, simple preparation, mature technology, facilitate industrial production of the 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 catalyst prepared by the method of the present invention at high speeds and long periods of operating conditions, exhibit excellent activity stability test results show that, in the synthesis gas space velocity of 2000 1Γ1, means 500 hours of operation, CO of conversion was more than 50%, more than 10% increase 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 process of binding and the effect of the method of the present invention.

[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] Commercially available silica gel was weighed (pore volume I. 06ml / g, a specific surface area of ​​386. 81m2 / g, was added dropwise 10 grams of this silica gel volume of distilled water is consumed to run early when 16ml, the following examples are the silica gel used) 30g, was charged in a fixed bed reactor, the gas replacement in order to ensure the hot hydrogen gas into a fixed bed volume of oxygen concentration less than 99.9%, the hydrogen gas from the hydrogen furnace heat temperature 500 ° C space velocity of 1500 1Γ1, 15H treatment time, the system pressure was 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。 The zirconium content of the catalyst according to the final count 3wt%, said zirconium nitrate was dissolved in 48 ml of taking, after the addition of 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。 Press 20wt% cobalt content of the finished catalyst basis, said cobalt nitrate was dissolved in 48 ml of taking, after the sample is added to the impregnating 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 resulting catalyst is referred to 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] The catalyst evaluation test was a continuous stirred tank reactor at high pressure as a paraffin solvent, pure hydrogen at 350 ° C and reduced for 12 hours, and a pressure of l.OMPa. 降温后切换合成气进行反应。 After cooling the reaction synthesis gas switching. 反应流出物分别由热阱、冷阱收集。 The reaction effluent from the heat sink, respectively, and the trapped. 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。 Operation time of the catalyst CI Tropsch synthesis reaction results are shown in Table 1. When the charge 500h.

[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] Commercially available silica gel was weighed 30g, loaded into a fixed bed reactor, the gas displacement volume to ensure that the oxygen concentration in the fixed bed is less than 99.9% of hydrogen into heat, the temperature of hot hydrogen from the hydrogen furnace to 350 ° C, space velocity of 1200 1Γ1, the processing time is 10h, the system pressure was 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 zirconium content of the catalyst according to the final count lwt%, said zirconium nitrate was dissolved in 48 ml of taking, after the addition of 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。 Press l〇wt final catalyst content in% cobalt, said cobalt nitrate was dissolved in 48 ml of taking, after the sample is added to the impregnating 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-2。 The resulting catalyst is referred to 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。 Catalyst C-2 Fischer-Tropsch synthesis 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] Commercially available silica gel was weighed 30g, loaded into a fixed bed reactor, the gas displacement volume to ensure that the oxygen concentration in the fixed bed is less than 99.9% of hydrogen into heat, the temperature of hot hydrogen from the hydrogen furnace to 400 ° C, space velocity of 1600 1Γ1, the processing time was 20h, pressure of the system 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。 The zirconium content of the catalyst according to the final count 6wt%, said zirconium nitrate was dissolved in 48 ml of taking, after the addition of 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。 Press 5wt% cobalt content of the finished catalyst basis, said cobalt nitrate was dissolved in 48 ml of taking, after the sample is added to the impregnating 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 resulting catalyst is referred to 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 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] Commercially available silica gel was weighed 30g, loaded into a fixed bed reactor, the gas displacement volume to ensure that the oxygen concentration in the fixed bed is less than 99.9% of hydrogen into heat, the temperature of hot hydrogen from the hydrogen furnace to 450 ° C, 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。 The final catalyst according to 4wt% zirconium content basis, said zirconium nitrate was dissolved in 48 ml of taking, after the addition of 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。 Press 15wt% cobalt content of the finished catalyst basis, said cobalt nitrate was dissolved in 48 ml of taking, after the sample is added to the impregnating 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 resulting catalyst is referred to 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 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] Commercially available silica gel was weighed 30g, loaded into a fixed bed reactor, the gas displacement volume to ensure that the oxygen concentration in the fixed bed is less than 99.9% of hydrogen into heat, the temperature of hot hydrogen from the hydrogen furnace to 550 ° C, space velocity of 2000 1Γ1, the processing time was 30h, pressure of the system 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。 The zirconium content of the catalyst according to the final count 5wt%, said zirconium nitrate was dissolved in 48 ml of taking, after the addition of 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。 Press 25wt% cobalt content of the finished catalyst basis, said cobalt nitrate was dissolved in 48 ml of taking, after the sample is added to the impregnating 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 resulting catalyst is referred to 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。 Results Tropsch synthesis reaction catalyst charge C-5 as 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] Commercially available silica gel was weighed 30g, loaded into a fixed bed reactor, the gas displacement volume to ensure that the oxygen concentration in the fixed bed is less than 99.9% of hydrogen into heat, the temperature of hot hydrogen from the hydrogen furnace to 600 ° C, space velocity of 1500 1Γ1, the processing time was 20h, pressure of the system 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 zirconium content of the catalyst according to the final count 2wt%, said zirconium nitrate was dissolved in 48 ml of taking, after the addition of 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。 Press 30wt% cobalt content of the finished catalyst basis, said cobalt nitrate was dissolved in 48 ml of taking, after the sample is added to the impregnating 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 resulting catalyst is referred to 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 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] Commercially available silica gel was weighed 30g, loaded into a fixed bed reactor, the gas displacement volume to ensure that the oxygen concentration in the fixed bed is less than 99.9% of hydrogen into heat, the temperature of hot hydrogen from the hydrogen furnace to 450 ° C, 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。 The zirconium content of the catalyst according to the final count I. 5wt%, said zirconium nitrate was dissolved in 48 ml of taking, after the addition of 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。 Press 35wt% cobalt content of the finished catalyst basis, said cobalt nitrate was dissolved in 48 ml of taking, after the sample is added to the impregnating 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 resulting catalyst is referred to as a 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 Fischer-Tropsch synthesis 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 process according CN200910011988. 0 to obtain a catalyst referred to as C-B1, the catalyst composition 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 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 process according CN200910011989. 5 and referred to as a catalyst to obtain C-B2, 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

Claims (10)

  1. 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, by weight content of the catalyst, comprising 0.5% to 6% metal promoter, 5% to 35% of the active cobalt component, said metal promoter is Re, Zr, Hf, Ce and Th of one or more, wherein: said silica carrier is treated with hot hydrogen silica support, the temperature of hot hydrogen 350_650 ° C, the treatment time l-30h, hot hydrogen space velocity is 1000 1 ^ -2000 h '
  2. 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, wherein: said cobalt based Fischer-Tropsch synthesis catalyst by weight content of the catalyst containing 1% _3% of metal additives, said additives is zirconium.
  3. 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。 3. The catalyst according to claim 1, wherein: a cobalt based Fischer-Tropsch catalyst for the synthesis of silica support during the thermal treatment with hydrogen pressure was controlled to 0. 5-2 5 MPa..
  4. 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' Cobalt based Fischer-Tropsch synthesis catalyst prepared according to claim 1, comprising the following process: silica gel support, firstly pretreated silica support, and the supported metal impregnation method auxiliaries and active components of Co; which characterized in that: the method wherein the silica support is pretreated silica carrier to a reaction temperature of 350-650 ° C in hot hydrogen, treatment time l_30h, hot hydrogen space velocity 10001 ^ -200 (¾ '
  5. 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' The method according to claim 4, wherein: the silica gel support pretreatment is passed through a silica support to a temperature of 400-600 ° C in hot hydrogen, treatment time not less than 10H, heat hydrogen space velocity of 12001 ^ -180 (¾ '
  6. 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, wherein: during the thermal treatment with hydrogen pressure was controlled to 0. 5-2 5 MPa0.
  7. 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 as claimed in claim 4, wherein: the thermal pretreatment of hydrogen in a fixed bed reactor, the gas needs to be replaced before introducing hot hydrogen, guarantee a fixed bed volume concentration of oxygen is less than 99.9 % hydrogen from the hydrogen furnace heat.
  8. 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: said metal is one or more adjuvants Re, Zr, Hf, Ce and Th of the weight percentage of metal promoter is square. 5% -6%; the weight percentage of the active component cobalt is 5% to 35% square
  9. 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. The method according to claim 4, wherein: the active ingredient and Co metal promoter metal impregnated using the first aid, and then stepwise impregnation method of impregnating the active ingredient Co.
  10. 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。 1-3 catalyst according to any one of claims Application to the Fischer-Tropsch synthesis as claimed in claim 10.
CN 201210408285 2012-10-24 2012-10-24 A Fischer-Tropsch synthesis catalyst and its preparation method and application CN103769100B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201210408285 CN103769100B (en) 2012-10-24 2012-10-24 A Fischer-Tropsch synthesis catalyst and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201210408285 CN103769100B (en) 2012-10-24 2012-10-24 A Fischer-Tropsch synthesis catalyst and its preparation method and application

Publications (2)

Publication Number Publication Date
CN103769100A true CN103769100A (en) 2014-05-07
CN103769100B true CN103769100B (en) 2015-08-12

Family

ID=50562134

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201210408285 CN103769100B (en) 2012-10-24 2012-10-24 A Fischer-Tropsch synthesis catalyst and its preparation method and application

Country Status (1)

Country Link
CN (1) CN103769100B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1031375A2 (en) * 1999-02-24 2000-08-30 CPC Cellular Process Chemistry GmbH Microreactor
US6765025B2 (en) * 2002-01-17 2004-07-20 Dalian Institute Of Chemical Physics, Chinese Academy Of Science Process for direct synthesis of diesel distillates with high quality from synthesis gas through Fischer-Tropsch synthesis
WO2008147014A3 (en) * 2007-05-29 2009-03-19 Jong-Wook Bae Synthetic methods for liquid hydrocarbons from syngas over alumina-silica based catalysts and preparation methods thereof
CN101920200A (en) * 2009-06-09 2010-12-22 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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8268046B2 (en) * 2008-05-16 2012-09-18 Matheson Tri-Gas Removal of impurities from hydrogen-containing materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1031375A2 (en) * 1999-02-24 2000-08-30 CPC Cellular Process Chemistry GmbH Microreactor
US6765025B2 (en) * 2002-01-17 2004-07-20 Dalian Institute Of Chemical Physics, Chinese Academy Of Science Process for direct synthesis of diesel distillates with high quality from synthesis gas through Fischer-Tropsch synthesis
WO2008147014A3 (en) * 2007-05-29 2009-03-19 Jong-Wook Bae Synthetic methods for liquid hydrocarbons from syngas over alumina-silica based catalysts and preparation methods thereof
CN101920200A (en) * 2009-06-09 2010-12-22 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

Also Published As

Publication number Publication date Type
CN103769100A (en) 2014-05-07 application

Similar Documents

Publication Publication Date Title
CN101411990A (en) Method for preparing catalyst used in method for preparing ethanediol by dimethyl oxalate hydrogenation
CN101264451A (en) Preparation of catalyst for synthesizing ethyl acetate
CN101920200A (en) Method for preparing long-life cobalt-based catalyst for Fischer-Tropsch synthesis
CN102441383A (en) Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas
CN102600888A (en) Benzene hydrogenation catalyst as well as preparation method and application thereof
CN101007277A (en) Catalyst for synthesis of indole and its preparation method
CN103657736A (en) Activated carbon/aluminum oxide composite type catalyst carrier and preparation method and application of activated carbon/aluminum oxide composite type catalyst carrier
CN101811047A (en) Iron base catalyst used for Fischer-Tropsch synthesis and preparation method and application thereof
CN102775262A (en) Method for preparation of olefin through light alkane dehydrogenation
CN101920199A (en) Fischer-Tropsch synthesis cobalt-based catalyst using modified silica gel as carrier and preparation method thereof
CN103586046A (en) Catalyst for preparing light olefins from synthetic gas and preparation method thereof
CN101856615A (en) Catalyst used for hydrogenation of oxalate for preparing ethylene glycol and preparation method thereof
CN102441400A (en) Preparation method of catalyst in process of producing light olefins by high-activity load type iron-based synthesis gas
CN101574659A (en) Catalyst for using coal tar to prepare clean fuel oil by catalytic hydrogenation, preparation method and applications
CN101314139A (en) Boron containing composite alumina support and preparation thereof
CN1557553A (en) Solid catalyst for preparing epoxy phenylethane by epoxidation of styrene and preparation method
CN1765492A (en) Alumina supporter containing modified gamma zeolite and its preparation method
CN103816908A (en) Catalyst for preparing alcohol by hydrogenising acetate and preparation method of catalyst
CN101602000A (en) Iron catalyst containing cobalt auxiliary agent for Fischer-Tropsch synthesis reaction and preparation method thereof
CN102688761A (en) Precipitated iron catalyst for catalyzing Fischer-Tropsch synthetic reaction and preparation method thereof
CN101972664A (en) Catalyst for dehydrogenation of propane for preparing propylene and preparation method thereof
CN103433042A (en) Red mud supported nickel catalyst used for ammonia decomposition for hydrogen production and preparation method thereof
CN103480375A (en) Carbon monoxide methanating catalyst and preparation method thereof
CN1792440A (en) Method for preparing NiB non-crystalline alloy catalyst with the aid of microwave
CN1887420A (en) Petroleum wax hydrofining catalyst and its prepn process

Legal Events

Date Code Title Description
C06 Publication
C10 Request of examination as to substance
C14 Granted